WO2007089230A2 - Nouvelle composition - Google Patents

Nouvelle composition Download PDF

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Publication number
WO2007089230A2
WO2007089230A2 PCT/US2006/003570 US2006003570W WO2007089230A2 WO 2007089230 A2 WO2007089230 A2 WO 2007089230A2 US 2006003570 W US2006003570 W US 2006003570W WO 2007089230 A2 WO2007089230 A2 WO 2007089230A2
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Prior art keywords
particles
nanomagnetic
magnetic
recited
iron
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PCT/US2006/003570
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English (en)
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WO2007089230A3 (fr
Inventor
Xingwu Wang
Howard J. Greenwald
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Biophan Technologies, Inc.
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Priority to PCT/US2006/003570 priority Critical patent/WO2007089230A2/fr
Publication of WO2007089230A2 publication Critical patent/WO2007089230A2/fr
Publication of WO2007089230A3 publication Critical patent/WO2007089230A3/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
    • H01F1/0045—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
    • H01F1/0063—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use in a non-magnetic matrix, e.g. granular solids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
    • A61K47/69—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit
    • A61K47/6949—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit inclusion complexes, e.g. clathrates, cavitates or fullerenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62802—Powder coating materials
    • C04B35/62842—Metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62892—Coating the powders or the macroscopic reinforcing agents with a coating layer consisting of particles
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62897—Coatings characterised by their thickness
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N2/00—Magnetotherapy
    • A61N2/06—Magnetotherapy using magnetic fields produced by permanent magnets
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C01P2006/33—Phase transition temperatures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/42—Magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite

Definitions

  • a mixture comprised of nanomagnetic material and a second material selected from the group consisting of a polymeric material, an elastomeric material, a ceramic material, and mixtures thereof.
  • the mixture also contains halloysite.
  • the nanomagnetic material contains particles with a particle size of from about 3 to about 100 nanometers; and said particles are at least triatomic, being comprised , of a first distinct atom, a second distinct atom, and a third distinct atom.
  • Figure 1 is a schematic illustration, not drawn to scale, of a coated substrate assembly 10 comprised of a substrate 12 and, disposed thereon, a coating 14 comprised of a multiplicity of nanomagnetic particles 16;
  • Figure 4 is a schematic illustration of a coated stent assembly 100
  • Figure 5 is a partial schematic view of a coated stent assembly 200
  • Figure 6 is a schematic of one preferred sputtering process
  • Figure 7 is a partial schematic of one preferred particle collection process
  • Figure 8 is a schematic of a plasma deposition process
  • Figure 9 is a schematic of one preferred forming process
  • Figures 10, 11, 12, 13, and 14 are schematic illustrations of preferred particles of the invention.
  • Figure 15 is a phase diagram showing various compositions that may contain moieties E, F, and
  • Figure 16 is a cross-sectional view of a preferred stent of this invention.
  • Figure 17 is a cross-sectional view of a coated strut 1020 of the stent of Figure 16;
  • Figure 18 shows the effect on the coated strut 1020 when a patient is exposed to an electromagnetic field 1090
  • Figure 19 is a cross-sectional view of another coated strut 1021;
  • Figure 20 shows the effect on the coated strut 1021 when a patient is exposed to an electromagnetic field 1090
  • Figure 21 is a cross-sectional view of another coated strut 1023;
  • Figure 22 shows the effect on the coated strut 1023 when a patient is exposed to an electromagnetic field 1090;
  • Figure 23 is a cross-sectional view of a coated strut 1027
  • Figure 24 is a schematic illustration of an inorganic tubular mineral composition
  • Figure 25 is a sectional view of the inorganic tubular mineral composition of Figure 24;
  • Figure 26 is a schematic view of an inorganic tubular mineral compositon comprised of nanomagnetic material on the exterior surfaces of the tubules;
  • Figure 27 is a schematic view of an inorganic tubular mineral composition comprised of nanomagnetic material on the interior surfaces of the tubulues;
  • Figure 28 is a schematic diagram of a flexed inorganic tubules comprised of a film of nanomagnetic material on its exterior surface;
  • Figure 29 is a flow diagram illustrating the adaptive shielding capabilities of the nanonomagnetic coatings of this invention.
  • Figure 30 is a graph illustrating how the susceptibility of the nanomagentic coatings of the invention varies in the presence of an alternating current electromagnetic field. Description of the preferred embodiments
  • the nanomagnetic material of this invention has a magnetic permeability of from about 0.7 to about 2.0.
  • magnetic permeability refers to "...a property of materials modifying the action of magnetic poles placed therein and modifying the magnetic induction resulting when the material is subjected to a magnetic field of magnetizing force.
  • the permeability of a substance may be defined as the ratio of the magnetic induction in the substance to the magnetizing field to which it is subjected.
  • the permeability of a vacuum is unity.” See, e.g., page F-102 of -Robert E. Weast et al.'s "Handbook of Chemistry and
  • permeability is " ...a factor, characteristic of a material, that is proportional to the magnetic induction produced in a material divided by the magnetic field strength; it is a tensor when these quantities are not parallel.
  • Nanomagnetic particles in the nanomagnetic material there is provided a multiplicity of nanomagnetic particles that may be in the form of a film, a powder, a solution, etc. This multiplicity of nanogmentic particles is hereinafter referred to as a collection of nanomagnetic particles.
  • the collection of nanomagnetic particles of this embodiment of the invention is generally comprised of at least about 0.05 weight percent of such nanomagnetic particles and, preferably, at least about 5 weight percent of such nanomagnetic particles. In one embodiment, such collection is comprised of at least about 50 weight percent of such magnetic particles. In another embodiment, such collection consists essentially of such nanomagnetic particles.
  • the te ⁇ n "compact" will be used to refer to such collection of nanomagnetic particles. Particle size of the nanomagnetic particles
  • the nanomagnetic particles of this invention are smaller than about 100 nanometers.
  • these nano-sized particles have a particle size distribution such that at least about 90 weight percent of the particles have a maximum dimension in the range of from about 1 to about 100 nanometers.
  • the average size of the nanomagnetic particles is preferably less than about 50 nanometers. In one embodiment, the nanomagnetic particles have an average size of less than about 20 nanometers. In another embodiment, the nanomagnetic particles have an average size of less than about 15 nanometers. In yet another embodiment, such average size is less than about 11 nanometers. In yet another embodiment, such average size is less than about 3 nanometers. Coherence length of the nanomagnetic particles
  • the term "coherence length” refers to the distance between adjacent nanomagnetic moieties, and it has the meaning set forth in applicants' published international patent document W003061755A2, the entire disclosure of which is hereby incorporated by reference into this specification. As is disclosed in such published international patent document, "Referring to
  • a moieties 5002, 5004, and 5006 are separated from each other either at the atomic level and/or at the nanometer level.
  • the spacing between adjacent particles is to be much less than .xi.GL to ensure strong coupling while the diameter of voids between dense-packed spheres should be comparable to .xi.GL in order to ensure maximum flux pinning
  • 5,098,178 which discloses that "In addition, the anisotropic shrinkage of the Sol-Gel during polymerization is utilized' to increase the concentration of the superconducting inclusions 22 so that the average particle distance... between the superconducting inclusions 22 approaches the coherence length as much as possible.
  • the coherence length (L) between adjacent magnetic particles is, on average, preferably from about 10 to about 200 nanometers and, more preferably, from about 50 to about 150 nanometers. In one preferred embodiment, the coherence length (L) between adjacent nanomagnetic particles is from about 75 to about 125 nanometers. In one embodiment, x is preferably equal to from about 0.00001 times L to about 100 times L.
  • the ratio of x/L is at least 0.5 and, preferably, at least 1.5. Ratio of the coherence length between nanomagnetic particles to their particle size
  • the ratio of the coherence length between adjacent nanomagnetic particles to their particle size is at least 2 and, preferably, at least 3. In one aspect of this embodiment, such ratio is at least 4. In another aspect of this embodiment, such ratio is at least 5.
  • the nanomagnetic particles of this invention preferably have a saturation magnetization ("magnetic moment") of from about 2 to about 3,000 electromagnetic units (emu) per cubic centimeter of material.
  • saturation magnetization is the maximum possible magnetization of a material.
  • the saturation magnetization of the nanomagnetic particles of this invention is preferably measured by a SQUID (superconducting quantum interference device).
  • SQUID superconducting quantum interference device
  • the entire disclosure of each of these United States patents is hereby incorporated by reference into this specification.
  • the saturation magnetization of the nanomagnetic particle of this invention is at least 100 electromagnetic units (emu) per cubic centimeter and, more preferably, at least about 200 electromagnetic units (emu) per cubic centimter. In one aspect of this embodiment, the saturation magnetization of such nanomagnetic particles is at least about 1 ,000 electromagnetic units per cubic centimeter.
  • the nanomagnetic material of this invention is present in the form a film with a saturization magnetization of at least about 2,000 electromagnetic units per cubic centimeter and, more preferably, at least about 2,500 electromagnetic units per cubic centimeter.
  • the nanomagnetic material in the film preferably has the formula AiA 2 (B) x C, (C 2 ) y , wherein y is 1, the C moieties are oxygen and nitrogen, respectively, and the A moieties and the B moiety are as described elsewhere in this specification.
  • the saturation magnetization of their nanomagnetic particles may be varied by varying the concentration of the "magnetic" moiety A in such particles, and/or the concentrations of moieties B and/or C.
  • the nanomagnetic particles used typically comprise one or more of iron, cobalt, nickel, gadolinium, and samarium atoms.
  • typical nanomagnetic materials include alloys of iron and nickel (permalloy), cobalt, niobium, and zirconium (CNZ), iron, boron, and nitrogen, cobalt, iron, boron, and silica, iron, cobalt, boron, and fluoride, and the like.
  • iron and nickel permalloy
  • CZ cobalt, niobium, and zirconium
  • iron, boron, and nitrogen cobalt, iron, boron, and silica, iron, cobalt, boron, and fluoride, and the like.
  • the nanomagnetic particles of this invention have a coercive force of from about 0.01 to about 5,000 Oersteds.
  • coercive force refers to the magnetic field, H, which must be applied to a magnetic material in a symmetrical, cyclicly magnetized fashion, to make the magnetic induction, B, vanish; this term often is referred to as magnetic coercive force.
  • the nanomagnetic particles have a coercive force of from about 0.01 to about 3,000 Oersteds. In yet another embodiment, the nanomagnetic particles have a coercive force of from about 0.1 to about 10.
  • the phase transition temperature of the nanomagnetic particles is the phase transition temperature of the nanomagnetic particles
  • the nanomagnetic particles have a phase transition temperature is from about 40 degrees Celsius to about 200 degrees Celsius.
  • phase transition temperature refers to temperature in which the magnetic order of a magnetic particle transitions from one magnetic order to another.
  • the phase transition temperature is the Curie temperature.
  • the phase transition temperature is known as the Neel temperature.
  • phase transition temperature For a discussion of phase transition temperature, reference may be had, e.g., to United States patents 4,804,274 (method and apparatus for determining phase transition temperature using laser attenuation), 5,758,968 (optically based method and apparatus for detecting a phase transition temperature of a material of interest), 5,844,643, 5,933,565 (optically based method and apparatus for detecting a phase transition temperature of a material of interest), 6,517,235 (using refractory metal silicidation phase transition temperature points to control and/or calibrate RTP low temperature operation), and the like.
  • the entire disclosure of each of these United States patents is hereby incorporated by reference into this specification.
  • Curie temperature For a discussion of Curie temperature, reference may be had, e.g., to United States patents 3,736,500 (liquid identification using magnetic particles having a preselected Curie temperature), 4,229,234 (passivated, particulate high Curie temperature magnetic alloys), 4,771,238, 4,778,867 (ferroelectric copolymers of vinylidene fluoride and trifluoroethyelene), 5,108,191 (method and apparatus for dete ⁇ nining Curie temperatures of ferromagnetic materials), 5,229,219 (magnetic recording medium having a Curie temperature up to 180 degrees C), 5,325,343 (magneto-optical recording medium having two RE-TM layers with the same Curie temperature), 5,420,728 (recording medium with several recording layers having different Curie temperatures), - 5,487,046 (magneto- optical recording medium having two magnetic layers with the same Curie temperature), 5,543,070 (magnetic recording powder having low Curie temperature and high saturation magnet
  • Curie temperature refers to the temperature marking the transition between ferromagnetism and paramagnetism, or between the ferroelectric phase and paraelectric phase. This term is also sometimes referred to as the "Curie point.”
  • Neel temperature refers to a temperature, characteristic of certain metals, alloys, and salts, below which spontaneous magnetic ordering takes place so that they become antiferromagnetic, and above which they are paramagnetic; this is also known as the Neel point.
  • Neel temperature is also disussed at page F-92 of the "Handbook of Chemistry and Physics," 63 rd Edition (CRC Press, Inc., Boca Raton, Florida, 1982-1983).
  • ferromagnetic materials are "those in which the magnetic moments of atoms or ions tend to assume an ordered but nonparallel arrangement in zero applied field, below a characteristic temperature called the Neel point.
  • a substantial net mangetization results form the antiparallel alignment of neighboring nonequivalent subslattices.
  • the macroscopic behavior is similar to that in ferromagnetism. Above the Neel point, these materials become paramagnetic.”
  • phase temperature of their nanomagnetic particles can be varied by varying the ratio of the A, B, and C moieties described hereinabove as well as the particle sizes of the nanoparticles.
  • the phase transition temperature of the nanomagnetic particles of is higher than the temperature needed to kill cancer cells but lower than the temperature needed to kill normal cells.
  • elevated temperatures i.e., hyperthermia
  • the use of elevated temperatures, i.e., hyperthermia, to repress tumors has been under continuous investigation for many years.
  • DNA synthesis is reduced and respiration is depressed.
  • At about 45° C irreversible destruction of structure, and thus function of chromosome associated proteins, occurs.
  • Autodigestion by the cell's digestive mechanism occurs at lower temperatures in tumor cells than in normal cells.
  • hyperthermia induces an inflammatory response which may also lead to tumor destruction.
  • Cancer cells are more likely to undergo these changes at a particular temperature. This may be due to intrinsic differences, between normal cells and cancerous cells. More likely, the difference is associated with the lop pH (acidity), low oxygen content and poor nutrition in tumors as a consequence of decreased blood flow. This is confirmed by the fact that recurrence of tumors in animals, after hyperthermia, is found in the tumor margins; probably as a consequence of better blood supply to those areas.”
  • the phase transition temperature of the nanomagnetic particles is less than about 50 degrees Celsius and, preferably, less than about 46 degrees Celsius. In one aspect of this embodiment, such phase transition temperature is less than about 45 degrees Celsius.
  • the nanomagnetic particles are depicted by the formula AiA 2 (B) x Ci (C 2 ) V , wherein each of Ai and A 2 are separate magnetic A moieties, as described below; B is as defined elsewhere in this specification; x is an integer from 0 to 1 ; each of Cj and C 2 is as descried elsewhere in this specification; and y is an integer from 0 to 1.
  • composition of these preferred nanomagnetic particles may be depicted by a phase diagram such as, e.g., the phase diagram depicted in Figures 37 et seq. of United States patent 6,765,144, the entire disclosure of which is hereby incorporated by reference into this specification. As is disclosed in such United States patent, "Referring to FIG. 37, and in the preferred embodiment depicted therein, a phase diagram 5000 is presented.
  • the nanomagnetic material used in the composition of this invention preferably is comprised of one or more of moieties A, B, and C....
  • the moiety A depicted in phase diagram 5000 is comprised of a magnetic element selected from the group consisting of a transition series metal, a rare earth series metal, or actinide metal, a mixture thereof, and/or an alloy thereof....As is known to those skilled in the art, the transition series metals include chromium, manganese, iron, cobalt, nickel.
  • alloys or iron, cobalt and nickel such as, e.g., iron— aluminum, iron—carbon, iron—chromium, iron—cobalt, iron—nickel, iron nitride (Fe3 N), iron phosphide, iron-silicon, iron-vanadium, nickel-cobalt, nickel-copper, and the like.
  • One may use compounds and alloys of the iron group, including oxides of the iron group, halides of the iron group, borides of the transition elements, sulfides of the iron group, platinum and palladium with the iron group, chromium compounds, and the like.”
  • United States patent 6,765,144 also discloses that: "One may use a rare earth and/or actinide metal such as, e.g., Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, La, mixtures thereof, and alloys thereof.
  • a rare earth and/or actinide metal such as, e.g., Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, La, mixtures thereof, and alloys thereof.
  • One may also use one or more of the actinides such as, e.g., Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf. Es, Fm, Md, No, Lr, Ac, and the like....These moieties, compounds thereof, and alloys thereof are well known and are described, e.g., in the aforementioned text of R. S. Tebble
  • moiety A is selected from the group consisting of iron, nickel, cobalt, alloys thereof, and mixtures thereof.
  • the moiety A is magnetic, i.e., it has a relative magnetic pe ⁇ rieability of from about 1 to about 500,000.
  • United States patent 6,765,144 also discloses that "The moiety A also preferably has a saturation magnetization of from about 1 to about 36,000 Gauss, and a coercive force of from about 0.01 to about 5,000 Oersteds....
  • the moiety A may be present in the nanomagnetic material either in its elemental form, as an alloy, in a solid solution, or as a compound...It is preferred at least about 1 mole percent of moiety A be present in the nanomagnetic material (by total moles of A, B, and C), and it is more preferred that at least 10 mole percent of such moiety A be present in the nanomagnetic material (by total moles of A, B, and C).
  • moiety B in addition to moiety A, it is preferred to have moiety B be present in the nanomagnetic material.
  • moieties A and B are admixed with each other.
  • the mixture may be a physical mixture, it may be a solid solution, it may be comprised of an alloy of the A/B moieties, etc.
  • the magnetic material A is dispersed within nonmagnetic material B.
  • This embodiment is depicted schematically in FIG. 38.
  • United States patent 6,765,144 also discloses that "Referring to FIG. 38, and in the preferred embodiment depicted therein, it will be seen that A moieties 5002, 5004, and 5006 are separated from each other either at the atomic level and/or at the nanometer level.
  • the A moieties may be, e.g., A atoms, clusters of A atoms, A compounds, A solid solutions, etc; regardless of the form of the A moiety, it has the magnetic properties described hereinabove....In the embodiment depicted in FIG. 38, each A moiety produces an independent magnetic moment.
  • United States patent 6,765,144 also discloses that "In one embodiment, and referring again to FIG. 38, x is preferably measured from the center 5001 of A moiety 5002 to the center 5003 of A moiety 5004; and x is preferably equal to from about 0.00001 xL to about 10OxL....In one embodiment, the ratio of x/L is at least 0.5 and, preferably, at least 1.5.” United States patent 6,765,144 also discloses that "Referring again to FIG. 37, the nanomagnetic material may be comprised of 100 percent of moiety A, provided that such moiety A has the required normalized magnetic interaction (M).
  • M normalized magnetic interaction
  • the nanomagnetic material may be comprised of both moiety A and moiety B ....
  • moiety B when moiety B is present in the nanomagnetic material, in whatever form or forms it is present, it is preferred that it be present at a mole ratio (by total moles of A and B) of from about 1 to about 99 percent and, preferably, from about 10 to about 90 percent....
  • the B moiety, in whatever form it is present, is nonmagnetic, i.e., it has a relative magnetic permeability of 1.0; without wishing to be bound to any particular theory, applicants believe that the B moiety acts as buffer between adjacent A moieties.
  • United States patent 6,765,144 also discloses that "The use of the B material allows one to produce a coated substrate with a springback angle of less than about 45 degrees. As is known to those skilled in the arty all materials have a finite modulus of elasticity; thus, plastic deformations followed by some elastic recovery when the load is removed. In bending, this recovery is called springback. See, e.g., page 462 of S. Kalparjian's “Manufacturing Engineering and Technology," Third Edition (Addison Wesley Publishing Company, New York, N. Y., 1995)....FIG. 39 illustrates how springback is determined in accordance with this invention. Referring to FIG.
  • a coated substrate 5010 is subjected to a force in the direction of arrow 5012 that bends portion 5014 of the substrate to an angle 5016 of 45 degrees, preferably in a period of less than about 10 seconds. Thereafter, when the force is released, the bent portion 5014 springs back to position 5018.
  • the springback angle 5020 is preferably less than 45 degrees and, preferably, is less than about 10 degrees.”
  • the nanomagnetic material is comprised of moiety A, moiety C, and optionally moiety B.
  • the moiety C is preferably selected from the group consisting of elemental oxygen, elemental nitrogen, elemental carbon, elemental fluorine, elemental chlorine, elemental hydrogen, and elemental helium, elemental neon, elemental argon, elemental krypton, elemental xenon, and the like....It is preferred, when the C moiety is present, that it be present in a concentration of from about 1 to about 90 mole percent, based upon the total number of moles of the A moiety and/or the B moiety and C moiety in the composition.”
  • the aforementioned moiety A is preferably comprised of a magnetic element selected from the group consisting of a transition series metal, a rare earth series metal, or actinide metal, a mixture thereof, and/or an alloy thereof.
  • the moiety A is iron.
  • moiety A is nickel.
  • moiety A is cobalt.
  • moiety A is gadolinium.
  • the A moiety is selected from the group consisting of samarium, holmium, neodymium, and one or more other member of the Lanthanide series of the periodic table of elements.
  • two or more A moieties are present, as atoms.
  • the magnetic susceptibilities of the atoms so present are both positive.
  • two or more A moieties are present, at least one of which is iron.
  • both iron and cobalt atoms are present.
  • from about 50 to about 90 mole percent of iron is present.
  • from about 60 to about 90 mole percent of iron is present.
  • from about 70 to about 90 mole percent of iron is present,
  • moiety A is selected from the group consisting of iron, nickel, cobalt, alloys thereof, and mixtures thereof.
  • the moiety A may be present in the nanomagnetic material either in its elemental form, as an alloy, in a solid solution, or as a compound. In one embodiment, it is preferred at least about 1 mole percent of moiety A be present in the nanomagnetic material (by total moles of A, B, and C), and it is more preferred that at least 10 mole percent of such moiety A be present in the nanomagnetic material (by total moles of A, B, and C).
  • the nanomagnetic material has the formula A 1 A 2 (B) x Ci (C 2 ) y , wherein each of A 1 and A 2 are separate magnetic A moieties, as described above; B is as defined elsewhere in this specification; x is an integer from 0 to 1; each of Ci and C 2 is as descried elsewhere in this specification; and y is an integer from 0 to 1.
  • a moieties such as, e.g., nickel and iron, iron and cobalt, etc.
  • the A moieties may be present in equimolar amounts; or they may be present in non- equimolar amount.
  • either or both of the Ai and A 2 moieties are radioactive.
  • either or both of the Ai and A 2 moieties may be selected from the group consisting of radioactive cobalt, radioactive iron, radioactive nickel, and the like. These radioactive isotopes are well known.
  • At least one of the Ai and A 2 moieties is radioactive cobalt.
  • This radioisotope is discussed, e.g., in United States patent 3,936,440, the entire disclosure of which is hereby incorporated by reference into this specification.
  • At least one of the Ai and A 2 is radioactive iron.
  • This radioisotope is also well known as is evidenced, e.g., by United States patent 4,459,356, the entire disclosure of which is also hereby incorporated by reference into this specification.
  • a radioactive stain composition is developed as a result of introduction of a radionuclide (e.g., radioactive iron isotope 59 Fe, which is a strong gamma emitter having peaks of 1.1 and 1.3 MeV) into BPS to form ferrous BPS ....
  • a radionuclide e.g., radioactive iron isotope 59 Fe, which is a strong gamma emitter having peaks of 1.1 and 1.3 MeV
  • BPS sodium bathophenanthroline sulfonate
  • ascorbic acid Tris buffer salts
  • Enzymes grade acrylamide, N 9 N 1 methylenebisacrylamide and N,N,N',N'-tetramethylethylenediamine are products of and were obtained from Eastman Kodak Co. (Rochester, N.Y.). Sodium dodecylsulfate (SDS) was obtained from Pierce Chemicals (Rockford, 111.). The radioactive isotope (59 FeC13 in 0.05M HCl, specific activity 15.6 mC/mg) was purchased from New England Nuclear (Boston, Mass.), but was diluted to 10 ml with 0.5N HCl to yield an approximately 0.1 mM Fe(III) solution.”
  • the nanomagnetic particles there may be, but need not be, a B moiety (such as, e.g., aluminum).
  • a B moiety such as, e.g., aluminum
  • C moieties such as, e.g., oxygen and nitrogen.
  • the A moieties, in combination, comprise at least about 80 mole percent of such a composition; and they preferably comprise at least 90 mole percent of such composition.
  • two C moieties When two C moieties are present, and when the two C moieties are oxygen and nitrogen,they preferably are present in a mole ratio such that from about 10 to about 90 mole percent of oxygen is present, by total moles of oxygen and nitrogen . It is preferred that at least about 60 mole percent of oxygen be present. In one embodiment, at least about 70 mole percent of oxygen is so present. In yet another embodiment, at least 80 mole percent of oxygen is so present.
  • the B moiety in one embodiment, in whatever form it is present, is preferably nonmagnetic, i.e., it has a relative magnetic permeability of about 1.0; without wishing to be bound to any particular theory, applicants believe that the B moiety acts as buffer between adjacent A moieties.
  • the B moiety has a relative magnetic permeability that is about equal to 1 plus the magnetic susceptilibity.
  • the nanomagnetic particles may be represented by the formula A x B y C 7 wherein x + y + z is equal to 1.
  • the ratio of x/y is at least 0.1 and preferably at least 0.2; and the ratio of z/x is from 0.001 to about 0.5.
  • the B material is aluminum and the C material is nitrogen, whereby an AlN moiety is formed.
  • the nanomagnetic material is comprised of moiety A, moiety C, and optionally moiety B.
  • the moiety C is preferably selected from the group consisting of elemental oxygen, elemental nitrogen, elemental carbon, elemental fluorine, elemental chlorine, elemental hydrogen, and elemental helium, elemental neon, elemental argon, elemental krypton, elemental xenon, elemental fluorine, elemental sulfur, elemental hydrogen, elemental helium, the elemental chlorine, elemental bromine, elemental iodine, elemental boron, elemental phosphorus, and the like.
  • the C moiety is selected from the group consisting of elemental oxygen, elemental nitrogen, and mixtures thereof.
  • the C moiety is chosen from the group of elements that, at room temperature, form gases by having two or more of the same elements combine.
  • gases include, e.g., hydrogen, the halide gases (fluorine, chlorine, bromine, and iodine), inert gases (helium, neon, argon, krypton, xenon, etc.), etc.
  • the C moiety is chosen from the group consisting of oxygen, nitrogen, and mixtures thereof.
  • the C moiety is a mixture of oxygen and nitrogen, wherein the oxygen is present at a concentration from about 10 to about 90 mole percent, by total moles of oxygen and nitrogen. It is preferred, when the C moiety (or moieties) is present, that it be present in a concentration of from about 1 to about 90 mole percent, based upon the total number of moles of the A moiety and/or the B moiety and the C moiety in the composition.
  • the C moiety is both oxygen and nitrogen.
  • the molar ratio of A/(A and B and C) generally is from about 1 to about 99 molar percent and, preferably, from about 10 to about 90 molar percent. In one embodiment, such molar ratio is from about 30 to about 60 molar percent.
  • the molar ratio of B/(A plus B plus C) generally is from about 1 to about 99 mole percent and, preferably, from about 10 to about 40 mole percent.
  • the molar ratio of C/(A plus B plus C) generally is from about 1 to about 99 mole percent and, preferably, from about 10 to about 50 mole percent.
  • the B moiety is added to the nanomagnetic A moiety, preferably with a
  • the resistivity of the mixture of the B moiety and the A moiety is from about 1 micro-ohm-cm to about 10,000 micro-ohm-cm.
  • the A moiety is iron
  • the B moiety is aluminum
  • the molar ratio of A/B is about 70:30
  • the resistivity of this mixture is about 8 micro-ohms-cm.
  • the squareness of a magnetic material is the ratio of the residual magnetic flux and the saturation magnetic flux density.
  • the squareness of applicants' nanomagnetic particles is from about 0.05 to about 1.0. In one aspect of this embodiment, such squareness is from about 0.1 to about 0.9. In another aspect of this embodiment, the squareness is from about 0.2 to about 0.8. In applications where a large residual magnetic moment is desired, the squareness is preferably at least about 0.8.
  • Figure 1 is a schematic illustration, not drawn to scale, of a coated substrate assembly 10 comprised of a substrate 12 and, disposed thereon, a coating 14 comprised of a multiplicity of nanomagnetic particles 16. Similar coated substrate assemblies are illustrated and described in applicants' United States patents .
  • the nanomagnetic particles 16 are preferably comprised of the "ABC” atoms described elsewhere in this specification.
  • the term “coherence length” refers to the smallest distance 18 between the surfaces 20 of any particles 16 that are adjacent to each other. In one aspect of this embodiment, it is preferred that such coherence length, with regard to such ABC particles, be less than about 100 nanometers and, preferably, less than about 50 nanometers. In one embodiment, such coherence length is less than about 20 nanometers. It is preferred that, regardless of the coherence length used, it be at least 2 times as great as the maximum dimension of the particles 16.
  • the mass density of the nanomagnetic particles In one embodiment, the nanomagnetic material preferably has a mass density of at least about
  • mass density refers to the mass of a give substance per unit volume. See, e.g., page 510 of the aforementioned "McGraw-Hill Dictionary of Scientific and Technical Terms.”
  • the material has a mass density of at least about 3 grams per cubic centimeter.
  • the nanomagnetic material has a mass density of at least about 4 grams per cubic centimeter. The thickness of the coating 14
  • the coating 14 may be comprised of one layer of material, two layers of material, or three or more layers of material. Regardless of the number of coating layers used, it is preferred that the total thickness 22 of the coating 14 be at least about 400 nanometers and, preferably, be from about 400 to about 4,000 nanometers. In one embodiment, thickness 22 is from about 600 to about 1,000 nanometers. In another embodiment, thickness 22 is from about 750 to about 850 nanometers.
  • the substrate 12 has a thickness 23 that is substantially greater than the thickness 22.
  • the coated substrate 10 is not drawn to scale.
  • the thickness 22 is preferably less than about 5 percent of thickness 23 and, more preferably, less than about 2 percent. In one embodiment, the thickness 22 is no greater than about 1.5 percent of the thickness 23.
  • substrate 12 is a conductor that preferably has a resistivity at 20 degrees Centigrade of from about 1 to about 100-microohom- centimeters.
  • a film 14 disposed above the conductor 12 is a film 14 comprised of nanomagnetic particles 16 that preferably have a maximum dimension of from about 10 to about 100 nanometers.
  • the film 114 also preferably has a saturation magnetization of from about 200 to about 26,000 Gauss and a thickness of less than about 2 microns.
  • conductor assembly 10 is flexible, having a bend radius of less than 2 centimeters.
  • a similar device is depicted in Figure 5 of United States patent 6,713,671; the entire disclosure of such United States patent is hereby incorporated by reference into this specification.
  • the term flexible refers to an assembly that can be bent to form a circle with a radius of less than 2 centimeters without breaking. Put another way, the bend radius of the coated assembly is preferably less than 2 centimeters.
  • nanomagnetic particles in their coatings and their articles of manufacture allows one to produce a flexible device that otherwise could not be produced were not the materials so used nano-sized (less than 100 nanometers).
  • the assembly 10 is not flexible.
  • the morphological density of the coating 14 In one preferred embodiment, and referring to Figure 1, the coating 14 has a morphological density of at least about 98 percent. In the embodiment depicted, the coating 14 has a thickness 22 of from about 400 to about 2,000 nanometers and , in one embodiment, has a thickness 22 of from about 600 to about 1200 nanometers.
  • the morphological density of a coating is a function of the ratio of the dense coating material on its surface to the pores on its surface; and it is usually measured by scanning electron microscopy.
  • Figure 3 A is a scanning electron microscope (SEM) image of a coating of "long" single-walled carbon nanotubes on a substrate. Referring to this SEM image, it will be seen that the white areas are the areas of the coating where pores occur.
  • SEM scanning electron microscope
  • the scanning electron microscope (SEM) images obtained in making morphological density measurements can be divided into a matrix., as is illustrated in Figures 2 and 3 which schematically illustrate the porosity of the side of coating 14, and the top of the coating 14.
  • the SEM image depicted shows two pores 34 and 36 in the cross-sectional area 38, and it also shows two pores 40 and 42 in the top 44.
  • the SEM image can be divided into a matrix whose adjacent lines 46/48, and adjacent lines 50/52 define a square portion with a surface area of 100 square nanometers (10 nanometers x 10 nanometers). Each such square portion that contains a porous area is counted, as is each such square portion that contains a dense area.
  • the ratio of dense areas/porous areas, x 100 is preferably at least 98.
  • the morphological density of the coating 14 is at least 98 percent. In one embodiment, the morphological density of the coating 14 is at least about 99 percent. In another embodiment, the morphological density of the coating 14 is at least about 99.5 percent.
  • the coating 14 has an average surface roughness of less than about 100 nanometers and, more preferably, less than about 10 nanometers.
  • the average surface roughness of a thin film is preferably measured by an atomic force microscope (AFM).
  • AFM atomic force microscope
  • the surface 17 of such coating By varying the surface roughness of the coating 14 (see Figure 1), one may make the surface 17 of such coating either hydrophobic or hydrophilic.
  • a hydrophobic material is antagonistic to water and incapable of dissolving in water.
  • the average water droplet has a minimum cross-sectional dimension of at least about 3 nanometers, the water droplets will tend not to bond to a coated surface
  • the coated substrate of this invention has durable magnetic properties that do not vary upon extended exposure to a saline solution. If the magnetic moment of a coated substrate is measured at "time zero" (i.e., prior to the time it has been exposed to a saline solution), and then the coated substrate is then immersed in a saline solution comprised of 7.0 mole percent of sodium chloride and 93 mole percent of water, and if the substrate/saline solution is maintained at atmospheric pressure and at temperature of 98.6 degrees Fahrenheit for 6 months, the coated substrate, upon removal from the saline solution and drying, will be found to have a magnetic moment that is within plus or minus 5 percent of its magnetic moment at time zero. In another embodiment, the coated substrate of this invention has durable mechanical properties when tested by the saline immersion test described above.
  • the substrate 12, prior to the time it is coated with coating 14 has a certain flexural strength, and a certain spring constant.
  • the flexural strength is the strength of a material in bending, i.e., its resistance to fracture. As is disclosed in ASTM C-790, the flexural strength is a property of a solid material that indicates its ability to withstand a flexural or transverse load.
  • the spring constant has units of force per unit length.
  • Means for measuring the spring constant of a material are well known to those skilled in the art. Reference may be had, e.g., to United States patents 6,360,589 (device and method for testing vehicle shock absorbers), 4,970,645 (suspension control method and apparatus for vehicle), 6,575,020, 4,157,060, 3,803,887, 4,429,574, 6,021,579, and the like. The entire disclosure of each of these United States patents is hereby incorporated by reference into this specification.
  • the flexural strength of the uncoated substrate 10 preferably differs from the flexural strength of the coated substrate 10 by no greater than about 5 percent.
  • the spring constant of the uncoated substrate 10 differs from the spring constant of the coated substrate 10 by no greater than about 5 percent.
  • the coating 14 biocompatible with biological organisms. As used herein, the term biocompatible refers to a coating whose chemical composition does not change substantially upon exposure to biological fluids.
  • the coated substrate 10 has a direct current (d.c.) magnetic susceptibility within a specified range.
  • d.c. direct current
  • magnetic susceptibility is the ratio of the magnetization of a material to the magnetic field strength; it is a tensor when these two quantities are not parallel; otherwise it is a simple number.
  • the substrate 12 is a stent that is comprised of wire mesh constructed in such a manner as to define a multiplicity of openings .
  • the mesh material is preferably a metal or metal alloy, such as, e.g., stainless steel, Nitinol (an alloy of nickel and titanium), niobium, copper, etc.
  • the materials used in stents tend to cause current flow when exposed to a radio frequency field.
  • the field is a nuclear magnetic resonance field, it generally has a direct current component, and a radio-frequency component.
  • MRI magnetic resonance imaging
  • a gradient component is added for spatial resolution.
  • the material or materials used to make the stent itself have certain magnetic properties such as, e.g., magnetic susceptibility.
  • magnetic susceptibility e.g., niobium has a magnetic susceptibility of 1.95 x 10 "6 centimeter-gram-second units.
  • Nitonol has a magnetic susceptibility of from about 2.5 to about 3.8 x
  • Copper has a magnetic susceptibility of from -5.46 to about -6.16 x
  • the total magnetic susceptibility of an object is equal to the mass of the object times its succeptibility.
  • an object has equal parts of niobium, Nitinol, and copper, its total susceptibility would be equal to (+ 1.95 +3.15 -5.46) x 10 "6 cgs, or about 0.36 x 10 "6 cgs.
  • the susceptibility in c.g.s. units, would be equal to 1.95 Mn + 3.15 Mni -5.46Mc, wherein Mn is the mass of niobium, Mni is th mass of Nitinol, and Mc is the mass of copper.
  • the coated substrate assembly 10 preferably materials that will provide the desired mechanical properties generally do not have desirable magnetic and/or electromagnetic properties, hi an ideal situation, the stent 500 will produce no loop currents and no surface eddy currents when exposed to magnetic resonance imaging
  • a d.c. ("direct current") magnetic susceptibility of precisely zero is often difficult to obtain.
  • the d.c. susceptibility of the coated substrate 10 is plus or minus 1 x 10 "3 centimeter-gram-seconds (cgs) and, more preferably, plus or minus
  • the coated substrate assembly 10 is in contact with biological tissue 11.
  • FIG. 1 only a portion of the biological tissue 11 actually contiguous with assembly 10 is shown for the sake of simplicity of representation, in such an embodiment, it is preferred that such biological tissue 11 be taken into account when determining the net susceptibility of the assembly, and that such net susceptibility of the assembly 10 in contact with bodily fluid is plus or minus plus or minus 1 x 10 "3 centimeter-gram-seconds (cgs), or plus or minus 1 x 10 "4 centimeter-gram-seconds, or plus or minus 1 x 10 "5 centimeter-gram-seconds, or plus or minus 1 x 10 "6 centimeter-gram-seconds.
  • the materials comprising the nanomagnetic coating 14 on the substrate 12 are chosen to have susceptibility values that, in combination with the susceptibility values of the other components of the assembly, and of the bodily fluid, will yield the desired values.
  • Applicants' invention allows one to compensate for the deficiencies of the current stents, and/or of the current stents in contact with bodily fluid, by canceling the undesirable effects due to their magnetic susceptibilities, and/or by compensating for such undesirable effects.
  • the slope of the graph of magnetization versus field strength for copper is negative; this negative slope indicates that copper, in response to the applied fields, is opposing the applied fields. Because the applied fields (including r.f. fields, and the gradient fields), are required for effective MRI imaging, the response of the copper to the applied fields tends to block the desired imaging.
  • the d.c. susceptibility of copper is equal to the mass of the copper present in the device 10 times its magnetic susceptibility.
  • the ideal magnetization response of a composite assembly (such as, e.g., assembly 10) will be a line whose slope is substantially zero.
  • substantially zero includes a slope will produce an effective magnetic susceptibility of from about 1 x 10 '7 to about 1 x 10 "8 centimeters-gram-second (cgs).
  • the desired correction for the slope of the copper graph may be obtained by coating the copper with a coating comprised of both nanomagnetic material and nanodielectric material.
  • the nanomagnetic material preferably has an average particle size of less than about 20 nanometers and a saturation magnetization of from 10,000 to about 26,000 Gauss.
  • the nanomagnetic material used is iron.
  • the nanomagentic material used is FeAlN.
  • the nanomagnetic material is FeAl.
  • Other suitable materials will be apparent to those skilled in the art and include, e.g., nickel, cobalt, magnetic rare earth materials and alloys, thereof, and the like.
  • the nanodielectric material used preferably has a resistivity at 20 degrees Centigrade of from about 1 x 10 "5 ohm-centimeters to about 1 x 10 13 ohm-centimeters.
  • a coated stent assembly 100 that is comprised of a stent 104 on which is disposed a coating 103 is illustrated.
  • the coating 103 is comprised of nanomagnetic material 120 that is preferably homogeneously dispersed within nanodielectric material 122, which acts as an insulating matrix.
  • the amount of nanodielectric material 122 in coating 103 exceeds the amount of nanomagnetic material 120 in such coating 103.
  • the coating 103 is comprised of at least about 70 mole percent of such nanodielectric material (by total moles of nanomagnetic material and nanodielectric material).
  • the coating 103 is comprised of less than about 20 mole percent of the nanomagnetic material 120, by total moles of nanomagnetic material and nanodielectric material.
  • the nanodielectric material used is aluminum nitride.
  • This nanoconductive material 124 generally has a resistivity at 20 degrees Centigrade of from about 1 x 10 "6 ohm-centimeters to about 1 x 10 "5 ohm-centimeters; and it generally has an average particle size of less than about 100 nanometers.
  • the nanoconductive material used is aluminum. Referring again to Figure 4, and in the embodiment depicted, it will be seen that two layers
  • the thickness 110 of coating 103 be from about 400 to about 4000 nanometers
  • the direct current susceptibility of the assembly depicted is equal to the sum of the (mass)x (susceptibility) for each individual layer 105/107 and for the substrate 104.
  • With a multiplicity of layers comprising the coating 103 which may have the same and/or different thicknesses, and/or the same and/or different masses, and/or the same and/or different compositions, and/or the same and/or different magnetic susceptibilities, more flexibility is provided in obtaining the desired correction.
  • each of the different species 120/122/124 within the coatings 105/107 retains its individual magnetic characteristics. These species are preferably not alloyed with each other; when such species are alloyed with each other, each of the species does not retain its individual magnetic characteristics.
  • An alloy as that te ⁇ n is used in this specification, is a substance having magnetic properties and consisting of two or more elements, which usually are metallic elements.
  • the bonds in the alloy are usually metallic bonds, and thus the individual elements in the alloy do not retain their individual magnetic properties because of the substantial "crosstalk" between the elements via the metallic bonding process.
  • each of the "magnetically distinct” materials may be, e.g., a material in elemental form, a compound, an alloy, etc.
  • the positively magnetized species include, e.g., those species that exhibit paramagetism, superparamagnetism, ferromagnetism, and/or ferrimagnetism.
  • Paramagnetism is a property exhibited by substances which, when placed in a magnetic field, are magnetized parallel to the field to an extent proportional to the field (except at very low temperatures or in extremely large magnetic fields).
  • Paramagnetic materials are well known to those skilled in the art. Reference may be had, e.g., to United States patents 5,578,922 (paramagnetic material in solution), 4,704,871 (magnetic refrigeration apparatus with belt of paramagnetic material), 4,243,939 (base paramagnetic material containing ferromagnetic impurity), 3,917,054 (articles of paramagnetic material), 3,796,4999 (paramagnetic material disposed in a gas mixture), and the like.
  • Superparamagnetic materials are also well known to those skilled in the art. Reference may be had, e.g., to United States patent 5,238,811, the entire disclosure of which is hereby incorporated by reference into this specification, it is disclosed (at column 5) that: "In one embodiment, the superparamagnetic material used is a substance which has a particle size smaller than that of a ferromagnetic material and retains no residual magnetization after disappearance of the external magnetic field. The superparamagnetic material and ferromagnetic material are quite different from each other in their hysteresis curve, susceptibility, Mesbauer effect, etc.
  • ferromagnetic materials are most suited for the conventional assay methods since they require that magnetic micro-particles used for labeling be efficiently guided even when a weak magnetic force is applied.
  • the preparation of these superparamagnetic materials is discussed at columns 6 et seq. of
  • the ferromagnetic substances can be selected appropriately, for example, from various compound magnetic substances such as magnetite and gamma-ferrite, metal magnetic substances such as iron, nickel and cobalt, etc.
  • the ferromagnetic substances can be converted into ultramicro particles using conventional methods excepting a mechanical grinding method, i.e., various gas phase methods and liquid phase methods. For example, an evaporation-in-gas method, a laser heating evaporation method, a coprecipitation method, etc. can be applied.
  • the ultramicro particles produced by the gas phase methods and liquid phase methods contain both superparamagnetic particles and ferromagnetic particles in admixture, and it is therefore necessary to separate and collect only those particles which show superparamagnetic property.
  • various methods including mechanical, chemical and physical methods can be applied, examples of which include centrifugation, liquid chromatography, magnetic filtering, etc.
  • the particle size of the superparamagnetic ultramicro particles may vary depending upon the kind of the ferromagnetic substance used but it must be below the critical size of single domain particles.
  • ferromagnetic material is magnetite or gamma- ferrite and it is not larger than 3 nm when pure iron is used as a ferromagnetic substance, for example.”
  • Ferromagnetic materials may also be used as the positively magnetized species.
  • ferromagnetism is a property, exhibited by certain metals, alloys, and compounds of the transition (iron group), rare-earth, and actinide elements, in which the internal magnetic moments spontaneously organize in a common direction; this property gives rise to a permeability considerably greater than that of a cuum, and also to magnetic hysteresis.
  • Ferrimagnetic materials may also be used as the positively magnetized specifies.
  • ferrimagnetism is a type of magnetism in which the magnetic moments of neighboring ions tend to align nonparallel, usually antiparallel, to each other, but the moments are of different magnitudes, so there is an appreciable, resultant magnetization. Reference may be had, e.g., to
  • some suitable positively magnetized species include, e.g., iron; iron/aluminum; iron/aluminum oxide; iron/aluminum nitride; iron/tantalum nitride; iron/tantalum oxide; nickel; nickel/cobalt; cobalt/iron; cobalt; samarium; gadolinium; neodymium; mixtures thereof; nano-sized particles of the aforementioned mixtures, where super-paramagnetic properties are exhibited; and the like.
  • materials with positive susceptibility include, e.g., aluminum, americium, cerium (beta form), cerium (gamma form), cesium, compounds of cobalt, dysprosium, compounds of dysprosium, europium, compounds of europium, gadolium, cmpounds of gadolinium, hafnium, compounds of holmium, iridium, compounds of iron, lithium, magnesium, manganese, molybdenum, neodymium, niobium, osmium, palladium, plutonium, potassium, praseodymium, rhodium, rubidium, ruthenium, samarium, sodium, strontium, tantalum, technicium, terbium, thorium, thulium, titanium, tungsten, uranium, vanadium, ytterbium, yttrium, and the like
  • negatively magnetized species include those materials with negative susceptibilities that are listed on such pages E-118 to E-123 of the CRC Handbook.
  • such species include, e.g.: antimony; argon; arsenic; barium; beryllium; bismuth; boron; calcium; carbon (dia); chromium; copper; gallium; germanium; gold; indium; krypton; lead; mercury; phosphorous; selenium; silicon; silver; sulfur; tellurium; thallium; tin (gray); xenon; zinc: and the link.
  • diamagnetic materials also are suitable negatively magnetized species.
  • diamagnetism is that property of a material that is repelled by magnets. The term
  • diamagnetic susceptibility refers to the susceptibility of a diamagnetic material, which is always negative. Diamagnetic materials are well known to those skilled in the art. Reference may be had, e.g., to United States patents 6,162,364 (diamagnetic objects); 6,159,271 (diamagnetic liquid); 5,408,178 (diamagnetic and paramagnetic objects); 5,315,997 (method of magnetic resonance imaging using diamagnetic contrast); 5,162,301; 5,047,392 (diamagnetic colloids); 5,043,101; 5,026,681 (diamagnetic colloid pumps); 4,908,347 (diamagnetic flux shield); 4,778,594; 4,735,796; 4,590,922; 4,290,070; 3,899,758; 3,864,824; 3,815,963 (pseudo-diamagnetic suspension); 3,597,022; 3,572,273; and the like. The entire disclosure of
  • the diamagnetic material used may be an organic compound with a negative suspceptibility.
  • such compounds include, e.g.: alanine; allyl alcohol; amylamine; aniline; asparagines; aspartic acid; butyl alcohol; chloresterol; coumarin; diethylamine; erythritol; eucalyptol; fructose; galactose; glucose; D-glucose; glutamic acid; glycerol; glycine; leucine; isoleucine; mannitol; mannose; and the like.
  • the alloying of A and B in equal proportions may not yield a zero magnetization compact.
  • nano-sized particles, or micro-sized particles tend to retain their magnetic properties as long as they remain in particulate form.
  • alloys of such materials often do not retain such properties. Nullification of the susceptibility contribution due to the substrate
  • the coating 103 depicted therein preferably has a positive susceptibility, and the coated substrate 100 thus has a substantially zero susceptibility.
  • some substrates such niobium, nitinol, stainless steel, etc.
  • the coatings should preferably be chosen to have a negative susceptibility so that, under the conditions of the MRI radiation (or of any other radiation source used), the net susceptibility of the coated object is still substantially zero.
  • the contribution of each of the materials in the coating(s) is a function of the mass of such material and its magnetic susceptibility.
  • ⁇ SUb + % coat - 0 wherein ⁇ sub is the susceptibility of the substrate , and ⁇ C0!1 , is the susceptibility of the coating, when each of these is present in a 1/1 ratio.
  • ⁇ sub is the susceptibility of the substrate
  • ⁇ C0!1 is the susceptibility of the coating, when each of these is present in a 1/1 ratio.
  • the aforementioned equation is used when the coating and substrate are present in a 1/1 ratio.
  • the uncoated substrate 104 may either comprise or consist essentially of niobium, which has a susceptibility of + 195.0 x 10 "6 centimeter-gram seconds at 298 degrees Kelvin.
  • the substrate 104 may contain at least 98 molar percent of niobium and less than 2 molar percent of zirconium.
  • Zirconium has a susceptibility of -122 x 0 x 10 "6 centimeter- gram seconds at 293 degrees Kelvin. As will be apparent, because of the predominance of niobium, the net susceptibility of the uncoated substrate will be positive.
  • the substrate may comprise Nitinol.
  • Nitinol is a paramagnetic alloy, an intermetallic compound of nickel and titanium; the alloy preferably contains from 50 to 60 percent of nickel, and it has a permeability value of about 1.002.
  • the susceptibility of Nitinol is positive.
  • Nitinols with nickel content ranging from about 53 to 57 percent are known as "memory alloys" because of their ability to "remember” or return to a previous shape upon being heated which is an alloy of nickel and titanium, in an approximate 1/1 ratio.
  • the susceptibility of Nitinol is positive.
  • the substrate 104 may comprise tantalum and/or titanium, each of which has a positive susceptibility. See, e.g., the CRC handbook cited above.
  • the coating to be used for such a substrate should have a negative susceptibility.
  • the values of negative susceptibilities for various elements are -9.0 for beryllium, -280.1 for bismuth (s), -10.5 for bismuth (1), - 6.7 for boron, - 56.4 for bromine (1), -73.5 for bromine(g), -19.8 for cadmium(s), -18.0 for cadmium(l), -5.9 for carbon(dia), -6.0 for carbon (graph), -5.46 for copper(s), - 6.16 for copper(l), -76.84 for germanium, -28.0 for gold(s), -34.0 for gold(l), -25.5 for indium, -88.7 for iodine(s), -23.0 for lead(s), -15.5 for lead(l), -19.5 for silver(s), -24.0 for silver(l), -15.5 for sulfur(alpha), -14.9 for sulfur(beta), -15.4 for sulfur(l), -39.5 for
  • each of these values is expressed in units equal to the number in question x 10 "6 centimeter- gram seconds at a temperature at or about 293 degrees Kelvin.
  • those materials which have a negative susceptibility value are often referred to as being diamagnetic.
  • a listing of organic compounds that are diamagnetic is presented on pages E123 to E134 of the aforementioned "Handbook of Chemistry and Physics,” 63rd edition (CRC Press, Inc., Boca Raton, Florida, 1974).
  • one or more of the following magnetic materials described below are preferably incorporated into the coating.
  • the desired magnetic materials in this embodiment, preferably have a positive susceptibility, with values ranging from + I x IO "6 centimeter-gram seconds at a temperature at or about 293 degrees Kelvin, to about 1 x 10 7 centimeter-gram seconds at a temperature at or about 293 degrees Kelvin.
  • materials such as Alnicol (see page E-112 of the CRC handbook), which is an alloy containing nickel, aluminum, and other elements such as, e.g., cobalt and/or iron.
  • silicon iron see page El 13 of the CRC handbook
  • steel see page 117 of the CRC handbook.
  • the uncoated substrate 104 has an effective inductive reactance at a d.c. field of 1.5 Tesla that exceeds its capacitative reactance, whereas the coating 103 has a capacitative reatance that exceeds its inductive reactance.
  • the coated (composite) substrate 100 706 has a net reactance that is preferably substantially zero.
  • the effective inductive reactance of the uncoated stent 104 may be due to a multiplicity of factors including, e.g., the positive magnetic susceptibility of the materials which it is comprised of it, the loop currents produced, the surface eddy produced, etc. Regardless of the source(s) of its effective inductive reactance, it can be "corrected” by the use of one or more coatings which provide, in combination, an effective capacitative reactance that is equal to the effective inductive reactance.
  • Imaging of restenosis Referring again to Figure 4, and in the embodiment depicted, plaque particles 130,132 are disposed on the inside of substrate 104.
  • the imaging field 140 can pass substantially unimpeded through the coating 103 and the substrate 104 and interact with the plaque particles 130/132 to produce imaging signals 141.
  • the imaging signals 141 are able to pass back through the substrate 104 and the coating 103 because the net reactance is substantially zero. Thus, these imaging signals are able to be received and processed by the MRI apparatus.
  • the desired object to be imaged such as, e.g., the plaque particles
  • the entire assembly 13, including the biological material 130/132 preferably presents a direct current magnetic susceptibility that is plus or minus I x 10 "3 centimeter-gram-seconds (cgs) and, more preferably, plus or minus 1 x 10 '4 centimeter-gram-seconds.
  • the d.c. susceptibility of the assembly 13 is equal to plus or minus 1 x 10 "5 centimeter-gram-seconds.
  • the d.c. susceptibility of the assembly 13 is equal to plus or minus 1 x 10 "6 centimeter-gram-seconds.
  • each of the components of assembly 13 has its own value of magnetic susceptibility.
  • the biological material 130/132 has a magnetic susceptibility of S].
  • the substrate 104 has a magnetic susceptibility of S 2
  • the coating 103 has a magnetic susceptibility of S 3 .
  • Each of the components of the assembly 13 makes a contribution to the total magnetic susceptibility of such assembly, depending upon (a) whether its magnetic susceptibility is positive or negative, (b) the amount of its positive or negative susceptibility value, and (c) the percentage of the total mass that the individual coponenent represents.
  • Mc is the weight fraction of that component (the weight of that component divided by the total weight of all components in the assembly 6000).
  • the McSc values for the nanomagentic material 120 are chosen to, when appropriate, correct for the total McSc values of all of the other components (including the biological material 130/132) such that, after such correction(s), the total susceptibility of the assembly 13 is plus or minus 1 x x 10 "3 centimeter-gram-seconds (cgs) and, more preferably, plus or minus 1 x 10 " 4 centimeter-gram-seconds.
  • the d.c. susceptibility of the assembly 13 is equal to plus or minus 1 x 10 "5 centimeter-gram-seconds.
  • the d.c. susceptibility of the assembly 13 is equal to plus or minus 1 x 10 "6 centimeter-gram-seconds.
  • the assembly 13 there may be other materials/components in the assembly 13 whose values of positive or negative susceptibility, and/or their mass, may be chosen such that the total magnetic susceptibility of the assembly is plus or minus 1 x x 10 "3 centimeter-gram-seconds (cgs) and, more preferably, plus or minus 1 x 10 '4 centimeter-gram-seconds.
  • the configuration of the substrate may be varied in order to vary its magnetic susceptibility properties and/or other properties.
  • a stent 200 constructed form Nitinol is comprised of struts 202, 204, 206, and 208 coated with a layer of elemental bismuth.
  • Nitinol is a paramagnetic alloy that was developed by the Naval Ordnance Laboratory; it is an intermetallic compound of nickel and titanium. See, e.g., page 552 of George S. Brady et al.'s "Materials Handbook," Thirteenth Edition (McGraw-Hill Company, New York, New York, 1991).
  • the stent 200 is preferably cylindrical with a diameter (not shown) of less than 1 centimeter and a length 210 of about 3 centimeters.
  • Each strut, such as strut 202 is preferably arcuate, having an effective diameter 212 of less than about 1 millimeter.
  • the magnetic permeability of the Nitinol material is about 1.003; and its susceptibility is about 0.03 centimeter-grams-seconds (cgs).
  • a diamagnetic material such as bismuth, that has a negative susceptibility.
  • a bismuth coating with a thickness of form about 10 to about 20 microns is deposited upon each of the struts 202.
  • the susceptibility for these struts 202 becomes substantially zero, whereby there is no substantial direct current (d.c.) susceptibility distortion in the MRI field.
  • substantially zero refers to a net susceptibility of from about 0.9 to about 1.1.
  • the amount and type of the coating is chosen such that the net susceptibility for the struts is still preferably substantially zero
  • susceptibility varies with both direct current and alternating current. It is desired that, with the composite coating 103 described hereinabove, the susceptibility at a direct current field of about 1.5 Tesla (which is also the slope of the plot of magnetization versus the applied magnetic field), should preferably be from about 0.9 to about 1.1. Incorporation by reference of United States patent 6,713,671
  • United States patent application U.S.S.N. 10/303,264 discloses a shielded assembly comprised of a substrate and, disposed above a substrate, a shield comprising from about 1 to about 99 weight percent of a first nanomagnetic material, and from about 99 to about 1 weight percent of a second material with a resistivity of from about 1 microohm- centimeter to about 1 x 1025 microohm centimeters; the nanomagnetic material comprises nanomagnetic particles, and these nanomagnetic particles respond to an externally applied magnetic field by realigning to the externally applied field.
  • a shielded assembly and/or the substrate thereof and/or the shield thereof may be used in the processes, compositions, and/or constructs of this invention.
  • the substrate used may be, e.g, comprised of one or more conductive material(s) that have a resistivity at 20 degrees Centigrade of from about 1 to about 100 microohm-centimeters.
  • the conductive material(s) may be silver, copper, aluminum, alloys thereof, mixtures thereof, and the like.
  • the substrate consists consist essentially of such conductive material.
  • conductive wires are coated with electrically insulative material.
  • Suitable insulative materials include nano-sized silicon dioxide, aluminum oxide, cerium oxide, yttrium-stabilized zirconia, silicon carbide, silicon nitride, aluminum nitride, and the like. In general, these nano-sized particles will have a particle size distribution such that at least about 90 weight percent of the particles have a maximum dimension in the range of from about 10 to about 100 nanometers.
  • the coated conductors may be prepared by conventional means such as, e.g., the process described in United States patent 5,540,959, the entire disclosure of which is hereby incorporated by reference into this specification.
  • cathodic arc plasma deposition see pages 229 et seq.
  • chemical vapor deposition see pages 257 et seq.
  • sol-gel coatings see pages 655 et seq.
  • Figure 2 of United States patent 6,713,671 is a sectional view of the coated conductors 14/16.
  • conductors 14 and 16 are separated by insulating material 42.
  • the insulating material 42 that is disposed between conductors 14/16 may be the same as the insulating material 44/46 that is disposed above conductor 14 and below conductor 16.
  • the insulating material 42 may be different from the insulating material 44 and/or the insulating material 46.
  • step 48 of the process of such Figure 2 describes disposing insulating material between the coated conductors 14 and 16. This step may be done simultaneously with step 40; and it may be done thereafter.
  • the insulating material 42, the insulating material 44, and the insulating material 46 each generally has a resistivity of from about 1,000,000,000 to about 10,000,000,000,000 ohm-centimeters.
  • the coated conductor assembly is prefeiably heat treated in step 50.
  • This heat treatment often is used m conjunction with coating processes m which the heat is lequired to bond the msulative material to the conductors 14/16.
  • the heat-treatment step may be conducted after the deposition of the insulating material 42/44/46, or it may be conducted simultaneously therewith In either event, and when it is used, it is preferred to heat the coated conductors 14/16 to a temperature of from about 200 to about 600 degrees Centigrade for from about 1 minute to about 10 minutes
  • step 52 of the process after the coated conductors 14/16 have been subjected to heat treatment step 50, they are allowed to cool to a temperature of from about 30 to about 100 degrees Centigrade over a period of time of from about 3 to about 15 minutes.
  • one need not invariably heat treat and/or cool.
  • one may immediately coat nanomagnetic particles onto to the coated conductors 14/16 in step 54 either after step 48 and/or after step 50 and/or after step 52.
  • nanomagnetic materials are coated onto the previously coated conductors 14 and 16. This is best shown m Figure 2 of such patent, wherein the nanomagnetic particles are identified as particles 24
  • nanomagnetic matenal is magnetic material which has an average particle size less than 100 nanometers and, preferably, in the range of from about 2 to 50 nanometers
  • the thickness of the layer of nanomagnetic material deposited onto the coated conductors 14/16 is less than about 5 microns and generally from about 0 1 to about 3 microns
  • the coated assembly may be optionally heat-treated m step 56 In this optional step 56, it is preferred to subject the coated conductors 14/16 to a temperature of from about 200 to about 600 degrees Centigrade for from about 1 to about 10 minutes
  • illustrated m Figure 3 of United States patent 6,713,671 one or more additional insulating layers 43 are coated onto the assembly depicted m Figure 2 of such patent This is conducted in optional step 58 (see Figure IA of such patent)
  • Figure 4 of United States patent 6,713,671 is a partial schematic view of the assembly 11 of Figure 2 of such patent, illustrating the current flow m such assembly
  • Figuie 4 of United States patent 6,713,671 it will be seen that current flows into conductor 14 in the direction of ai ⁇ ow 60, and it flows out of conductor 16 in the direction of arrow 62.
  • the net current flow through the assembly 11 is zero; and the net Lorentz force in the assembly 11 is thus zero. Consequently, even high current flows in the assembly 1 1 do not cause such assembly to move,
  • conductors 14 and 16 are substantially parallel to each other, As will be apparent, without such parallel orientation, there may be some net current and some net Lorentz effect.
  • the conductors 14 and 16 preferably have the same diameters and/or the same compositions and/or the same length.
  • the nanomagnetic particles 24 are present in a density sufficient so as to provide shielding from magnetic flux lines 64. Without wishing to be bound to any particular theory, applicant believes that the nanomagnetic particles 24 trap and pin the magnetic lines of flux 64.
  • the nanomagnetic particles 24 preferably have a specified magnetization, As is known to those skilled in the art, magnetization is the magnetic moment per unit volume of a substance. Reference may be had, e.g., to United States patents 4,169,998, 4,168,481, 4,166,263, 5,260,132, 4,778,714, and the like. The entire disclosure of each of these United States patents is hereby incorporated by reference into this specification.
  • the layer of nanomagnetic particles 24 preferably has a saturation magnetization, at 25 degrees Centigrade, of from about 1 to about 36,000 Gauss, or higher.
  • the saturation magnetization at room temperature of the nanomagentic particles is from about 500 to about 10,000 Gauss.
  • a thin film with a thickness of less than about 2 microns and a saturation magnetization in excess of 20,000 Gauss.
  • the thickness of the layer of nanomagentic material is measured from the bottom surface of the layer that contains such material to the top surface of such layer that contains such material; and such bottom surface and/or such top surface may be contiguous with other layers of material (such as insulating material) that do not contain nanomagnetic particles.
  • the film 104 is adapted to reduce the magnetic field strength at point 108 (which is disposed less than 1 centimeter above film 104) by at least about 50 percent.
  • the film 104 has a magnetic shielding factor of at least about 0.5.
  • the film 104 has a magnetic shielding factor of at least about 0.9, i.e., the magnetic field strength at point 110 is no greater than about 10 percent of the magnetic field strength at point 108.
  • the static magnetic field strength at point 108 can be, e.g., one Tesla
  • the static magnetic field strength at point 110 can be, e.g., 0.1 Tesla.
  • the time-varying magnetic field strength of a 100 milliTesla would be reduced to about 10 milliTesla of the time-varying field.
  • a coated stent 100 is imaged by an MRI imaging process.
  • the process depicted in Figure 4 can be used with reference to other medical devices such as, e.g., a coated brachytherapy seed.
  • the coated stent 100 is contacted with the radio-frequency, direct current, and gradient fields normally associated with MRI imaging processes; these fields are discussed elsewhere in this specification. They are depicted as an MRI imaging signal 140 in Figure 4
  • the MRI imaging signal 140 penetrates the coated stent 100 and interacts with material disposed on the inside of such stent, such as, e.g., plaque particles 130 and 132. This interaction produces a signal best depicted as arrow 141 in Figure 4.
  • the signal 440 is substantially unaffected by its passage through the coated stent 100.
  • the radio-frequency field that is disposed on the outside of the coated stent 100 is substantially the same as the radio-frequency field that passes through and is disposed on the inside of the coated stent 100.
  • the characteristics of the signal 140 are substantially varied by its passage through the uncoated stent.
  • the radio-frequency signal that is disposed on the outside of the stent (not shown) differs substantially from the radio-frequency field inside of the uncoated stent (not shown). In some cases, because of substrate effects, substantially none of such radio-frequency signal passes through the uncoated stent (not shown).
  • the MRI field(s) interact with material disposed on the inside of coated stent 100 such as, e.g., plaque particles 130 and 132. This interaction produces a signal 141 by means well known to those in the MRI imaging art.
  • the signal 141 passes back through the coated stent 100 in a manner .such that it is substantially unaffected by the coated stent 100.
  • the radio-frequency field that is disposed on the inside of the coated stent 100 is substantially the same as the radio-frequency field that passes through and is disposed on the outside of the coated stent 100.
  • the characteristics of the signal 141 are substantially varied by its passage through the uncoated stent.
  • the radio-frequency signal that is disposed on the inside of the stent (not shown) differs substantially from the radio-frequency field outside of the uncoated stent (not shown).
  • substantially none of such signal 141 passes through the uncoated stent (not shown).
  • a sputtering technique is used to prepare an AlFe thin film or particles, as well as comparable thin films containing other atomic moieties, or particles, such as, e.g., elemental nitrogen, and elemental oxygen.
  • Conventional sputtering techniques may be used to prepare such films by sputtering. See, for example, R. Herrmann and G. Brauer, "D. C- and R.F. Magnetron Sputtering," in the "Handbook of Optical Properties: Volume I — Thin Films for Optical Coatings," edited by R.E. Hummel and K.H. Guenther (CRC Press, Boca Raton, Florida, 1955). Reference also may be had, e.g., to M.
  • a typical sputtering system is described in United States patent 5,178,739, the entire disclosure of which is hereby incorporated by reference into this specification.
  • a typical sputtering system is described in United States patent 5,178,739, the entire disclosure of which is hereby incorporated by reference into this specification.
  • “...a sputter system 10 includes a vacuum chamber 20, which contains a circular end sputter target 12, a hollow, cylindrical, thin, cathode magnetron target 14, a RF coil 16 and a chuck 18, which holds a semiconductor substrate 19.
  • the atmosphere inside the vacuum chamber 20 is controlled through channel 22 by a pump (not shown).
  • the vacuum chamber 20 is cylindrical and has a series of permanent, magnets 24 positioned around the chamber and in close proximity therewith to create a multiple field configuration near the interior surface 15 of target 12.
  • Magnets 26, 28 are placed above end sputter target 12 to also create a multipole field in proximity to target 12.
  • a singular magnet 26 is placed above the center of target 12 with a plurality of other magnets 28 disposed in a circular formation around magnet 26. For convenience, only two magnets 24 and 28 are shown.
  • the configuration of target 12 with magnets 26, 28 comprises a magnetron sputter source 29 known in the prior art, such as the Torus-10E system manufactured by K. Lesker, Inc.
  • a sputter power supply 30 (DC or RF) is connected by a line 32 to the sputter target 12.
  • a RF supply 34 provides power to RF coil 16 by a line 36 and through a matching network 37.
  • Variable impedance 38 is connected in series with the cold end 17 of coil 16.
  • a second sputter power supply 39 is connected by a line 40 to cylindrical sputter target 14.
  • a bias power supply 42 (DC or RF) is connected by a line 44 to chuck 18 in order to provide electrical bias to substrate 19 placed thereon, in a manner well known in the prior art.”
  • a magnetron sputtering technique is utilized, with a Lesker Super System III system
  • the vacuum chamber of this system is preferably cylindrical, with a diameter of approximately one meter and a height of approximately 0.6 meters.
  • the base pressure used is from about 0.001 to 0.0001 Pascals.
  • the target is a metallic FeAl disk, with a diameter of approximately 0.1 meter.
  • the molar ratio between iron and aluminum used in this aspect is approximately 70/30.
  • the starting composition in this aspect is almost non-magnetic. See, e.g., page 83 ( Figure 3.1aii) of R.S.
  • a DC power source is utilized, with a power level of from about 150 to about 550 watts (Advanced Energy Company of Colorado, model MDX Magnetron
  • the sputtering gas used in this aspect is argon, with a flow rate of from about 0.0012 to about 0.0018 standard cubic meters per second.
  • a pulse-forming device is utilized, with a frequency of from about 50 to about 250 MHz (Advanced Energy Company, model Sparc-le V).
  • a typical argon flow rate is from about (0.9 to about 1.5) x 10 "3 standard cubic meters per second; a typical nitrogen flow rate is from about (0.9 to about 1.8) x 10 "3 standard cubic meters per second; and a typical oxygen flow rate is from about. (0.5 to about 2) x 10 "3 standard cubic meters per second.
  • the pressure typically is maintained at from about 0.2 to about 0.4 Pascals. Such a pressure range has been found to be suitable for nanomagnetic materials fabrications.
  • the substrate used maybe either flat or curved.
  • a typical flat substrate is a silicon wafer with or without a thermally grown silicon dioxide layer, and its diameter is preferably from about 0.1 to about 0.15 meters.
  • a typical curved substrate is an aluminum rod or a stainless steel wire, with a length of from about 0.10 to about 0..56 meters and a diameter of from (about 0.8 to about 3.0) x 10 '3 meters The distance between the substrate and the target is preferably from about 0.05 to about 0.26 meters.
  • the wafer in order to deposit a film on a wafer, the wafer is fixed on a substrate holder.
  • the substrate may or may not be rotated during deposition.
  • the rod or wire is rotated at a rotational speed of from about 0.01 to about 0.1 revolutions per second, and it is moved slowly back and forth along its symmetrical axis with a maximum speed of about 0.01 meters per second.
  • the power required for the FeAl film is 200 watts, and the power required for the FeAlN film is 500 watts
  • the resistivity of the FeAlN film is approximately one order of magnitude larger than that of the metallic FeAl film.
  • the resistivity of the FeAlO film is about one order of magnitude larger than that of the metallic FeAl film.
  • Iron containing magnetic materials such as FeAl, FeAlN and FeAlO, FeAlNO, FeCoAlNO, and the like, may be fabricated by sputtering.
  • the magnetic properties of those materials vary with stoichiometric ratios, particle sizes, and fabrication conditions; see, e.g., R.S. Tebble and D.J. Craik, "Magnetic Materials", pp. 81-88, Wiley-Interscience, New York, 1969 As is disclosed in this reference, when the iron molar ratio in bulk FeAl materials is less than 70 percent or so, the materials will no longer exhibit magnetic properties.
  • Figure 6 is a schematic of a deposition system 300 comprised of a power supply 302 operatively connected via line 304 to a magnetron 306. Disposed on top of magnetron 306 is a target 308. The target 308 is contacted by gas 310 and gas 312, which cause sputtering of the target 308. The material so sputtered contacts substrate 314 when allowed to do so by the absence of shutter 316.
  • the target 308 is mixture of aluminum and magnesium atoms in a molar ratio of from about 0.05 to about 0.5 Mg/(A1 + Mg). In one aspect of this embodiment, the ratio of Mg/(A1 + Mg) is from about 0.08 to about 0.12 .
  • These targets are commercially available and are custom made by companies such as, e.g., Kurt Lasker and Company of Pittsburgh, Pa.
  • the power supply 302 preferably provides pulsed direct current. Generally, power supply 302 provides power in excess of 300 watts, preferably in excess of 500 watts, and more preferably in excess of 1,000 watts. In one embodiment, the power supplied by power supply 302 is from about 1800 to about 2500 watts.
  • the power supply preferably provides rectangular-shaped pulses with a duration (pulse width) of from about 10 nanoseconds to about 100 nanoseconds. In one embodiment, the pulse width is from about 20 to about 40 nanoseconds.
  • the time between adjacent pulses is generally from about 1 microsecond to about 10 microseconds and is generally at least 100 times greater than the pulse width. In one embodiment, the repetition rate of the rectangular pulses is preferably about 150 kilohertz.
  • d.c. pulsed direct current
  • a magnetic field has a magnetic flux density of from about 0.01 Tesla to about 0.1 Tesla.
  • the energy provided to magnetron 306 preferably comprises intermittent pulses
  • the resulting magnetic fields produced by magnetron 306 will also be intermittent.
  • the process depicted therein preferably is conducted within a vacuum chamber 318 in which the base pressure is from about 1 x 10 "8 Torr to about 0.000005 Torr. In one embodiment, the base pressure is from about 0.000001 to about 0.000003 Torr.
  • the temperature in the vacuum chamber 318 generally is ambient temperature prior to the time sputtering occurs.
  • argon gas is fed via line 310, and nitrogen gas is fed via line 312 so that both impact target 308, preferably in an ionized state.
  • argon gas, nitrogen gas, and oxygen gas are fed via target 312.
  • the argon gas, and the nitrogen gas are fed at flow rates such that the flow rate of the argon gas divided by the flow rate of the nitrogen gas preferably is from about 0.6 to about 1.2. In one aspect of this embodiment, such ratio of argon to nitrogen is from about 0.8 to about 0.95.
  • the flow rate of the argon may be 20 standard cubic centimeters per minute, and the flow rate of the nitrogen may be 23 standard cubic feet per minute.
  • the argon gas, and the nitrogen gas contact a target 308 that is preferably immersed in an electromagnetic field. This field tends to ionize the argon and the nitrogen, providing ionized species of both gases. It is such ionized species that bombard target 308.
  • target 308 may be, e.g., pure aluminum. In one preferred embodiment, however, target 308 is aluminum doped with minor amounts of one or more of the aforementioned moieties B. In the latter embodiment, the moieties B are preferably present in a concentration of from about 1 to about 40 molar percent, by total moles of aluminum and moieties B. It is preferred to use from about 5 to about 30 molar percent of such moieties B.
  • the shutter 316 prevents the sputtered particles from contacting substrate 314.
  • the sputtered particles 320 can contact and coat the substrate 314.
  • the temperature of substrate 314 is controlled by controller 322 that can heat the substrate (by means such as a conduction heater or an infrared heater) and/or cool the substrate (by means such as liquid nitrogen or water).
  • the sputtering operation increases the pressure within the region of the sputtered particles 320.
  • the pressure within the area of the sputtered particles 320 is at least 100 times, and preferably 1000 times, greater than the base pressure.
  • a cryo pump 324 is preferably used to maintain the base pressure within vacuum chamber 318.
  • a mechanical pump (dry pump) 326 is operatively connected to the cryo pump 324. Atmosphere from chamber 318 is removed by dry pump 326 at the beginning of the evacuation. At some point, shutter 328 is removed and allows cryo pump 324 to continue the evacuation.
  • a valve 330 controls the flow of atmosphere to dry pump 326 so that it is only open at the beginning of the evacuation. It is preferred to utilize a substantially constant pumping speed for cryo pump 324, i.e., to maintain a constant outflow of gases through the cryo pump 324. This may be accomplished by sensing the gas outflow via sensor 332 and, as appropriate, varying the extent to which the shutter 328 is open or partially closed.
  • a substantially constant gas outflow rate insures a substantially constant deposition of sputtered nitrides.
  • an organic solvent such as acetone, isopropryl alcohol, toluene, etc.
  • the cleaned substrate 314 is presputtered by suppressing sputtering of the target 308 and sputtering the surface of the substrate 314.
  • a substrate is cooled so that nanomagnetic particles are collected on such substrate.
  • a precursor 400 that preferably contains moieties A, B, and C (which are described elsewhere in this specification) are charged to reactor 402.
  • the reactor 402 may be a plasma reactor.
  • Plasma reactors are described in applicants' United States patents 5,100,868 (process for preparing superconducting films), 5,120,703 (process for preparing oxide superconducting films by radio-frequency generated aerosol-plasma deposition in atmosphere), 5,157,015 (process for preparing superonducting films by radio-frequency generated aerosol-plasma deposition in atmosphere), 5,213,851 (process for preparing ferrite films by radio- frequency generated aerosol plasma deposition in atmosphere), 5,260,105 (aerosol plasma deposition of films for electrochemical cells), 5,364,562 (aerosol plasma deposition of insulating oxide powder), 5,366,770 (aerosol plasma deposition of films for electronic cells), and the like. The entire disclosure of each of these United States patents is hereby incorporated by reference into this specification.
  • the reactor 402 may be sputtering reactor 300 depicted in Figure 6.
  • an energy source 4045 is preferably used in order to cause reaction between moieties A, B, and C.
  • the energy source 404 may be an electromagnetic energy source that supplies energy to the reactor 400.
  • the two preferred moiety C species are oxygen and nitrogen.
  • moieties A, B, and C are preferably combined into a metastable state. This metastable state is then caused to travel towards collector 406. Prior to the time it reaches the collector 406, the ABC moiety is formed, either in the reactor 3 and/or between the reactor 402 and the collector 406.
  • collector 406 is preferably cooled with a chiller 408 so that its surface 410 is at a temperature below the temperature at which the ABC moiety interacts with surface 410; the goal is to prevent bonding between the ABC moiety and the surface 410.
  • the surface 410 is at a temperature of less than about 30 degrees Celsius. In another embodiment, the temperature of surface 410 is at the liquid nitrogen temperature, i.e., about 77 degrees Kelvin.
  • Figure 8 is a schematic illustration of one process of the invention that may be used to make nanomagnetic material. This Figure 8 is similar in many respects to the Figure 1 of United States patent 5,213,851, the entire disclosure of which is hereby incorporated by reference into this specification.
  • ferrite refers to a material that exhibits feiTomagnetism. Ferromagnetism is a property, exhibited by certain metals, alloys, and compounds of the transition (iron group) rare earth and actinide elements, in which the internal magnetic moments spontaneously organize in a common direction; ferromagnetism gives rise to a permeability considerably greater than that of vacuum and to magnetic hysteresis. See, e.g, page 706 of Sybil B.
  • the ferromagnetic material contains Fe 2 O 3 .
  • Fe 2 O 3 See, for example, United States patent 3,576,672 of Harris et al, the entire disclosure of which is hereby incorporated by reference into this specification. As will be apparent, the corresponding nitrides also may be made.
  • the ferromagnetic material contains garnet. Pure iron garnet has the formula M 3 Fe 5 O 12 ; see, e.g., pages 65-256 of Wilhelm H. Von Aulock's "Handbook of Microwave Ferrite Materials” (Academic Press, New York, 1965).
  • Garnet ferrites are also described, e.g., in United States patent 4,721,547, the disclosure of which is hereby incorporated by reference into this specification. As will be apparent, the corresponding nitrides also may be made.
  • the ferromagnetic material contains a spinel ferrite.
  • Spinel ferrites usually have the formula MFe 2 O 4 , wherein M is a divalent metal ion and Fe is a trivalent iron ion.
  • M is typically selected from the group consisting of nickel, zinc, magnesium, manganese, and like.
  • the ferromagnetic material contains a lithium ferrite.
  • Lithium ferrites are often described by the fonnula (Li o .s Fe o .s)2 + (Fe 2 )3 + O 4 .
  • Some illustrative lithium ferrites are described on pages 407-434 of the aforementioned Von Aulock book and in United States patents 4,277,356, 4,238,342, 4,177,438, 4,155,963, 4,093,781, 4,067,922, 3,998,757, 3,767,581, 3,640,867, and the like. The disclosure of each of these patents is hereby incorporated by reference into this specification. As will be apparent, the corresponding nitrides also may be made.
  • the ferromagnetic material contains a hexagonal ferrite.
  • These ferrites are well known and are disclosed on pages 451-518 of the Von Aulock book and also in United States patents 4,816,292, 4,189,521, 5,061,586, 5,055,322, 5,051,201, 5,047,290, 5,036,629, 5,034,243, 5,032,931, and the like. The disclosure of each of these patents is hereby incorporated by reference into this specification. As will be apparent, the corresponding nitrides also may be made.
  • the ferromagnetic material contains one or more of the moieties A, B, and C disclosed in the phase diagram disclosed elsewhere in this specification and discussed elsewhere in this specification.
  • the solution 509 will preferably comprise reagents necessary to form the required magnetic material.
  • the solution in order to form the spinel nickel ferrite of the formula NiFe 2 O 4 , the solution should contain nickel and iron, which may be present in the form of nickel nitrate and iron nitrate.
  • nickel chloride and iron chloride may be used to form the same spinel.
  • nickel sulfate and iron sulfate may be used.
  • the solution 509 contains the reagent needed to produce a desired ferrite in stoichiometric ratio.
  • one mole of nickel nitrate may be charged with every two moles of iron nitrate.
  • the starting materials are powders with purities exceeding 99 percent.
  • compounds of iron and the other desired ions are present in the solution in the stoichiometric ratio.
  • ions of nickel, zinc, and iron are present in a stoichiometric ratio of 0.5/0.5/2.0, respectively.
  • ions of lithium and iron are present in the ratio of 0.5/2.5.
  • ions of magnesium and iron are present in the ratio of 1.0/2.0.
  • ions of manganese and iron are present in the ratio 1.0/2.0.
  • ions of yttrium and iron are present in the ratio of 3.0/5.0.
  • ions of lanthanum, yttrium, and iron are present in the ratio of 0.5/2.5/5.0.
  • ions of neodymium, yttrium, gadolinium, and iron are present in the ratio of
  • ions of samarium and iron are present in the ratio of 3.0/5.0.
  • ions of neodymium, samarium, and iron are present in the ratio of 0.1/2.9/5.0, or 0.25/2.75/5.0, or 0.375/2.625/5.0.
  • ions of neodymium, erbium, and iron are present in the ratio of 1.5/1.5/5.0.
  • samarium, yttrium, and iron ions are present in the ratio of 0.51/2.49/5.0, or 0.84/2.16/5.0, or 1.5/1.5/5.0.
  • ions of yttrium, gadolinium, and iron are present in the ratio of 2.25/0.75/5.0, or 1.5/1.5/5.0, or 0.75/2.25/5.0.
  • ions of terbium, yttrium, and iron are present in the ratio of 0.8/2.2/5.0, or 1.0/2.0/5.0.
  • ions of dysprosium, aluminum, and iron are present in the ratio of 3/x/5-x, when x is from 0 to 1.0.
  • ions of dysprosium, gallium, and iron are also present in the ratio of
  • ions of dysprosium, chromium, and iron are also present in the ratio of 3/x/5-x.
  • the ions present in the solution may be holmium, yttrium, and iron, present in the ratio of z/3-z/5.0, where z is from about 0 to 1.5.
  • the ions present in the solution may be erbium, gadolinium, and iron in the ratio of 1.5/1.5/5.0.
  • the ions may be erbium, yttrium, and iron in the ratio of 1.5/1.5/1.5, or 0.5/2.5/5.0.
  • the ions present in the solution may be thulium, yttrium, and iron, in the ratio of 0.06/2.94/5.0.
  • the ions present in the solution may be ytterbium, yttrium, and iron, in the ratio of 0.06/2.94/5.0.
  • the ions present in the solution may be lutetium, yttrium, and iron in the ratio of y/3-y/5.0, wherein y is from 0 to 3.0.
  • the ions present in the solution may be iron, which can be used to form Fe 6 O 8 (two formula units of Fe 3 C ⁇ ).
  • the ions present may be barium and iron in the ratio of 1.0/6.0, or 2.0/8.0.
  • the ions present may be strontium and iron, in the ratio of 1.0/12.0.
  • the ions present may be strontium, chromium, and iron in the ratio of 1.0/1.0/10.0, or 1.0/6.0/6.0.
  • the ions present may be suitable for producing a ferrite of the formula (Me x ) 3 + Ba ]-x Fei 2 Oi 9 , wherein Me is a rare earth selected from the group consisting of lanthanum, promethium, neodymium, samarium, europium, and mixtures thereof.
  • the ions present in the solution may contain barium, either lanthanum or promethium, iron, and cobalt in the ratio of l-a/a/12-a/a, wherein a is from 0.0 to 0.8.
  • the ions present in the solution may contain barium, cobalt, titanium, and iron in the ratio of
  • the ions present in the solution may contain barium, nickel or cobalt or zinc, titanium, and iron in the ratio of 1.0/c/c/12-2c, wherein c is from 0.0 to 1.5.
  • the ions present in the solution may contain barium, iron, iridium, and zinc in the ratio of 1.0/12-2d/d/d, wherein d is from 0.0 to 0.6.
  • the ions present in the solution may contain barium, nickel, gallium, and iron in the ratio of
  • the ions may contain barium, zinc, gallium or aluminum, and iron in the ratio of 1.0/2.0/3.0/13.0.
  • each of these ferrites is well known to those in the ferrite art and is described, e.g., in the aforementioned Von Aulock book.
  • the ions described above are preferably available in solution 509 in water-soluble form, such as, e.g., in the form of water-soluble salts.
  • water-soluble salts such as, e.g., in the form of water-soluble salts.
  • Other anions which form soluble salts with the cation(s) also may be used.
  • salts soluble in solvents other than water include nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, and the like.
  • solvents include nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, and the like.
  • suitable solvents see, e.g., J. A. Riddick et al., "Organic Solvents, Techniques of Chemistry," Volume II, 3rd edition (Wiley-Interscience, New York, N. Y., 1970).
  • each of the cations is present in the form of one or more of its oxides.
  • nickel oxide in hydrochloric acid, thereby forming a chloride may be readily apparent to those skilled in the art.
  • reagent grade materials In general, one may use commercially available reagent grade materials. Thus, by way of illustration and not limitation, one may use the following reagents available in the 1988-1989 Aldrich catalog (Aldrich Chemical Company, Inc., Milwaukee, Wis.): barium chloride, catalog number 31,866- 3; barium nitrate, catalog number 32,806-5; barium sulfate, catalog number 20,276-2; strontium chloride hexhydrate, catalog number 20,466- 3; strontium nitrate, catalog number 20,449-8; yttrium chloride, catalog number 29,826-3; yttrium nitrate tetrahydrate, catalog number 21,723-9; yttrium sulfate octahydrate, catalog number 20,493-5.
  • any of the desired reagents also may be obtained from the 1989-1990 AESAR catalog (Johnson Matthey/AESAR Group, Seabrook, N.H.), the 1990/1991 Alfa catalog (Johnson Matthey/Alfa Products, Ward Hill, Ma.), the Fisher 88 catalog (Fisher Scientific, Pittsburgh, Pa.), and the like.
  • AESAR catalog Johnson Matthey/AESAR Group, Seabrook, N.H.
  • the 1990/1991 Alfa catalog Johnson Matthey/Alfa Products, Ward Hill, Ma.
  • the Fisher 88 catalog Fisher 88 catalog
  • the metals present in the desired ferrite material are present in solution 509 in the desired stoichiometry, it does not matter whether they are present in the form of a salt, an oxide, or in another form.
  • the solution contains either the salts of such metals, or their oxides.
  • the solution 509 of the compounds of such metals preferably will be at a concentration of from about 0.01 to about 1,000 grams of said reagent compounds per liter of the resultant solution.
  • the term liter refers to 1,000 cubic centimeters.
  • solution 509 have a concentration of from about 1 to about 300 grams per liter and, preferably, from about 25 to about 170 grams per liter. It is even more preferred that the concentration of said solution 9 be from about 100 to about 160 grams per liter. In an even more preferred embodiment, the concentration of said solution 509 is from about 140 to about 160 grams per liter.
  • aqueous solutions of nickel nitrate, and iron nitrate with purities of at least 99.9 percent are mixed in the molar ratio of 1 :2 and then dissolved in distilled water to form a solution with a concentration of 150 grams per liter.
  • aqueous solutions of nickel nitrate, zinc nitrate, and iron nitrate with purities of at least 99.9 percent are mixed in the molar ratio of 0.5:0.5:2 and then dissolved in distilled water to form a solution with a concentration of 150 grams per liter.
  • aqueous solutions of zinc nitrate, and iron nitrate with purities of at least 99.9 percent are mixed in the molar ratio of 1 :2 and then dissolved in distilled water to form a solution with a concentration of 150 grams per liter.
  • aqueous solutions of nickel chloride, and iron chloride with purities of at least 99.9 percent are mixed in the molar ratio of 1:2 and then dissolved in distilled water to form a solution with a concentration of 150 grams per liter.
  • aqueous solutions of nickel chloride, zinc chloride, and iron chloride with purities of at least 99.9 percent are mixed in the molar ratio of 0.5:0.5:2 and then dissolved in distilled water to form a solution with a concentration of 150 grams per liter.
  • aqueous solutions of zinc chloride, and iron chloride with purities of at least 99.9 percent are mixed in the molar ratio of 1:2 and then dissolved in distilled water to form a solution with a concentration of 150 grams per liter.
  • mixtures of chlorides and nitrides may be used.
  • the solution is comprised of both iron chloride and nickel nitrate in the molar ratio of 2.0/1.0.
  • the solution 509 in misting chamber 511 is preferably caused to form into an aerosol, such as a mist.
  • aerosol refers to a suspension of ultramicroscopic solid or liquid particles in air or gas, such as smoke, fog, or mist. See, e.g., page 15 of "A dictionary of mining, mineral, and related terms," edited by Paul W. Thrush (U.S. Department of the Interior, Bureau of Mines, 1968), the disclosure of which is hereby incorporated by reference into this specification.
  • mist refers to gas-suspended liquid particles which have diameters less than 10 microns.
  • the aerosol/mist consisting of gas-suspended liquid particles with diameters less than 10 microns may be produced from solution 509 by any conventional means that causes sufficient mechanical disturbance of said solution. Thus, one may use mechanical vibration.
  • ultrasonic means are used to mist solution 9. As is known to those skilled in the art, by varying the means used to cause such mechanical disturbance, one can also vary the size of the mist particles produced.
  • ultrasonic sound waves may be used to mechanically disturb solutions and cause them to mist.
  • the ultrasonic nebulizer sold by the DeVilbiss Health Care, Inc. of Somerset, Pennsylvania; see, e.g., the "Instruction Manual” for the "Ultra-Neb 99 Ultrasonic Nebulizer, publication A-850-C (published by DeVilbiss, Somerset, Pa., 1989).
  • the oscillators of ultrasonic nebulizer 513 are shown contacting an exterior surface of misting chamber 511.
  • the ultrasonic waves produced by the oscillators are transmitted via the walls of the misting chamber 511 and effect the misting of solution 509.
  • the oscillators of ultrasonic nebulizer 513 are in direct contact with solution 509.
  • the ultrasonic power used with such machine is in excess of one watt and, more preferably, in excess of 10 watts. In one embodiment, the power used with such machine exceeds about 50 watts.
  • the time solution 509 is being caused to mist it is preferably contacted with carrier gas to apply pressure to the solution and mist. It is preferred that a sufficient amount of carrier gas be introduced into the system at a sufficiently high flow rate so that pressure on the system is in excess of atmospheric pressure.
  • the flow rate of the carrier gas was from about 100 to about 150 milliliters per minute.
  • the carrier gas 515 is introduced via feeding line 517 at a rate sufficient to cause solution 509 to mist at a rate of from about 0.5 to about 20 milliliters per minute. In one embodiment, the misting rate of solution 9 is from about 1.0 to about 3.0 milliliters per minute.
  • carrier gas 515 any gas that facilitates the formation of plasma may be used as carrier gas 515.
  • carrier gas 515 may be any gas that facilitates the formation of plasma.
  • the carrier gas used be a compressed gas under a pressure in excess 760 millimeters of mercury. In this embodiment, the use of the compressed gas facilitates the movement of the mist from the misting chamber 511 to the plasma region 521.
  • the misting container 511 may be any reaction chamber conventionally used by those skilled in the art and preferably is constructed out of such acid-resistant materials such as glass, plastic, and the like.
  • the mist from misting chamber 511 is fed via misting outlet line 519 into the plasma region 521 of plasma reactor 525.
  • the mist is mixed with plasma generated by plasma gas 527 and subjected to radio frequency radiation provided by a radio-frequency coil 529.
  • the plasma reactor 525 provides energy to fo ⁇ n plasma and to cause the plasma to react with the mist. Any of the plasmas reactors well known to those skilled in the art may be used as plasma reactor 525. Some of these plasma reactors are described in J. Mort et al.'s “Plasma Deposited Thin Films” (CRC Press Inc., Boca Raton, FIa., 1986); in “Methods of Experimental Physics,” Volume 9- Parts A and B, Plasma Physics (Academic Press, New York, 1970/1971); and in N. H. Burlingame's "Glow Discharge Nitriding of Oxides," Ph.D. thesis (Alfred University, Alfred, N.Y., 1985), available from University Microfilm International, Ann Arbor, Mich.
  • the plasma reactor 525 is a "model 56 torch" available from the TAFA Inc. of Concord, N.H. It is preferably operated at a frequency of about 4 megahertz and an input power of 30 kilowatts.
  • the plasma gas used is a mixture of argon and oxygen.
  • the plasma gas is a mixture of nitrogen and oxygen.
  • the plasma gas is pure argon or pure nitrogen.
  • the plasma gas is pure argon or pure nitrogen
  • the concentration of oxygen in the mixture preferably is from about 1 to about 40 volume percent and, more preferably, from about 15 to about 25 volume percent.
  • the flow rates of each gas in the mixture should be adjusted to obtain the desired gas concentrations.
  • the argon flow rate is 15 liters per minute
  • the oxygen flow rate is 40 liters per minute.
  • auxiliary oxygen 533 is fed into the top of reactor 25, between the plasma region 521 and the flame region 540, via lines 536 and 538.
  • the auxiliary oxygen is not involved in the formation of plasma but is involved in the enhancement of the oxidation of the ferrite material.
  • Radio frequency energy is applied to the reagents in the plasma reactor 525, and it causes vaporization of the mist.
  • the energy is applied at a frequency of from about 100 to about 30,000 kilohertz.
  • the radio frequency used is from about 1 to 20 megahertz. In another embodiment, the radio frequency used is from about 3 to about 5 megahertz.
  • radio frequency alternating currents may be produced by conventional radio frequency generators.
  • said TAPA Inc. "model 56 torch” may be attached to a radio frequency generator rated for operation at 35 kilowatts which manufactured by Lepel Company (a division of TAFA Inc.) and which generates an alternating current with a frequency of 4 megaherz at a power input of 30 kilowatts.
  • Lepel Company a division of TAFA Inc.
  • an induction coil driven at 2.5-5.0 megahertz that is sold as the "PLASMOC 2" by ENI Power Systems, Inc. of Rochester, New York.
  • the plasma vapor 523 fo ⁇ ned in plasma reactor 525 is allowed to exit via the aperture 542 and can be visualized in the flame region 540. In this region, the plasma contacts air that is at a lower temperature than the plasma region 521 , and a flame is visible.
  • a theoretical model of the plasma/flame is presented on pages 88 et seq. of said McPherson thesis.
  • vapor 544 present in flame region 540 is propelled upward towards substrate 546.
  • Any material onto which vapor 544 will condense may be used as a substrate.
  • substrate 46 consists essentially of a magnesium oxide material such as single crystal magnesium oxide, polycrystalline magnesium oxide, and the like.
  • the substrate 546 consists essentially of zirconia such as, e.g., yttrium stabilized cubic zirconia.
  • the substrate 546 consists essentially of a material selected from the group consisting of strontium titanate, stainless steel, alumina, sapphire, and the like.
  • the aforementioned listing of substrates is merely meant to be illustrative, and it will be apparent that many other substrates may be used. Thus, by way of illustration, one may use any of the substrates mentioned in M. Sayer's “Ceramic Thin Films . . . " article, supra. Thus, for example, in one embodiment it is preferred to use one or more of the substrates described on page 286 of "Superconducting Devices," edited by S. T. Ruggiero et al. (Academic Press, Inc., Boston, 1990).
  • the substrate may be of substantially any size or shape, and it may be stationary or movable. Because of the speed of the coating process, the substrate 546 may be moved across the aperture 542 and have any or all of its surface be coated.
  • the substrate 546 and the coating 548 are not drawn to scale but have been enlarged to the sake of ease of representation.
  • the substrate 546 may be at ambient temperature. Alternatively, one may use additional heating means to heat the substrate prior to, during, or after deposition of the coating.
  • a heater (not shown) is used to heat the substrate to a temperature of from about 100 to about 800 degrees centigrade.
  • temperature sensing means may be used to sense the temperature of the substrate and, by feedback means (not shown), adjust the output of the heater (not shown).
  • feedback means may be used to adjust the output of the heater (not shown).
  • optical pyrometry measurement means may be used to measure the temperature near the substrate.
  • a shutter (not shown) is used to selectively interrupt the flow of vapor 544 to substrate 546. This shutter, when used, should be used prior to the time the flame region has become stable; and the vapor should preferably not be allowed to impinge upon the substrate prior to such time.
  • the substrate 546 may be moved in a plane that is substantially parallel to the top of plasma chamber 525. Alternatively, or additionally, it may be moved in a plane that is substantially perpendicular to the top of plasma chamber 525. In one embodiment, the substrate 46 is moved stepwise along a predetermined path to coat the substrate only at certain predetermined areas.
  • rotary substrate motion is utilized to expose as much of the surface of a complex-shaped article to the coating.
  • This rotary substrate motion may be effectuated by conventional means. See, e.g., "Physical Vapor Deposition,” edited by Russell J. Hill (Temescal Division of The BOC Group, Inc., Berkeley, Calif., 1986).
  • the process of this embodiment of the invention allows one to coat an article at a deposition rate of from about 0.01 to about 10 microns per minute and, preferably, from about 0.1 to about 1.0 microns per minute, with a substrate with an exposed surface of 35 square centimeters.
  • a deposition rate of from about 0.01 to about 10 microns per minute and, preferably, from about 0.1 to about 1.0 microns per minute, with a substrate with an exposed surface of 35 square centimeters.
  • the film thickness can be monitored in situ, while the vapor is being deposited onto the substrate.
  • an IC-6000 thin film thickness monitor also referred to as "deposition controller” manufactured by Leybold Inficon Inc. of East Syracuse, N.Y.
  • the deposit formed on the substrate may be measured after the deposition by standard pro ⁇ lometry techniques.
  • a DEKTAK Surface Profiler model number 900051 (available from Sloan Technology Corporation, Santa Barbara, California).
  • at least about 80 volume percent of the particles in the as-deposited film are smaller than about 1 micron. It is preferred that at least about 90 percent of such particles are smaller than 1 micron. Because of this fine grain size, the surface of the film is relatively smooth.
  • the as-deposited film is post-annealed. It is preferred that the generation of the vapor in plasma rector 525 be conducted under substantially atmospheric pressure conditions.
  • substantially atmospheric refers to a pressure of at least about 600 millimeters of mercury and, preferably, from about 600 to about 1,000 millimeters of mercury. It is preferred that the vapor generation occur at about atmospheric pressure.
  • atmospheric pressure at sea level is 760 millimeters of mercury.
  • the process of this invention may be used to produce coatings on a flexible substrate such as, e.g., stainless steel strips, silver strips, gold strips, copper strips, aluminum strips, and the like. One may deposit the coating directly onto such a strip. Alternatively, one may first deposit one or more buffer layers onto the strip(s). In other embodiments, the process of this invention may be used to produce coatings on a rigid or flexible cylindrical substrate, such as a tube, a rod, or a sleeve.
  • the coating 548 is being deposited onto the substrate 546, and as it is undergoing solidification thereon, it is preferably subjected to a magnetic field produced by magnetic field generator 550.
  • the magnetic field produced by the magnetic field generator 550 have a field strength of from about 2 Gauss to about 40 Tesla.
  • the term "substantially aligned” means that the inductance of the device being formed by the deposited nano-sized particles is at least 90 percent of its maximum inductance. One may determine when such particles have been aligned by, e.g., measuring the inductance, the permeability, and/or the hysteresis loop of the deposited material.
  • the degree of alignment of the deposited particles is measured with an inductance meter.
  • a conventional conductance meter such as, e.g., the conductance meters disclosed in United States patents 4,779,462, 4,937,995, 5,728,814 (apparatus for determining and recording injection does in syringes using electrical inductance), 6,318,176, 5,014,012, 4,869,598, 4,258,315 (inductance meter), 4,045,728 (direct reading inductance meter), 6,252,923, 6,194,898, 6,006,023 (molecular sensing apparatus), 6,048,692 (sensors for electrically sensing binding events for supported molecular receptors), and the like.
  • a conventional conductance meter such as, e.g., the conductance meters disclosed in United States patents 4,779,462, 4,937,995, 5,728,814 (apparatus for determining and recording injection does in syringes using electrical inductance), 6,318,176, 5,014,012, 4,869,598, 4,258,315 (inductance
  • the inductance is preferably measured using an applied wave with a specified frequency. As the magnetic moments of the coated samples align, the inductance increases until a specified value; and it rises in accordance with a specified time constant in the measurement circuitry.
  • the deposited material is contacted with the magnetic field until the inductance of the deposited material is at least about 90 percent of its maximum value under the measurement circuitry. At this time, the magnetic particles in the deposited material have been aligned to at least about 90 percent of the maximum extent possible for maximizing the inductance of the sample.
  • a metal rod with a diameter of 1 micron and a length of 1 millimeter when uncoated with magnetic nano-sized particles, might have an inductance of about 1 nanohenry.
  • this metal rod is coated with, e.g., nano-sized ferrites, then the inductance of the coated rod might be 5 nanohenries or more.
  • the inductance might increase to 50 nanohenries, or more.
  • the inductance of the coated article will vary, e.g., with the shape of the article and also with the frequency of the applied electromagnetic field.
  • the magnetic field is 1.8 Tesla or less.
  • the magnetic field can be applied with, e.g., electromagnets disposed around a coated substrate.
  • no magnetic field is applied to the deposited coating while it is being solidified.
  • the magnetic field 552 is preferably delivered to the coating 548 in a direction that is substantially parallel to the surface 556 of the substrate 546.
  • the magnetic field 558 is delivered in a direction that is substantially perpendicular to the surface 556.
  • the magnetic field 560 is delivered in a direction that is angularly disposed vis-a-vis surface 556 and may form, e.g., an obtuse angle (as in the case of field 62). As will be apparent, combinations of these magnetic fields may be used.
  • Figure 9 is a flow diagram of another process that may be used to make the nanomagnetic compositions of this invention.
  • nano-sized ferromagnetic material(s) with a particle size less than about 100 nanometers, is preferably charged via line 660 to mixer 63. It is preferred to charge a sufficient amount of such nano-sized material(s) so that at least about 10 weight percent of the mixture formed in mixer 663 is comprised of such nano-sized material. In one embodiment, at least about 40 weight percent of such mixture in mixer 663 is comprised of such nano-sized material. In another embodiment, at least about 50 weight percent of such mixture in mixer 663 is comprised of such nano-sized material.
  • one or more binder materials are charged via line 664 to mixer 662.
  • the binder used is a ceramic binder. These ceramic binders are well known. Reference may be had, e.g., to pages 172-197 of James S. Reed's "Principles of Ceramic Processing," Second Edition (John Wiley & Sons, Inc., New York, New York, 1995).
  • the binder may be a clay binder (such as fine kaolin, ball clay, and bentonite), an organic colloidal particle binder (such as microcrystalline cellulose), a molecular organic binder (such as natural gums, polyscaccharides, lignin extracts, refined alginate, cellulose ethers, polyvinyl alcohol, polyvinylbutyral, polymethyl methacrylate, polyethylene glycol, paraffin, and the like.), etc.
  • a clay binder such as fine kaolin, ball clay, and bentonite
  • an organic colloidal particle binder such as microcrystalline cellulose
  • a molecular organic binder such as natural gums, polyscaccharides, lignin extracts, refined alginate, cellulose ethers, polyvinyl alcohol, polyvinylbutyral, polymethyl methacrylate, polyethylene glycol, paraffin, and the like.
  • the binder is a synthetic polymeric or inorganic composition.
  • the binder may be acrylonitrile-butadiene-styrene (see pages 5-6), an acetal resin (see pages 6- 7), an acrylic resin (see pages 10-12), an adhesive composition (see pages 14-18), an alkyd resin (see page 27-28), an allyl plastic (see pages 31-32), an amorphous metal (see pages 53-54), a biocompatible material (see pages 95-98), boron carbide (see page 106), boron nitride (see page 107), camphor (see page 135), one or more carbohydrates (see pages 138-140), carbon steel (see pages 146-151), casein plastic (see page 157), cast iron (see pages 159-164), cast steel (see pages 166-168), cellulose (see
  • lubricating grease see pages 488-492
  • magnetic materials see pages 505-509
  • melamine resin see pages 5210-521
  • metallic materials see pages 522-524
  • nylon see pages 567-569
  • olefin copolymers see pages 574-576
  • phenol-formaldehyde resin see pages 615-617
  • plastics see pages 637-639
  • polyarylates see pages 647-648
  • polycarbonate resins see pages 648)
  • polyester thermoplastic resins see pages 648-650
  • polyester thermosetting resins see pages 650-651
  • polyethylenes see pages 651- 654)
  • polyphenylene oxide see pages 644-655
  • polypropylene plastics see pages 655-656
  • polystyrenes see pages 656-658
  • proteins see pages 666-670
  • refractories see pages 691-697
  • resins see pages 697-698
  • rubber see pages 706-708
  • silicones see pages 747-749
  • starch see pages
  • the mixture within mixer 63 is preferably stirred until a substantially homogeneous mixture is formed. Thereafter, it may be discharged via line 665 to former 66.
  • nanomagnetic fluid further comprises a polymer binder, thereby forming a nanomagnetic paint.
  • the nanomagnetic paint is formulated without abrasive particles of cerium dioxide.
  • the nanomagnetic fluid further comprises a polymer binder, and aluminum nitride is substituted for cerium dioxide.
  • iron carbonyl particles or other ferromagnetic particles of the paint may be further reduced to a size on the order of 100 nanometers or less, and/or thoroughly mixed with a binder polymer and/or a liquid solvent by the use of a ball mill, a sand mill, a paint shaker holding a vessel containing the paint components and hard steel or ceramic beads; a homogenizer (such as the Model Ytron Z made by the Ytron Quadro Corporation of Chesham, United Kingdom, or the Microfluidics M700 made by the MFIC Corporation of Newton, Ma.), a powder dispersing mixer (such as the Ytron Zyclon mixer, or the Ytron Xyclon mixer, or the Ytron PID mixer by the Ytron Quadro Corporation); a grinding mill (such as the Model FlO Mill by the Ytron Quadro Corporation); high shear mixers (such as the Ytron Y mixer by the Ytron Quadro Corporation), the Silverson Laboratory
  • a homogenizer such
  • the former 666 is preferably equipped with an input line 68 and an exhaust line 670 so that the atmosphere within the former can be controlled.
  • One may utilize an ambient atmosphere, an inert atmosphere, pure nitrogen, pure oxygen, mixtures of various gases, and the like.
  • lines 668 and 670 may be used to afford subatmospheric pressure, atmospheric pressure, or superatomspheric pressure within former 666.
  • former 666 is also preferably comprised of an electromagnetic coil 672 that, in response from signals from controller 674, can control the extent to which, if any, a magnetic field is applied to the mixture within the former 666 (and also within the mold 667 and/or the spinnerette 669).
  • the controller 674 is also adapted to control the temperature within the former 666 by means of heating/cooling assembly.
  • a heater (not shown) is used to heat the substrate 546 to a temperature of from about 100 to about 800 degrees centigrade.
  • temperature sensing means may be used to sense the temperature of the substrate 546 and, by feedback means (not shown), adjust the output of the heater (not shown).
  • optical pyrometry measurement means may be used to measure the temperature near the substrate.
  • a shutter (not shown) is used to selectively interrupt the flow of vapor 544 to substrate 546.
  • This shutter when used, should be used prior to the time the flame region has become stable; and the vapor should preferably not be allowed to impinge upon the substrate prior to such time.
  • the substrate 546 may be moved in a plane that is substantially parallel to the top of plasma chamber 525. Alternatively, or additionally, it may be moved in a plane that is substantially perpendicular to the top of plasma chamber 525. In one embodiment, the substrate 546 is moved stepwise along a predetermined path to coat the substrate only at certain predetermined areas.
  • rotary substrate motion is utilized to expose as much of the surface of a complex-shaped article to the coating.
  • This rotary substrate motion may be effectuated by conventional means. See, e.g., "Physical Vapor Deposition,” edited by Russell J. Hill (Temescal Division of The BOC Group, Inc., Berkeley, Calif., 1986).
  • the process of this embodiment of the invention allows one to coat an article at a deposition rate of from about 0.01 to about 10 microns per minute and, preferably, from about 0.1 to about 1.0 microns per minute, with a substrate with an exposed surface of 35 square centimeters.
  • a deposition rate of from about 0.01 to about 10 microns per minute and, preferably, from about 0.1 to about 1.0 microns per minute, with a substrate with an exposed surface of 35 square centimeters.
  • the film thickness can be monitored in situ, while the vapor is being deposited onto the substrate.
  • an IC-6000 thin film thickness monitor also referred to as "deposition controller” manufactured by Leybold Inf ⁇ con Inc. of East Syracuse, N. Y.
  • the deposit formed on the substrate may be measured after the deposition by standard profilometry techniques.
  • a DEKTAK Surface Profiler model number 900051 (available from Sloan Technology Corporation, Santa Barbara, California).
  • At least about 80 volume percent of the particles in the as-deposited film are smaller than about 1 micron. It is preferred that at least about 90 percent of such particles are smaller than 1 micron. Because of this fine grain size, the surface of the film is relatively smooth.
  • the as-deposited film is post-annealed.
  • the generation of the vapor in plasma rector 525 be conducted under substantially atmospheric pressure conditions.
  • substantially atmospheric refers to a pressure of at least about 600 millimeters of mercury and, preferably, from about 600 to about 1,000 millimeters of mercury. It is preferred that the vapor generation occur at about atmospheric pressure.
  • atmospheric pressure at sea level is 760 millimeters of mercury.
  • the process of this invention may be used to produce coatings on a flexible substrate such as, e.g., stainless steel strips, silver strips, gold strips, copper strips, aluminum strips, and the like. One may deposit the coating directly onto such a strip. Alternatively, one may first deposit one or more buffer layers onto the strip(s). In other embodiments, the process of this invention may be used to produce coatings on a rigid or flexible cylindrical substrate, such as a tube, a rod, or a sleeve.
  • the coating 548 is being deposited onto the substrate 546, and as it is undergoing solidification thereon, it is preferably subjected to a magnetic field produced by magnetic field generator 550.
  • the magnetic field produced by the magnetic field generator 550 have a field strength of from about 2 Gauss to about 40 Tesla. Substrates with composite coatings disposed thereon
  • Figures 10-14 are sectional views of coated substrates wherein the coatings comprise two more discrete layers of different materials.
  • Figure 10 is a sectional view one preferred coated assembly 731 that is comprised of a conductor 733 and, disposed around such conductor 733, a layer of nanomagnetic material 735,
  • the layer 735 of nanomagnetic material preferably has a thickness of at least 150 nanometers and, more preferably, at least about 200 nanometers. In one embodiment, the thickness of layer 735 is from about 500 to about 1,000 nanometers.
  • Figure 11 is a schematic sectional view of a magnetically shielded assembly 739 that is similar to assembly 731 but differs therefrom in that a layer 741 of nanoelectrical material is disposed around layer 735.
  • the layer of nanoelectrical material 741 preferably has a thickness of from about 0.5 to about 2 microns.
  • the nanoelectrical material comprising layer 741 has a resistivity of from about 1 to about 100 microohm-centimeters.
  • WO9820719 in which reference is made to United States patent 4,963,291; each of these patents and patent applications is hereby incorporated by reference into this specification.
  • electromagnetic shielding resins comprised of electroconductive particles, such as iron, aluminurn.copper, silver and steel in sizes ranging from 0.5 to.50 microns.
  • electroconductive particles such as iron, aluminurn.copper, silver and steel in sizes ranging from 0.5 to.50 microns.
  • the nanoelectrical particles used in this aspect of the invention preferably have a particle size within the range of from about 1 to about 100 microns, and a resistivity of from about 1.6 to about 100 microohm-centimeters.
  • such nanoelectrical particles comprise a mixture of iron and aluminum.
  • such nanoelectrical particles consist essentially of a mixture of iron and aluminum.
  • At least 9 moles of aluminum are present for each mole of iron.
  • at least about 9.5 moles of aluminum are present for each mole of iron.
  • at least 9.9 moles of aluminum are present for each mole of iron.
  • the layer 741 of nanoelectrical material has a thermal conductivity of from about 1 to about 4 watts/centimeter-degree Kelvin.
  • the nanoelectrical material and the nanomagnetic material may be produced by simultaneously depositing the nanoelectrical particles and the nanomagnetic particles with, e.g., sputtering technology such as, e.g., the sputtering technology described elsewhere in this specification.
  • Figure 12 is a sectional schematic view of a magnetically shielded assembly 743 that differs from assembly 731 in that it contains a layer 745 of nanothermal material disposed around the layer 735 of nanomagnetic material.
  • the layer 745 of nanothermal material preferably has a thickness of less than 2 microns and a thermal conductivity of at least about 150 watts/meter-degree Kelvin and, more preferably, at least about 200 watts/meter-degree Kelvin. It is preferred that the resistivity of layer 745 be at least about 10 10 microohm-centimeters and, more preferably, at least about 10 12 microohm- centimeters. In one embodiment, the resistivity of layer 745 is at least about 10 13 microohm centimeters.
  • the nanothermal layer is comprised of AlN.
  • the thickness 747 of all of the layers of material coated onto the conductor 733 is preferably less than about 20 microns.
  • FIG. 13 a sectional view of an assembly 749 is depicted that contains, disposed around conductor 733, layers of nanomagnetic material 735, nanoelectrical material 741 , nanomagnetic material 735, and nanoelectrical material 741.
  • a sectional view of an assembly 751 is depicted that contains, disposed around conductor 733, a layer 735 of nanomagnetic material, a layer 741 of nanoelectrical material, a layer 735 of nanomagnetic material, a layer 745 of nanothermal material, and a layer 735 of nanomagnetic material.
  • antithrombogenic material that is biocompatible with the living organism in which the assembly 751 is preferably disposed.
  • the coatings 735, and/or 741, and/or 745, and/or 753, are disposed around a conductor 733.
  • the conductor so coated is preferably part of medical device, preferably an implanted medical device (such as, e.g., a pacemaker).
  • an implanted medical device such as, e.g., a pacemaker.
  • the actual medical device itself is coated.
  • nanoelectrical material with an average particle size of less than 100 nanometers, a surface area to volume ratio of from about 0.1 to about 0.05 1/nanometer, and a relative dielectric constant of less than about 1.5.
  • the nanoelectrical particles of this aspect of the invention have an average particle size of less than about 100 nanometers. In one embodiment, such particles have an average particle size of less than about 50 nanometers. In yet another embodiment, such particles have an average particle size of less than about 10 nanometers.
  • the nanoelectrical particles of this invention have surface area to volume ratio of from about
  • the collection of particles preferably has a relative dielectric constant of less than about 1.5. In one embodiment, such relative dielectric constant is less than about 1.2. In one embodiment, the nanoelectrical particles of this invention are preferably comprised of aluminum, magnesium, and nitrogen atoms. This embodiment is illustrated in Figure 15.
  • Figure 15 illustrates a phase diagram 800 comprised of moieties E, F, and G.
  • Moiety E is preferably selected from the group consisting of aluminum, copper, gold, silver, and mixtures thereof. It is preferred that the moiety E have a resistivity of from about 2 to about 100 microohm-centimeters. In one preferred embodiment, moiety E is aluminum with a resistivity of about 2.824 microohm- centimeters. As will apparent, other materials with resistivities within the desired range also may be used.
  • moiety G is selected from the group consisting of nitrogen, oxygen, and mixtures thereof.
  • C is nitrogen
  • A is aluminum
  • aluminum nitride is present as a phase in the system.
  • moiety F is preferably a dopant that is present in a minor amount in the preferred aluminum nitride. In general, less than about 50 percent (by weight) of the F moiety is present, by total weight of the doped aluminum nitride. In one aspect of this embodiment, less than about 10 weight percent of the F moiety is present, by total weight of the doped aluminum nitride.
  • the F moiety may be, e.g., magnesium, zinc, tin, indium, gallium, niobium, zirconium, strontium, lanthanum, tungsten, mixtures thereof, and the like.
  • F is selected from the group consisting of magnesium, zinc, tin, and indium.
  • the F moiety is magnesium. Referring again to Figure 15, and when E is aluminum, F is magnesium, and G is nitrogen, it will be seen that regions 802 and 804 correspond to materials which have a low relative dielectric constant (less than about 1.5), and a high relative dielectric constant (greater than about 1.5), respectively, A preferred drug delivery assembly In this section of the specification, applicants will describe a medical device with improved drug delivery capabilities.
  • This medical device is similar to the medical device disclosed in published United States patent application 2004/0030379, the entire disclosure of which is hereby incorporated by reference into this specification. However, because applicants use an improved form of magnetic particles in the device, applicants device provides superior magnetic performance and, additionally, superior MRI imageability.
  • the medical system described in this section of the specification is preferably a stent 1010 (see Figure 16) comprised of wire like struts 1020 (also see Figure 16).
  • the system of the present invention comprises (1) a medical device having a coating containing a biologically active material, and (2) a source of electromagnetic energy or a source for generating an electromagnetic field.
  • the present invention can facilitate and/or modulate the delivery of the biologically active material from the medical device.
  • the release of the biologically active material from the medical device is facilitated or modulated by the electromagnetic energy source or field.
  • the practitioner may implant the coated medical device using regular procedures.
  • the coating of the medical device of the present invention further comprises particles comprising a magnetic material, i.e., magnetic particles
  • Figure 17 shows a cross-sectional view of a coated strut 1020 of the stent.
  • the coated strut 1020 comprises a strut 1025 having a surface 1030.
  • the coated strut 1020 has a composite coating that comprises a first coating layer 1040 that contains a biologically active material 1045; in one embodiment, this first coating layer 1040 also contains polymeric material.
  • a second coating layer 1050 comprising nanomagnetic particles
  • This second coating layer 1055 is disposed over the first coating layer 1040.
  • This second coating layer 1055 in one embodiment, also includes polymeric material.
  • a third coating layer or sealing layer 1060 is disposed on top of the second coating layer 1050.
  • Figure 18 is similar to Figure 2B of United States published patent application 2004/0030379; and it illustrates the effect of exposing a patient (not shown), who is implanted with a stent having struts 1020 shown in Figure 17, to an electromagnetic energy source or field 1090.
  • an electromagnetic energy source or field 1090 When such a field 1090 is applied, the magnetic particles 1055 move out of the second coating layer 1050 in the direction of upward arrow 1 110. This movement disrupts the sealing layer 1160 and forms channels 1100 in such sealing layer 1060.
  • the size of the channels 1100 formed generally depends on the size of the magnetic particles 1055 used.
  • the biologically active material 1045 can then be released from the coating through the disrupted sealing layer 1060 into the surrounding tissue 1 120.
  • the duration of exposure to the field and the strength of the electromagnetic field 1090 determine the rate of delivery of the biologically active material 1045.
  • Figure 19 illustrates another coated stent 1003; this Figure is similar to Fugure 3A of United States published patent application 2004/0030379.
  • the coated strut 1021 contains a coating comprised of a first coating layer 1040 comprising a biologically active material 1045 and preferably a polymeric material disposed over the surface 1030 of the strut 1025.
  • a second coating layer or sealing layer 1070 comprising magnetic particles 1055 and a polymeric material is disposed on top of the first coating layer 1040.
  • Figure 20 illustrates the effect of exposing a patient (not shown) who is implanted with a stent having struts 1021 shown in Figure 19 to an electromagnetic field 1090; this Figure is similar to Figure 3B of United States published patent application 2004/0030379.
  • the magnetic particles 1055 move through the sealing layer 1070 as shown by the upward arrow 1110, and they create channels 1100 in the sealing layer 1070.
  • the biologically active material 1045 in the underlying first coating layer 1040 is allowed to travel through the channels 1 100 in the sealing layer 1070 and be released to the surrounding tissue 1120. Since the biologically active material 1045 is in a separate first coating layer 1040 and must migrate through the second coating layer or the sealing layer 1070, the release of the biologically active material 1045 is controlled after formation of the channels 1100.
  • Figure 21 is similar to Figure 4A of published United States patent application 2004/0030379, and it shows another embodiment of a coated stent strut 1023.
  • the coating comprises a coating layer 1080 comprising a biologically active material 1045, magnetic particles 1055, and a polymeric material.
  • Figure 22 which is similar to Figure 4B of published United States patent application
  • the medical device 1001 of the present invention may be a stent having struts coated with a coating comprising more than one coating layer containing a magnetic material.
  • Figure 23 illustrates such a coated strut 1027.
  • the coating comprises a first coating layer 1040 containing a polymeric material and a biologically active material 1045 which is disposed on the surface 1030 of a strut 1025.
  • a second coating layer 1050 comprising a polymeric material and magnetic particles 1055 is disposed over the first coating layer 1040.
  • a third coating layer 1044 comprising a polymeric material and a biologically active material 1045 is disposed over the second coating layer 1050.
  • a fourth coating layer 1054 comprising a polymeric material and magnetic particles 1055 is disposed over this third layer 1044.
  • a sealing layer 1060 of a polymeric material is disposed over the fourth coating layer 1054.
  • the permeability of the coating layers may be different from layer to layer so that the release of the biologically active material from each layer can differ.
  • the magnetic susceptibility of the magnetic particles may differ from layer to layer.
  • the magnetic susceptibility may be varied using different concentrations or percentages of magnetic particles in the coating layers.
  • the magnetic susceptibility of the magnetic particles may also be varied by changing the size and type of material used for the magnetic particles.
  • different excitation intensity and/or frequency are required to activate the magnetic particles in each layer.
  • the nanomagnetic particles preferably used in the embodiment depicted in Figure 23 may be coated with a biologically active material and then incorporated into a coating for the medical device.
  • the biologically active material is a nucleic acid molecule.
  • the nucleic acid coated nanomagnetic magnetic particles may be formed by painting, dipping, or spraying the magnetic particles with a solution comprising the nucleic acid.
  • the nucleic acid molecules may adhere to the nanomagnetic particles via adsorption.
  • the nucleic acid molecules may be linked to the magnetic particles chemically, via linking agents, covalent bonds, or chemical groups that have affinity for charged molecules.
  • Application of an external electromagnetic field can cause the adhesion between the biologically active material and the magnetic particle to break, thereby allowing for release of the biologically active material.
  • the magnetic particles may be molded into or coated onto a non-metallic medical device, including a bio-absorb able medical device.
  • the magnetic properties of the preferred nanomagnetic particles allow the non-metallic implant to be extracorporally imaged, vibrated, or moved.
  • the nanomagnetic particles are painted, dipped or sprayed onto the outer surface of the device.
  • the naomagnetic particles may also be suspended in a curable coating, such as a UV curable epoxy, or they may be electrostatically sprayed onto the medical device and subsequently coated with a UV or heat curable polymeric material.
  • the movement of the magnetic particles that occurs when the patient implanted with the coated device is exposed to an external electromagnetic field releases mechanical energy into the surrounding tissue in which the medical device is implanted and triggers histamine production by.the surrounding tissues.
  • the histamine has a protective effect in preventing the formation of scar tissues in the vicinity at which the medical device is implanted.
  • the movement of the preferred nanomagnetic particles creates a sufficient amount of heat to kill cells by hyperthermia.
  • This embodiment is described elsewhere in this specification, wherein nanomagnetic particles with specified Curie temperatures that preferentially kill cancer cells when heated are described.
  • the application of the external electromagnetic field 9090 activates the biologically active material in the coating of the medical device.
  • a biologically active material that may be used in this embodiment may be a thermally sensitive substance that is coupled to nitric oxide, e.g., nitric oxide adducts, which prevent and/or treat adverse effects associated with use of a medical device in a patient, such as restenosis and damaged blood vessel surface.
  • the nitric oxide is attached to a carrier molecule and suspended in the polymer of the coating, but it is only biologically active after a bond breaks, thereby releasing the smaller nitric oxide molecule in the polymer and eluting into the surrounding tissue.
  • Typical nitric oxide adducts include, e.g., nitroglycerin, sodium nitroprusside, S- nitroso-proteins, S-nitroso-thiols, long carbon-chain lipophilic S-nitrosothiols, S-nitrosodithiols, iron- nitrosyl compounds, thionitrates, thionitrites, sydnonimines, furoxans, organic nitrates, and nitrosated amino acids, preferably mono- or poly-nitrosylated proteins, particularly polynitrosated albumin or polymers or aggregates thereof.
  • the albumin is preferably human or bovine, including humanized bovine serum albumin.
  • nitric oxide adducts are disclosed in U.S. Pat. No. 6,087,479 to Stamler et al., the entire disclosure of which is incorporated herein by reference into this specification.
  • the application of the electromagnetic field 1090 effects a chemical change in the polymer coating, thereby allowing for faster release of the biologically active material from the coating.
  • Another embodiment of the present invention is a system for delivering a biologically active material to a body of a patient that comprises a mechanical vibrational energy source and an insertable medical device comprising a coating containing the biologically active material.
  • the coating can optionally contain magnetic particles.
  • the biologically active material can be delivered to the patient on-demand or when the material is needed by the patient.
  • the patient is exposed to an extracorporal or external mechanical vibrational energy source.
  • the mechanical vibrational energy source includes various sources which cause vibration such as sonic or ultrasonic energy. Exposure to such energy source causes disruption in the coating that allows for the biologically active material to be released from the coating and delivered to body tissue.”
  • the biologically active material contained in the coating of the medical device is in a modified form.
  • the modified biologically active material has a chemical moiety bound to the biologically active material. The chemical bond between the moiety and the biologically active material is broken by the mechanical vibrational energy. Since the biologically active material is generally smaller than the modified biologically active material, it is more easily released from the coating. Examples of such modified biologically active materials include the nitric oxide adducts described above.”
  • the coating comprises at least a coating layer containing a polymeric material whose structural properties are changed by mechanical vibrational energy. Such change facilitates release of the biologically active material which is contained in the same coating layer or another coating layer.
  • Paragraphs 36, 37, 38, 39, 40, and 41 of published United States patent application 2004/0030379 are also applicable to the medical devices of this invention. They are presented below in their entireties.
  • the medical devices of .the present invention are insertable into the body of a patient. Namely, at least a portion of such medical devices may be temporarily inserted into or ' semi-permanently or permanently implanted in the body of a patient.
  • the medical devices of the present invention comprise a tubular portion which is insertable into the body of a patient.
  • the tubular portion of the medical device need not to be completely cylindrical.
  • the cross-section of the tubular portion can be any shape, such as rectangle, a triangle, etc., not just a circle.”
  • the medical devices suitable for the present invention include, but are not limited to, stents, surgical staples, catheters, such as central venous catheters and arterial catheters, guidewires, balloons, filters (e.g., vena cava filters), cannulas, cardiac pacemaker leads or lead tips, cardiac defibrillator leads or lead tips, implantable vascular access ports, stent grafts, vascular grafts or other grafts, interluminal paving system, intra-aortic balloon pumps, heart valves, cardiovascular sutures, total artificial hearts and ventricular assist pumps.”
  • stents surgical staples
  • catheters such as central venous catheters and arterial catheters, guidewires, balloons, filters (e.g., vena cava filters), cannulas, cardiac pacemaker leads or lead tips, cardiac defibrillator leads or lead tips, implantable vascular access ports, stent grafts, vascular grafts or other grafts, interluminal paving
  • Medical devices which are particularly suitable for the present invention include any kind of stent for medical purposes, which are known to the skilled artisan.
  • Suitable stents include, for example, vascular stents such as self-expanding stents and balloon expandable stents.
  • self- expanding stents useful in the present invention are illustrated in U.S. Pat. Nos. 4,655,771 and 4,954,126 issued to Wallsten and U.S. Pat. No. 5,061,275 issued to Wallsten et al.
  • Examples of appropriate balloon-expandable stents are shown in U.S. Pat. No. 4,733,665 issued to Palmaz, U.S. Pat. No. 4,800,882 issued to Gianturco, U.S. Pat. No. 4,886,062 issued to Wiktor and U.S. Pat. No. 5,449,373 issued to Pinchasik et al.
  • a bifurcated stent is also included among the medical devices suitable for the present
  • the medical devices suitable for the present invention may be fabricated from polymeric and/or metallic materials.
  • polymeric materials include polyurethane and its copolymers, silicone and its copolymers, ethylene vinyl-acetate, poly(ethylene terephthalate), thermoplastic elastomer, polyvinyl chloride, polyolephines, cellulosics, polyamides, polyesters, polysulfones, polytetrafluoroethylenes, acrylonitrile butadiene styrene copolymers, acrylics, polyactic acid, polyclycolic acid, polycaprolactone, polyacetal, poly(lactic acid), polylactic acid-polyethylene oxide copolymers, polycarbonate cellulose, collagen and chitins.
  • suitable metallic materials include metals and alloys based on titanium (e.g., nitinol, nickel titanium alloys, thermo- memory alloy materials), stainless steel, platinum, tantalum, nickel-chrome, certain cobalt alloys including cobalt-chromium-nickel alloys (e.g., Elgiloy® and Phynox®) and gold/platinum alloy.
  • Metallic materials also include clad composite filaments, such as those disclosed in WO 94/16646.” Paragraphs 42-47 of published United States patent application 2004/0030379 describes the magnetic particles used in the device of such application. In applicants' preferred device, the magnetic particles of such device are replaced with certain nanomagnetic particles described elsewhere in this specification These nanomangetic particles preferably have the properties described below.
  • the nanomagnetic particles are usually in to form of a coating a nanomagnetic material comprised of such particles.
  • An assembly comprised of a device, wherein said device comprises a substrate and, disposed over such substrate, nanomagnetic material and magetoresistive material, wherein the nanomagnetic material has a saturation magentization of from about 2 to about 3000 electromagnetic units per cubic centimeter.
  • the nanomagnetic particles generally have an average particle size of less than about 100 nanometers, wherein the average coherence length between adjacent nanomagnetic particles is less than 100 nanometers.
  • the nanomagnetic material has an average particle size of less than about 20 nanometers and a phase transition temperature of less than about 200 degrees Celsius.
  • the average particle size of such nanomagnetic particles is less than about 15 nanometers.
  • the nanomagentic material has a saturation magnetization of at least 2,000 electromagnetic units per cubic centimeter.
  • the nanomagnetic material has a saturation magnetization of at least 2,500 electromagnetic units per cubic centimeter.
  • the nanomagnetic, the particles of nanomagnetic material have a squareness of from about 0.05 to about 1.0.
  • the nanomagnetic, the particles of nanomagnetic material are at least triatomic, being comprised of a first distinct atom, a second distinct atom, and a third distinct atom.
  • the first distinct atom is an atom selected from the group consisting of atoms of actinium, americium, berkelium, californium, cerium, chromium, cobalt, curium, dysprosium, einsteinium, erbium, europium, fermium, gadolinium, holmium, iron, lanthanum, lawrencium, lutetium, manganese, mendelevium, nickel, neodymium, neptunium, nobelium, plutonium, praseodymium, promethium, protactinium, samarium, terbium, thorium, thulium, uranium, and ytterbium.
  • the distinct atom is an atom selected from the group consisting of
  • the particles of nanomagnetic material are comprised of atoms of cobalt and atoms of iron.
  • such first distinct atom is a radioactive cobalt atom.
  • the particles of nanomagnetic material are comprised of a said first distinct atom, said second distinct atom, said third distinct atom, and a fourth distinct atom.
  • the particles of nanomagnetic material are comprised of a fifth distinct atom.
  • such particles of nanomagnetic material have a sqareness of from about 0.1 to about 0.9.
  • such particles of nanomagnetic material have a squarenesss is from about 0.2 to about 0.8.
  • the nanomagnetic particles have an average size of less of less than about 3 nanometers.
  • the nanomagnetic particles have an average size of less than about 15 nanometers. In yet another embodiment, the nanomagnetic particles have an average size is less than about 11 nanometers. In yet another embodiment, the nanomagnetic particles have a phase transition temperature of less than 46 degrees Celsius. In yet another embodiment, the nanomagnetic particles have a a phase transition temperature of less than about 50 degrees Celsius.
  • the nanomagnetic material has a coercive force of from about 0.1 to about 10 Oersteds. In yet another embodiment, the nanomagnetic particles have a relative magnetic permeability of from about 1.5 to about 2,000.
  • the nanomagnetic particles have a saturation magnetization of at least 100 electromagnetic units per cubic centimeter. In one aspect of this embodiment, the particles of nanomagnetic material have a saturation magnetization of at least about 200 electromagnetic units (emu) per cubic centimeter. Ih yet another aspect of this embodiment, the particles of nanomagnetic material have a saturation magnetization of at least about 1,000 electromagnetic units per cubic centimeter.
  • the nanomagnetic particles have a coercive force of from about 0.01 to about 5,000 Oersteds. In one aspect of this embodiment, such particles of nanomagnetic material have a coercive force of from about 0.01 to about 3,000 Oersteds.
  • the nanomagnetic particles have a relative magnetic permeability of from about 1 to about 500,000. In one aspect of this embodiment, such particles have a relative magnetic permeability of from about 1.5 to about 260,000.
  • the nanomagnetic particles have a mass density of at least about 0.001 grams per cubic centimeter. In one aspect of this embodiment, such particles of nanomagnetic material have a mass density of at least about 1 gram per cubic centimeter. In another aspect of this embodiment, such particles of nanomagnetic material have a mass density of at least about 3 grams per cubic centimeter. In yet another aspect of this embodiment, such particles of nanomagnetic material have a mass density of at least about 4 grams per cubic centimeter. In yet another embodiment, the second distinct atom of such nanomagnetic particles has a relative magnetic permeability of about 1.0.
  • such second distinct atom is an atom selected from the group consisting of aluminum, antimony, barium, beryllium, boron, bismuth, calcium, gallium, germanium, gold, indium, lead, magnesium, palladium, platinum, silicon, silver, strontium, tantalum, tin, titanium, tungsten, yttrium, zirconium, magnesium, and zinc.
  • the nanomagnetic particles are comprised of a third distinct atom that is an atom selected from the group consisting of argon, bromine, carbon, chlorine, fluorine, helium, helium, hydrogen, iodine, krypton, oxygen, neon, nitrogen, phosphorus, sulfur, and xenon.
  • the third distinct atom is nitrogen.
  • the nanomagnetic particles are represented by the fo ⁇ nula AxByCz, wherein A is said first distinct atom, B is said second distinct atom, C is said third distinct atom, and x + y + z is equal to 1.
  • such nanomagnetic particles are comprised of atoms of oxygen.
  • the nanomagnetic particles are comprised of atoms of iro which optionally me be radioactive.
  • such nanomagnetic particles are comprised of atoms of cobalt which, optinally, may be radioactive.
  • the particles of nanomagnetic material are present in the form of a coating with a thickness of from about 400 to about 2000 nanometers.
  • the coating has a thickness of from about 600 to about 1200 nanometers.
  • the coating has a morphological density of at least about 98 percent, preferably at least about 99 percent, and more preferably at least about 99.5 percent.
  • such coating has an average surface roughness of less than about 100 nanometers, and preferably of less than about 10 nanometers.
  • such coating is biocompatiable.
  • such coating is is hydrophobic.
  • such coating is hydrophilic.
  • the term 'biologically active material' encompasses therapeutic agents, such as drugs, and also genetic materials and biological materials.
  • the genetic materials mean DNA or RNA, including, without limitation, of DNA/RNA encoding a useful protein stated below, anti-sense DNA/RNA, intended to be inserted into a human body including viral vectors and non- viral vectors. Examples of DNA suitable for the present invention include DNA encoding... anti-sense RNA...
  • tRNA or rRNA to replace defective or deficient endogenous molecules
  • angiogenic factors including growth factors, such as acidic and basic fibroblast growth factors, vascular endothelial growth factor, epidermal growth factor, transforming growth factor ⁇ and ⁇ , platelet-derived endothelial growth factor, plateletderived growth factor, tumor necrosis factor ⁇ , hepatocyte growth factor and insulin like growth factor...cell cycle inhibitors including CD inhibitors... thymidine kinase ("TK”) and other agents useful for interfering with cell proliferation, and...the family of bone morphogenic proteins (“BMPs”) as explained below.
  • growth factors such as acidic and basic fibroblast growth factors, vascular endothelial growth factor, epidermal growth factor, transforming growth factor ⁇ and ⁇ , platelet-derived endothelial growth factor, plateletderived growth factor, tumor necrosis factor ⁇ , hepatocyte growth factor and insulin like growth factor
  • cell cycle inhibitors including CD inhibitors... thymidine kina
  • Viral vectors include adenoviruses, gutted adenoviruses, adeno-associated virus, retroviruses, alpha virus (Semliki Forest, Sindbis, etc.), lentiviruses, herpes simplex virus, ex vivo modified cells (e.g., stem cells, fibroblasts, myoblasts, satellite cells, pericytes, cardiomyocytes, sketetal myocytes, macrophage), replication competent viruses (e.g., ONYX-015), and hybrid vectors.
  • adenoviruses include adenoviruses, gutted adenoviruses, adeno-associated virus, retroviruses, alpha virus (Semliki Forest, Sindbis, etc.), lentiviruses, herpes simplex virus, ex vivo modified cells (e.g., stem cells, fibroblasts, myoblasts, satellite cells, pericytes, cardiomyocytes, sketetal myocytes
  • Non-viral vectors include artificial chromosomes and mini-chromosomes, plasmid DNA vectors (e.g., pCOR), cationic polymers (e.g., polyethyleneimine, polyethyleneimine (PEI)) graft copolymers (e.g., polyether-PEI and polyethylene oxide-PEI), neutral polymers PVP, SP1017 (SUPRATEK), lipids or lipoplexes, nanoparticles and microparticles with and without targeting sequences such as the protein transduction domain (PTD)." "The biological materials include cells, yeasts, bacteria, proteins, peptides, cytokines and hormones.
  • peptides and proteins examples include growth factors (FGF, FGF-I, FGF-2, VEGF, Endotherial Mitogenic Growth Factors, and epidermal growth factors, transforming growth factor ⁇ and ⁇ , platelet derived endothelial growth factor, platelet derived growth factor, tumor necrosis factor ⁇ , hepatocyte growth factor and insulin like growth factor), transcription factors, proteinkinases, CD inhibitors, thymidine kinase, and bone morphogenic proteins (BMP's), such as BMP-2, BMP-3, BMP -4, BMP-5, BMP-6 (Vgr-1), BMP-7 (OP-I), BMP-8.
  • growth factors FGF, FGF-I, FGF-2, VEGF, Endotherial Mitogenic Growth Factors, and epidermal growth factors, transforming growth factor ⁇ and ⁇ , platelet derived endothelial growth factor, platelet derived growth factor, tumor necrosis factor ⁇ , hepatocyte growth factor and insulin like growth
  • BMP's are BMP-2, BMP-3, BMP-4, BMP-5, BMP-6, BMP-7.
  • molecules capable of inducing an upstream or downstream effect of a BMP can be provided.
  • Such molecules include any of the "hedgehog" proteins, or the DNA's encoding them. These dimeric proteins can be provided as homodimers, heterodimers, or combinations thereof, alone or together with other molecules.
  • Cells can be of human origin (autologous or allogeneic) or from an animal source (xenogeneic), genetically engineered, if desired, to deliver proteins of interest at the transplant site.
  • the delivery media can be formulated as needed to maintain cell function and viability.
  • Cells include whole bone marrow, bone marrow derived mono-nuclear cells, progenitor cells (e.g., endothelial progentitor cells) stem cells (e.g., mesenchymal, hematopoietic, neuronal), pluripotent stem cells, fibroblasts, macrophage, and satellite cells.”
  • Bioly active material also includes non-genetic therapeutic agents, such as:...anti-thrombogenic agents such as heparin, heparin derivatives, urokinase, and PPack (dextrophenylalanine proline arginine chloromethylketone); ...antiproliferative agents such as enoxaprin, angiopeptin, or monoclonal antibodies capable of blocking smooth muscle cell proliferation, hirudin, and acetylsalicylic acid, amlodipine and doxazosin; ...
  • non-genetic therapeutic agents such as:...anti-thrombogenic agents such as heparin, heparin derivatives, urokinase, and PPack (dextrophenylalanine proline arginine chloromethylketone); ...antiproliferative agents such as enoxaprin, angiopeptin, or monoclonal antibodies capable of blocking smooth muscle cell proliferation, hirudin, and acetylsalicylic acid, am
  • anti-inflammatory agents such as glucocorticoids, betamethasone, dexamethasone, prednisolone, corticosterone, budesonide, estrogen, sulfasalazine, and mesalamine; ...
  • immunosuppressants such as sirolimus (RAPAMYCIN), tacrolimus, everolimus and dexamethasone,...antineoplastic/antiproliferative/anti-miotic agents such as paclitaxel, 5-fluorouracil, cisplatin, vinblastine, vincristine, epothilones, methotrexate, azathioprine, halofuginone, adriamycin, actinomycin and mutamycin; cladribine; endostatin, angiostatin and thymidine kinase inhibitors, and its analogs or derivatives; ...anesthetic agents such as lidocaine, bupivacaine, and ropivacaine; ...anticoagulants such as D-Phe-Pro-Arg chloromethyl keton, an RGD peptide-containing compound, heparin, antithrombin compounds, platelet receptor antagonists, anti-thrombin antibodies, anti-platelet receptor antibodies
  • anti-oxidants such as probucol
  • antibiotic agents such as penicillin, cefoxitin, oxacillin, tobranycin...angiogenic substances, such as acidic and basic fibrobrast growth factors, estrogen including estradiol (E2), estriol (E3) and 17-Beta Estradiol
  • FDAD angiotensin-converting enzyme
  • the biologically active materials of the present invention include trans-retinoic acid and nitric oxide adducts.
  • a biologically active material may be encapsulated in micro-capsules by the known methods. Paragraphs 73 through 82 of published United States patent application 1004/0030379 describe coating compositons that may be used in the device of the instant invention; and they are reproduced in their entireties below.
  • Coating Compositions can be applied by any method to a surface of a medical device to form a coating. Examples of such methods are painting, spraying, dipping, rolling, electrostatic deposition and all modern chemical ways of immobilization of bio-molecules to surfaces.”
  • the coating composition used in the present invention may be a solution or a suspension of a polymeric material and/or a biologically active material and/or magnetic particles in an aqueous or organic solvent suitable for the medical device which is known to the skilled artisan.
  • a slurry, wherein the solid portion of the suspension is comparatively large, can also be used as a coating composition for the present invention.
  • Such coating composition may be applied to a surface, and the solvent may be evaporated, and optionally heat or ultraviolet (UV) cured.”
  • the solvents used to prepare coating compositions include ones which can dissolve the polymeric material into solution and do not alter or adversely impact the therapeutic properties of the biologically active material employed.
  • useful solvents for silicone include tetrahydrofuran
  • a coating of a medical device of the present invention may consist of various combinations of coating layers.
  • the first layer disposed over the surface of the medical device can contain a polymeric material and a first biologically active material.
  • the second coating layer that is disposed over the first coating layer, contains magnetic particles and optionally a polymeric material.
  • the second coating layer protects the biologically active material in the first coating layer from exposure during implantation and prior to delivery.
  • the second coating layer is substantially free of a biologically active material.”
  • Another layer i.e. sealing layer, which is free of magnetic particles
  • the first and second biologically active materials may be identical or different. When the first and second biologically active material are identical, the concentration in each layer may be different.
  • the layer containing the second biologically active material may be covered with yet another coating layer containing magnetic particles.
  • the magnetic particles in two different layers may have an identical or a different average particle size and/or an identical or a different concentrations. The average particle size and concentration can be varied to obtain a desired release profile of the biologically active material. In addition, the skilled artisan can choose other combinations of those coating layers.”
  • the coating of a medical device of the present invention may comprise a layer containing both a biologically active material and magnetic particles.
  • the first coating layer may contain the biologically active material and magnetic particles
  • the second coating layer may contain magnetic particles and be substantially free of a biologically active material.
  • the average particle size of the magnetic particles in the first coating layer may be different than the average particle size of the magnetic particles in the second coating layer.
  • the concentration of the magnetic particles in the first coating layer may be different than the concentration of the magnetic particles in the second coating layer.
  • the magnetic susceptibility of the magnetic particles in the first coating layer may be different than the magnetic susceptibility of the magnetic particles in the second coating layer.”
  • the polymeric material should be a material that is biocompatible and avoids irritation to body tissue.
  • the polymeric materials used in the coating composition of the present invention include, but not limited to, polycarboxylic acids, cellulosic polymers, including cellulose acetate and cellulose nitrate, gelatin, polyvinylpyrrolidone, cross-linked polyvinylpyrrolidone, polyanhydrides including maleic anhydride polymers, polyamides, polyvinyl alcohols, copolymers of vinyl monomers such as EVA, polyvinyl ethers, polyvinyl aromatics, polyethylene oxides, glycosaminoglycans, polysaccharides, polyesters including polyethylene terephthalate, polyacrylamides, polyethers, polyether sulfone, polycarbonate, polyalkylenes including polypropylene, polyethylene and high molecular weight polyethylene, halogenated polyalkylenes including polytetrafluoroethylene, polyurethanes, polyortho
  • polymers include polyurethane (BAYHDROL®, etc.) fibrin, collagen and derivatives thereof, polysaccharides such as celluloses, starches, dextrans, alginates and derivatives, hyaluronic acid, and squalene.
  • polyurethane BAYHDROL®, etc.
  • fibrin such as celluloses, starches, dextrans, alginates and derivatives, hyaluronic acid, and squalene.
  • polysaccharides such as celluloses, starches, dextrans, alginates and derivatives, hyaluronic acid, and squalene.
  • polymeric materials used in the coating composition of the present invention include other polymers which can be used include ones that can be dissolved and cured or polymerized on the medical device or polymers having relatively low melting points that can be blended with biologically active materials.
  • Additional suitable polymers include, thermoplastic elastomers in general, polyolefins, polyisobutylene, ethylene-alphaolefm copolymers, acrylic polymers and copolymers, vinyl halide polymers and copolymers such as polyvinyl chloride, polyvinyl ethers such as polyvinyl methyl ether, polyvinylidene halides such as polyvinylidene fluoride and polyvinylidene chloride, polyacrylonitrile, polyvinyl ketones, polyvinyl aromatics such as polystyrene, polyvinyl esters such as polyvinyl acetate, copolymers of vinyl monomers, copolymers of vinyl monomers and olefins such as ethyl ene-methyl methacrylate copolymers, acrylonitrile-styrene copolymers, ABS (acrylonitrile-butadiene-styrene) resins, ethylene-vinyl
  • polyacrylic acid available as HYDROPLUS® (Boston Scientific Corporation, Natick, Mass.), and described in U.S. Pat. No. 5,091,205, the disclosure of which is hereby incorporated herein by reference.
  • the polymer is a copolymer of polylactic acid and polycaprolactone.”
  • the polymeric materials should be selected from elastomeric polymers such as silicones (e.g.
  • polysiloxanes and substituted polysiloxanes polyurethanes
  • thermoplastic elastomers thermoplastic elastomers
  • ethylene vinyl acetate copolymers polyolefm elastomers
  • EPDM rubbers EPDM rubbers. Because of the elastic nature of these polymers, the coating composition adheres better to the surface of the medical device when the device is subjected to forces, stress or mechanical challenge.”
  • the amount of the polymeric material present in the coatings can vary based on the application for the medical device. One skilled in the art is aware of how to determine the desired amount and type of polymeric material used in the coating.
  • the polymeric material in the first coating layer may be the same as or different than the polymeric material in the second coating layer.
  • the thickness of the coating is not limited, but generally ranges from about 25 ⁇ m to about 0.5 mm. Preferably, the thickness is about 30 ⁇ m to 100 ⁇ m.”
  • Electromagnetic Sources ...An external electromagnetic source or field may be applied to the patient having an implanted coated medical device using any method known to skilled artisan. In the method of the present invention, the electromagnetic field is oscillated. Examples of devices which can be used for applying an electromagnetic field include a magnetic resonance imaging ("MRI") apparatus. Generally, the magnetic field strength suitable is within the range of about 0.50 to about 5 Tesla (Webber per square meter).
  • MRI magnetic resonance imaging
  • the duration of the application may be determined based on various factors including the strength of the magnetic field, the magnetic substance contained in the magnetic particles, the size of the particles, the material and thickness of the coating, the location of the particles within the coating, and desired releasing rate of the biologically active material.”
  • an electromagnetic field is uniformly applied to an object under inspection.
  • a gradient magnetic field superposing the electromagnetic field, is applied to the same.
  • the object is applied with a selective excitation pulse of an electromagnetic wave with a resonance frequency which corresponds to the electromagnetic field of a specific atomic nucleus.
  • a magnetic resonance (MR) is selectively excited.
  • a signal generated is detected as an MR signal. See U.S. Pat. No. 4,115,730 to Mansfield, U.S. Pat. No. 4,297,637 to Crooks et al., and U.S. Pat. No. 4,845,430 to Nakagayashi.
  • the function to create an electromagnetic field is useful for the present invention.
  • the implanted medical device of the present can be located as usually done for MRI imaging, and then an electromagnetic field is created by the MRI apparatus to facilitate release of the biologically active material.
  • the duration of the procedure depends on many factors, including the desired releasing rate and the location of the inserted medical device.
  • One skilled in the art can determine the proper cycle of the electromagnetic field, proper intensity of the electromagnetic field, and time to be applied in each specific case based on experiments using an animal as a model.'
  • the excitation source frequency of the elecromagnetic energy source can have an excitation source frequency in the range of about 1 Hertz to about 300 kiloHertz.
  • the shape of the frequency can be of different types.
  • the frequency can be in the form of a square pulse, ramp, sawtooth, sine, triangle, or complex.
  • each form can have a varying duty cycle.”
  • the mechanical vibrational energy source includes various sources which cause vibration such as ultrasound energy. Examples of suitable ultrasound energy are disclosed in U.S. Pat. No. 6,001,069 to Tachibana et al. and U.S. Pat. No. 5,725,494 to Brisken, PCT publications WO00/16704, WO00/18468, WOOO/00095, WOOO/07508 and WO99/33391, which are all incorporated herein by reference. Strength and duration of the mechanical vibrational energy of the application may be determined based on various factors including the biologically active material contained in the coating, the thickness of the coating, structure of the coating and desired releasing rate of the biologically active material.”
  • U.S. Pat. No. 5,895,356 discloses a probe for transurethrally applying focused ultrasound energy to produce hyperthermal and thermotherapeutic effect in diseased tissue.
  • U.S. Pat. No. 5,873,828 discloses a device having an ultrasonic vibrator with either a microwave or radio frequency probe.
  • U.S. Pat. No. 6,056,735 discloses an ultrasonic treating device having a probe connected to a ultrasonic transducer and a holding means to clamp a tissue. Any of those methods and devices can be adapted for use in the method of the present invention.”
  • Ultrasonic vibrator or probe can be inserted into a subject's body through a body lumen, such as blood vessels, bronchus, urethral tract, digestive tract, and vagina.
  • a body lumen such as blood vessels, bronchus, urethral tract, digestive tract, and vagina.
  • an ultrasound probe can be appropriately modified, as known in the art, for subcutaneous application. The probe can be positioned closely to an outer surface of the patient body proximal to the inserted medical device.”
  • the duration of the procedure depends on many factors, including the desired releasing rate and the location of the inserted medical device.
  • the procedure may be performed in a surgical suite where the patient can be monitored by imaging equipment. Also, a plurality of probes can be used simultaneously.
  • One skilled in the art can determine the proper cycle of the ultrasound, proper intensity of the ultrasound, and time to be applied in each specific case based on experiments using an animal as a model.”
  • the excitation source frequency of the mechanical vibrational energy source can have an excitation source frequency in the range of about 1 Hertz to about 300 kiloHertz.
  • the shape of the frequency can be of different types.
  • the frequency can be in the form of a square pulse, ramp, sawtooth, sine, triangle, or complex.
  • each form can have a varying duty cycle.”
  • the present invention provides a method of treatment to reduce or prevent the degree of restenosis or hyperplasia after vascular intervention such as angioplasty, stenting, atherectomy and grafting. All forms of vascular intervention are contemplated by the invention, including, those for treating diseases of the cardiovascular and renal system.
  • Such vascular intervention include, renal angioplasty, percutaneous coronary intervention (PCI), percutaneous transluminal coronary angioplasty (PTCA); carotid percutaneous transluminal angioplasty (PTA); coronary by-pass grafting, angioplasty with stent implantation, peripheral percutaneous transluminal intervention of the iliac, femoral or popliteal arteries, carotid and cranial vessels, surgical intervention using impregnated artificial grafts and the like.
  • PCI percutaneous coronary intervention
  • PTCA percutaneous transluminal coronary angioplasty
  • PTA carotid percutaneous transluminal angioplasty
  • coronary by-pass grafting angioplasty with stent implantation, peripheral percutaneous transluminal intervention of the iliac, femoral or popliteal arteries, carotid and cranial vessels, surgical intervention using impregnated artificial grafts and the like.
  • the system described in the present invention can be used for treating vessel walls, portal and hepatic veins, esophagus, intestine, ureters, urethra, intracerebrally, lumen, conduits, channels, canals, vessels, cavities, bile ducts, or any other duct or passageway in the human body, either in-born, built in or artificially made. It is understood that the present invention has application for both human and veterinary use.”
  • the present invention also provides a method of treatment of diseases and disorders involving cell overproliferation, cell migration, and enlargement.
  • Diseases and disorders involving cell overproliferation that can be treated or prevented include but are not limited to malignancies, premalignant conditions (e.g., hyperplasia, metaplasia, dysplasia), benign tumors, hyperproliferative disorders, benign dysproliferative disorders, etc. that may or may not result from medical intervention.
  • premalignant conditions e.g., hyperplasia, metaplasia, dysplasia
  • benign tumors e.g., hyperproliferative disorders, benign dysproliferative disorders, etc.
  • hyperproliferative disorders e.g., benign dysproliferative disorders
  • benign dysproliferative disorders e.g., etc.
  • Whether a particular treatment of the invention is effective to treat restenosis or hyperplasia of a body lumen can be determined by any method known in the art, for example but not limited to, those methods described in this section.
  • the safety and efficiency of the proposed method of treatment of a body lumen may be tested in the course of systematic medical and biological assays on animals, toxicological analyses for acute and systemic toxicity, histological studies and functional examinations, and clinical evaluation of patients having a variety of indications for restenosis or hyperplasia in a body lumen.”
  • the efficacy of the method of the present invention may be tested in appropriate animal models, and in human clinical trials, by any method known in the art.
  • the animal or human subject may be evaluated for any indicator of restenosis or hyperplasia in a body lumen that the method of the present invention is intended to treat.
  • the efficacy of the method of the present invention for treatment of restenosis or hyperplasia can be assessed by measuring the size of a body lumen in the animal model or human subject at suitable time intervals before, during, or after treatment. Any change or absence of change in the size of the body lumen can be identified and correlated with the effect of the treatment on the subject.
  • the size of the body lumen can be determined by any method known in the art, for example, but not limited to, angiography, ultrasound, fluoroscopy, magnetic resonance imaging, optical coherence tumography and histology.”
  • a medical preparation for treating arthrosis, arthritis, and other diseases for example, but not limited to, angiography, ultrasound, fluoroscopy, magnetic resonance imaging, optical coherence tumography and histology.
  • a novel medical preparation comprised of applicants' nanomagnetic particles is provided. This preparation is similar to the preparation described in United States patent 6,669,623.
  • a medical preparation including nanoscalar particles that generate heat when an alternating electromagnetic field is applied said nanoscalar particles comprising: a core containing iron oxide and an inner shell with groups that are capable of forming cationic groups, wherein the iron oxide concentration is in the range from 0.01 to 50 mg/ml of synovial fluid at a power absorption in the range from 50 to 500 mW/mg of iron and heating to a temperature in the range from 42 to 50° C; and pharmacologically active species bound to said inner shell selected from the group consisting of thermosensitizers and thermosensitive chemotherapeutics or isotopes thereof; wherein said preparation is used for treating arthrosis, arthritis and rheumatic joint diseases by directly injecting said nanoscalar particles into the synovial fluid, said nanoscalar particles being absorbed by said fluid and transported to the inflamed synovial membrane where they
  • Applicants' medical preparation is similar to the preparation of United States patent 6,669,623 but differs therefrom in that, instead of an iron oxide core, applicants' preparation is comprised of the nanomagnetic material described elsewhere in this specification.
  • nanoscalar particles designed based on the description given in DE 197 26 282 for treating rheumatic joint diseases, said particles comprising, in a first embodiment, a core containing iron oxide, an inner shell that encompasses said core and comprises groups capable of forming cationic groups, and an outer shell made of species comprising neutral and/or anionic groups, and radionuclides and cytotoxic substances bound to said inner shell.
  • These nanoscalar particles may also be one-shelled, i.e.
  • a suspension of nanoscalar particles formed by an iron oxide core and two shells, with doxorubicin as a heat-sensitive cytotoxic material and beta emitting radionuclides bound to said particles is directly injected into the joint cavity to be treated.
  • the suspension will stay there without generating heat for a period of time that is determined before the therapy begins. This period can be from 1 hour to 72 hours.
  • the two-shelled nanoparticles according to the invention are absorbed by the synovial fluid and flow into the inflamed synovial membrane.
  • the therapist then ascertains using magnetic resonance tomography whether the nanoparticles are really deposited in the synovial membrane, the adjacent lymph nodes, and in the healthy tissue. If required, an extravasation to adjacent areas may be performed but this should not be necessary due to the high rate of phagocytosis....Subsequently, the area is exposed to an alternating electromagnetic field with an excitation frequency in the range from 1 IcHz and 100 MHz. Its actual value depends on the location of the diseased joint. While hands and arms are treated at higher frequencies, 500 kHz will be sufficient for back pain, the lower joints and the thigh joints.
  • the alternating electromagnetic field brings out the localized heat; at the same time, the radionuclide and the cytotoxic substances (here: doxorubicin) are activated, and success of treatment beyond the added effects of its components is achieved due to the trimodal combinatorial effect of therapies and the differential endocytosis and high rate of phagocytosis of the nano-particles.
  • doxorubicin cytotoxic substances
  • the synovial membrane shows increased and sustained sclerosing with this treatment as compared to other medical preparations and methods of treating rheumatic diseases.
  • the heat that can be generated by the alternating electromagnetic field applied to the nanoparticles, or, in other words, the duration of applying the alternating electromagnetic field to obtain a specific equilibrium temperature is calculated in advance based on the iron oxide concentration that is typically in the range from 0.01 to 50 mg/ml of synovial fluid and power absorption that is typically in the range from 50 to 500 mW/mg of iron. Then the field strength is reduced to keep the temperature on a predefined level of, for example, 45° C.
  • the particles When applying static magnetic field gradients, the particles can be concentrated in the treated joint ('magnetic targeting')."
  • the iron-oxide core of the particles of this United states patent 6,669,223 may advantageously be replaced with the nanomagnetic material core of the present invention.
  • Nanoscale particles having an iron oxide-containing core and at least two shells surrounding said core the (innermost) shell adjacent to the core being a coat that features groups capable of forming cationic groups and that is degraded by the human or animal body tissue at such a low rate that an association of the core surrounded by said coat with the surfaces of cells and the incorporation of said core into the inside of cells, respectively is possible, and the outer shell(s) being constituted by species having neutral and/or anionic groups which, from without, make the nanoscale particles appear neutral or negatively charged and which is (are) degraded by the human or animal body tissue to expose the underlying shell(s) at a rate which is higher than that for the innermost shell but still low enough to ensure a sufficient distribution of said nanoscale particles within a body tissue which has been punctually infiltrated therewith.”
  • the particles of this published application comprise an iron-oxide- contianing core with at least two shells (coats).
  • Such particles can be obtained by providing a (preferably superparamagnetic) iron oxide-containing core with at least two shells (coats), the shell adjacent to the core having many positively charged functional groups which permits an easy incorporation of the thus encased iron oxide-containing cores into the inside of the tumor cells, said inner shell additionally being degraded by the (tumor) tissue at such a low rate that the cores encased by said shell have sufficient time to adhere to the cell surface (e.g. through electrostatic interactions between said positively charged groups and negatively charged groups on the cell surface) and to subsequently be incorporated into the inside of the cell.
  • a (preferably superparamagnetic) iron oxide-containing core with at least two shells (coats), the shell adjacent to the core having many positively charged functional groups which permits an easy incorporation of the thus encased iron oxide-containing cores into the inside of the tumor cells, said inner shell additionally being degraded by the (tumor) tissue at such a low rate that the cores encased by said shell have sufficient time to adhere
  • the outer shell(s) is (are) constituted by species which shield (mask) or compensate, respectively, or even overcompensate the underlying positively charged groups of the inner shell (e.g. by negatively charged functional groups) so that, from without, the nanoscale particle having said outer shell(s) appears to have an overall neutral or negative charge.
  • the outer shell(s) is (are) degraded by the body tissue at a (substantially) higher rate than the innermost shell, said rate being however still low enough to give the particles sufficient time to distribute themselves within the tissue if they are injected punctually into the tissue (e.g. in the form of a magnetic fluid). In the course of the degradation of said outer shell(s) the shell adjacent to the core is exposed gradually.
  • the present invention relates to nanoscale particles having an iron oxide- containing core (which is ferro-, ferri- or, preferably, superparamagnetic) and at least two shells surrounding said core, the (innermost) shell adjacent to the core being a coat that features groups capable of forming cationic groups and that is degraded by the human or animal body tissue at such a low rate that an association of the core surrounded by said coat with the surfaces of cells and the incorporation of said core into the inside of cells, respectively is possible, and the outer shell(s) being constituted by species having neutral and/or anionic groups which, from without, make the nanoscale particles appear neutral or negatively charged and which
  • Paragraph 0007 of published United States patent application US2003/0180370 indicates that the core of the particles of this patent application "...consists of pure iron oxide." Applicants advantageously substitute their nanomagnetic material of this invention for such " ...pure iron oxide." The shells of published United States patent application US2003/0180370 are discussed in paragraphs 0013 through 0016 of such patent application.
  • one or more (preferably one) outer shells are provided on the described innermost shell....the outer shell serves to achieve a good distribution within the tumor tissue of the iron oxide-containing cores having said inner shell, said outer shell being required to be biologically degradable (i.e., by the tissue) after having served its purpose to expose the underlying innermost shell, which permits a smooth incoiporation into the inside of the cells and an association with the surfaces of the cells, respectively.
  • the outer shell is constituted by species having no positively charged functional groups, but on the contrary having preferably negatively charged functional groups so that, from without, said nanoscale particles appear to have an overall neutral charge (either by virtue of a shielding (masking) of the positive charges inside thereof and/or neutralization thereof by negative charges as may, for example, be provided by carboxylic groups) or even a negative charge (for example due to an excess of negatively charged groups).
  • the present invention for said purpose there may be employed, for example, readily (rapidly) biologically degradable polymers featuring groups suitable for coupling to the underlying shell (particularly innermost shell), e.g., (co)polymers based on ⁇ -hydroxycarboxylic acids (such as, e.g., polylactic acid, polyglycolic acid and copolymers of said acids) or polyacids (e.g., sebacic acid).
  • ⁇ -hydroxycarboxylic acids such as, e.g., polylactic acid, polyglycolic acid and copolymers of said acids
  • polyacids e.g., sebacic acid
  • the use of optionally modified, naturally occurring substances, particularly biopolymers is particularly preferred for said purpose.
  • the carbohydrates (sugars) and particularly the dextrans may, for example, be cited.
  • covalent interactions there may, for example, be employed the conventional bond-forming reactions of organic chemistry, such as, e.g., ester formation, amide formation and imine formation. It is, for example, possible to react a part of or all of the amino groups of the innermost shell with carboxylic groups or aldehyde groups of corresponding species employed for the synthesis of the outer shell(s), whereby said amino groups are consumed (masked) with formation of (poly-)amides or imines. The biological degradation of the outer shell(s) may then be effected by (e.g., enzymatic) cleavage of said bonds, whereby at the same time said amino groups are regenerated.”
  • organic chemistry such as, e.g., ester formation, amide formation and imine formation.
  • the essential elements of the nanoscale particles according to the present invention are (i) the iron oxide-containing core, (ii) the inner shell which in its exposed state is positively charged and which is degradable at a lower rate, and (iii) the outer shell which is biologically degradable at a higher rate and which, from without, makes the nanoscale particles appear to have an overall neutral or negative charge, the particles according to the invention still may comprise other, additional components.
  • the particles according to the invention still may comprise other, additional components.
  • there may particularly be cited substances which by means of the particles of the present invention are to be imported into the inside of cells (preferably tumor cells) to enhance the effect of the cores excited by an alternating magnetic field therein or to fulfill a function independent thereof.
  • Such substances are coupled to the -inner shell preferably via covalent bonds or electrostatic interactions (preferably prior to the synthesis of the outer shell(s)). This can be effected according to the same mechanisms as in the case of attaching the outer shell to the inner shell.
  • part of the amino groups present could be employed for attaching such compounds.
  • Not more than 10% of the amino groups present should in general be consumed for the importation of other substances into the inside of the cells.
  • silanes different from aminosilanes and having different functional groups for the synthesis of the inner shell, to subsequently utilize said different functional groups for the attachment of other substances and/or the outer shell to the inner shell.
  • other functional groups are, e.g., unsaturated bonds or epoxy groups as they are provided by, for example, silanes having (meth)acrylic groups or epoxy groups.”
  • thermosensitive chemotherapeutic agents cytostatic agents, thermosensitizers such as doxorubicin, proteins, etc.
  • thermosensitizers such as doxorubicin, proteins, etc.
  • thermosensitive cytotoxic agents are also referred to in paragraph 18 of published United States patent application US 2003/0180370, wherein it is disclosed that: "According to the present invention it is particularly preferred to link to the inner shell substances which become completely effective only at slightly elevated temperatures as generated by the excitation of the iron oxide-containing cores of the particles according to the invention by an alternating magnetic field, such as, e.g., thermosensitive chemotherapeutic agents (cytostatic agents, thermosensitizers such as doxorubicin, proteins, etc.). If for example a thermosensitizer is coupled to the innermost shell (e.g. via amino groups) the corresponding thermosensitizer molecules become reactive only after the degradation of the outer coat (e.g. of dextran) upon generation of heat (by the alternating magnetic field)."
  • thermosensitive chemotherapeutic agents cytostatic agents, thermosensitizers such as doxorubicin, proteins, etc.
  • compositions of published United States patent application US2003/0180370 (and of applicants' derivative compositions) is described in paragarphs 0019-0020 of published United States patent application 2003/0180370.
  • excitation frequency of the alternating magnetic field applicator must be tuned to the size of the nanoscale particles according to the present invention in order to achieve a maximum energy yield.
  • the particles in question are nano-sized (as is the case with applicants' nanomagnetic particles), they do not leave the tissue in which they have been applied.
  • ...nanoparticles do not leave the tissue into which they have been applied, but get caught within the interstices of the tissue. They will get transported away only via vessels that have been perforated in the course of the application.
  • High molecular weight substances leave the tissue already due to diffusion and tumor pressure or become deactivated by biodegradation.
  • the nanoscale particles of the present invention cannot take place with the nanoscale particles of the present invention since on the one hand they are already small enough to be able to penetrate interstices of the tissue (which is not possible with particles in the ⁇ m range, for example, liposomes) and on the other hand are larger than molecules and, therefore cannot leave the tissue through diffusion and capillary pressure.
  • the nanoscale particles lack osmotic activity and hardly influence the tumor growth, which is absolutely necessary for an optimum distribution of the particles within the tumor tissue... Jf an early loading of the primary tumor is effected the particles will be incorporated to a high extent by the tumor cells and will later also be transferred to the daughter cells at a probability of 50% via the parental cytoplasm.
  • composition of published United States patent application US 2003/0180370, and also of applicants 1 related composition also effect an anti-mitotic activity because of "selective embolization.”
  • paragraphs 24-25 of such United States patent application "Due to the two- stage interlesional application a selective accumulation is not necessary.
  • applicants' "two-shell nanomagnetic compositons" are incorporated into tumor cells and, with the use of an external electromagnetic field, used to cause a regioselective embolization. Thereafter, when the tumor cells have been deprived of serum, the nanomagnetic materials permanently disposed within the cells are caused to heat up and kill the cells, which are now more sensitive to hyperthermia.
  • a fiberoptical temperature probe having a diameter of, e g , 0.5 mm is introduced angiographically and the temperature is measuied m the vicinity of the point of congestion while, again by external application of an alternating magnetic field, a microregional heating and activation of said proteolytic enzymes is caused.
  • a determination of the temperature can even be dispensed with on principle since the energy absorption to be expected can already be estimated with relatively high accuracy on the basis of the amount of magnetic fluid applied and the known field strength and frequency.
  • the field is reapplied in intervals of about 6 to 8 hours In the intervals of no excitation the body has the opportunity to partly transport away cell debris until eventually, supported by the body itself, the clogging is removed. Due to the small size of the particles of the invention the migration of said particles through the ventricles of the heart and the blood vessels is uncritical Eventually the particles again reach liver and spleen via RES.”
  • thermoablation can be conducted with the nanoscale particles of the present invention
  • mainly interstitial laser systems that are m part also used m surgery are employed for thermoablative purposes
  • a big disadvantage of said method is the high mvasivity of the microcatheter-guided fiberoptical laser provision and the hard to control expansion of the target volume.
  • the nanoparticles according to the present invention can be used for such purposes in a less traumatic way following MRT-aided accumulation of the particle suspension m the target region, at higher amplitudes of the alternating field also temperatures above 50° C. can homogeneously be generated.
  • Temperature control may, for example, also be effected through an extremely thm fiberoptical probe having a diameter of less than 0.5 mm.
  • the energy absorption as such is non-mvasive."
  • the compositions described in published United States patent application US 2003/0180370 maybe used in the processes desc ⁇ bed by the claims of United States patent 6,541,039, the entre disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of United States patent 6,541,039 describes "1 A method of hyperthermic treatment of a region of the body selected from the group consisting of hyperthermic tumor theiapy, heat-mduced lysis of a thrombus, and thermoablation of a target region, comprising, (a) accumulating in the region of the body a magnetic fluid comprising nanoscale particles suspended m a fluid medium, each particle having an iron oxide-contammg core and at least two shells surrounding said coie, (1) the innermost shell adjacent to the core being a shell that: (a) is formed from polycondensable silanes comprising at least one aminosilane and comprises groups that are positively charged or positively chargeable, and (b) is degraded by human or animal body tissue at such a low rate that adhesion of the core surrounded by the innermost shell with the surface of a cell through said positively charged or positively chargeable groups of the innermost shell and incorporation of the core into the interior of the cell are possible, and (2) the outer shell or
  • Claim 3 describes " 3.
  • the method of claim 1 that is a method of heat-induced lysis of a thrombus, comprising accumulating in the thrombus the magnetic fluid, and applying an alternating magnetic field to generate heat by excitation of the iron oxide-containing cores of the particles to cause heat-induced lysis of the thrombus.”
  • Claim 4 describes " 4.
  • the method of claim 1 that is a method of thermoablation of a target region, comprising accumulating in the target region the magnetic fluid, and applying an alternating magnetic field to generate heat by excitation of the iron oxide-containing cores of the particles to cause thermoablation of the target region.”
  • Claim 10 describes "10.
  • Claim 11 describes "11. The method of claim 1 where the at least one species comprising the outer shell or shells is selected from carbohydrates optionally modified by carboxylic groups.” Claim 12 describes “12. The method of claim 11 where the at least one species comprising the outer shell or shells is selected from dextrans optionally modified by carboxylic groups.” Claim 13 describes “13. The method of claim 12 where the at least one species comprising the outer shell or shells is selected from dextrans modified by carboxylic groups.” Claim 14 describes “4. The method of claim 1 where at least one pharmacologically active species is linked to the innermost shell," Claim 15 describes “15. The method of claim 14 where the at least one pharmacologically active species is selected from the group consisting of thermosensitizers and thermosensitive chemotherapeutic agents
  • a method of tumor therapy by hyperthermia comprising: (a) accumulating in the tumor a magnetic fluid comprising nanoscale particles suspended in a fluid medium, each particle having a superparamagnetic iron oxide-containing core having an average particle size of 3 to 30 nm comprising magnetite, maghemite, or stoichiometric intermediate forms thereof and at least two shells surrounding said core, (1) the innermost shell adjacent to the core being a shell that(a) is formed from polycondensable aminosilanes and comprises groups that are positively charged or positively chargeable, and (b) is degraded by human or animal body tissue at such a low rate that adhesion of the core surrounded by the innermost shell with the surface of a cell through said positively charged or positively chargeable groups of the innermost shell and incorporation of the core into the interior of the cell are possible, and (2) the outer shell or shells being a shell or shells comprising at least one species that: (a)
  • Claim 17 describes "17.
  • Claim 18 describes "18.
  • the nanosize iron-containing oxide particles used in the process of United States patent 6,541,039 may be prepared by conventional means such as, e.g., the process desrcribed in United States patent 6, 183,658.
  • a process for producing an-agglomerate-free suspension of stably coated nanosize iron-containing oxide particles comprising the following steps in the order indicated: (1) preparing an aqueous suspension of nanosize iron-containing oxide particles which are partly or completely present in the form of agglomerates; (2) adding (i) a trialkoxysilane which has a hydrocarbon group which is directly bound to Si and to which is bound at least one group selected from amino, carboxyl, epoxy, mercapto, cyano, hydroxy, acrylic, and methacrylic, and (ii) a water-miscible polar organic solvent whose boiling point is at least 10° C.
  • a microcapsule for hyperthermia treatment is made by coating nanomagnetic particles with cis-platinum diamine dichloride (CDDP) 5 and then covering the layer of anticancer agent with a mixture of hydroxy lpropyl cellulse and mannitol.
  • CDDP cis-platinum diamine dichloride
  • This microcapsule is similar to the microcapsule described in an article by Tomoya Sato et al., "The Development of Anticancer Agent Releasing Microcapusle Made of Ferromagnetic Amorphous Flakes for Mratissue Hyperthermia," EEEE Transactions on Magnetics, Volume 29, Noumber 6, November, 1993.
  • the "core" of the Sato et al. microcapsule was ferromagnetic amorphous flakes with an average size of about 50 microns and a Curie temperature of about 45 degrees Centigrade.
  • the Sato et al.ferromagnetic material is replaced with the nanomagnetic material of this invention.
  • the core of the Sato et al. microcapsule was then coated with an anticancer agent, such as Cis- platinum diammine dichloride (CDDP). Thereafter, the coated cores were then coated with a material that did not react with the anticancer agent.
  • an anticancer agent such as Cis- platinum diammine dichloride (CDDP).
  • CDDP Cis- platinum diammine dichloride
  • the coating used in the Sato et al. microcapsule was designed to dissolve in bodily fluid when it was heated to a temperature greater than about 40 degrees Centigrade.
  • a temperature greater than about 40 degrees Centigrade As is disclosed at page 3329 of the Sato et al. article, "We noted the characteristics of HPC-H that it becomes a viscous gel in water at 38 degrees C. or below but loses its viscosity above 40 degrees C. Because of this property, we expected that it would remain a viscous gel and slowly release CDDP at body temperatures of 36 to 37 degrees C but would lose its viscosity and release more CDDP when it is heated to 40 degrees C or above, and we attempted to regulate the release of CDDP by hyperthermia.” Mixtures of nanomagnetic material and a clay mineral
  • a mixture is provided of the nanomagnetic material of this invention (described elsewhere in this specification) and a second material selected from the group consisting of a clay mineral material and an organic materal.
  • the nanomagnetic material is present in this composition at aconcentration of from about 1 to about 99 percent, by weight of the nanomagnetic material and the second material.
  • nanomagnetic material is present at a concentration of from about 5 to about 95 weight percent, by total weight of the two materials.
  • the nanomagnetic material is present at a concentration of from about 10 to about 90 percent.
  • at least 50 weight percent of the mixture of the two materials is nanomagentic material.
  • the second material is a mineral.
  • a mineral is a native, nonorganic or fossilized organic substance having a definite chemical composition and formed by inorganic reactions. See, e.g., page 431 of Julius Grant 's "Hackh's Chemical Dictionary,” Fourth Edition (McGraw-Hill Book Company, New York, New York, 1972).
  • the mineral used is a clay mineral, i.e., a mineral found in clay.
  • clay mineral i.e., a mineral found in clay.
  • These materials are well known in the patent literature. Reference may be had, e.g., to United States patents 3,873,585; 3,915,731; 4,405,371 (clay mineral color developer); 4,600,437; 4,798,630; 4,810,737; 4,839,221(gasket containing PTFE and clay mineral); 4,929,580(process for treating clay minerals); 4,990,544; 5,908,500(activated clay composition); 5,322,879; 5,936,023(clay mineral/rubber composition); 5, 973, 053 (composite clay material); 6,103,817; 6, 121,361 (clay rubber); 6,416,573(pigment); 6,562,891 (modified clay mineral); 6,737,166; and the like. The entire disclosure of each of these United States patents is hereby incorporated by reference into
  • the clay mineral used is a fibrous clay mineral, as that term is described in United States patent 4,364,857, the entire disclosure of which is hereby incorporated by reference into this specification.
  • This patent claims (in claim 1) " L A porous composition of matter comprising codispersed rods of a first fibrous clay and a second fibrous clay, said first fibrous clay having predominantly rods with the length range of 0.5-2 microns and a diameter range of 0.04-0.2 microns and said second fibrous clay having predominantly rods with a length range of 1-5 microns and a diameter range of 50-100 Angstroms.”
  • These "fibrous clays,” and their preparation and processing, are described at columns 2-4 of United States patent 4,365,857, wherein it is disclosed that "The clay halloysite is readily available from natural deposits.
  • halloysite In its natural state, halloysite often comprises bundles of tubular rods or needles consolidated or bound together in weakly parallel orientation. These rods have a length range of about 0.5-2 microns and a diameter range of about 0.04-0.2 microns. Halloysite rods have a central co-axial hole approximately 100-300 Angstroms in diameter forming a scroll-like structure.” United States patent 4,364,857 also discloses that "It has been found that halloysite can make a suitable catalyst for use in demetalizing and hydroprocessing asphaltenes. The halloysite is processed to break up the bundles of rods so that each rod is freely movable with respect to the other rod.
  • the rods When substantially all the rods are freely movable with respect to all the other rods, the rods are defined herein as "dispersed". When the dispersed rod clay is dried and calcined, the random orientation of the rods provides pores of an appropriate size for hydroprocessing and hydrodemetalizing asphaltene fractions.”
  • United States patent 4,364,857 also discloses that "When halloysite rods or other rods of similar dimensions are agitated in a fluid such as water to disperse the rods, the dispersion can be shaped, dried and calcined to provide a porous body having a large pore volume present as 200-700 Angstroms diameter pores.
  • the shaping is by extrusion, however, it has been found that mixtures of dispersed clay rods of the halloysite type, do not extrude well. The rods on the surface of the extruded bodies tend to realign, destroying the desirable pore structure at the surface of the catalyst. This is defined herein as a "skin effect".
  • Codispersed is defined herein as having rod- or tube-like clay particles of at least two distinct types substantially randomly oriented to one another.”
  • United States patent 4,364,857 also discloses that "The second fibrous clay should have long slender fibers typically about 1-5 microns in length with a diameter range of about 50-100 Angstroms. Clays for use as the second component include attapulgite, crysotile, immogolite, palygorskite, sepiolite and the like.” United States patent 4,364,857 also discloses that "The composition of the present invention is prepared by vigorously agitating a mix comprising the first fibrous clay and a second fibrous clay in a liquid dispersing medium. Water is a satisfactory dispersing agent. It is preferred that the slurry contain no more than 25 weight percent of total solids. The vigorous agitation can be accomplished in any suitable manner.
  • a refractory inorganic binder oxide such as alumina, silica, boria, titania, magnesia, or the like can be added to the composition.
  • the finished catalyst support contains less than about 15 weight percent binder oxide, based on the total weight of clay plus binder oxide.
  • An especially preferable inorganic oxide range is about 3-7 percent by weight of the support.”
  • United States patent 4,364,857 also discloses that "If an inorganic oxide component is to be present into the composition of the present invention, codispersal of the rods of the fibrous clay is preferably carried out in the presence of an aqueous hydrogel or the sol precursor of the inorganic oxide gel component.
  • the preferred inorganic oxide is alumina. Mixture of two or more inorganic oxides are suitable for the present invention for example, silica and alumina.”
  • United States patent 4,364,857 also discloses that "A function of the inorganic oxide gel component is to act as a bonding agent for holding or bonding the clay rods in a rigid, three- dimensional matrix. The resulting rigid skeletal framework provides a catalyst body with high crush strength and attrition resistance.”
  • the catalyst may also include one or more catalytically active metals, such as transition metals.
  • a first preferred group of catalytically active metals for use in catalysts of this invention is the group of chromium, molybdenum, tungsten and vanadium.
  • a second preferred group of catalytically active metals is the group of iron, nickel, and cobalt.
  • one or more of the metals of the first group is present in the catalyst at a total amount as metal of about 0.1-10 weight percent and one or more of the metals of the second group is present at a total amount as metal of from about 0.1-10 weight percent, based on the total catalyst weight.
  • Especially preferred combinations include between 0.1 and 10 weight percent of at least one metal from both the first and second preferred groups, for example, molybdenum and cobalt, molybdenum and nickel, tungsten and nickel, and vanadium and nickel.”
  • metals or metal compounds can be added to the slurry as solids or in solution, preferably before dispersion of the clay rods.
  • an aqueous solution of metal can impregnate the dried or calcined bodies.
  • the metals can be present in reduced form or as one or more metal compounds such as oxides or sulfides.
  • One preferred method is impregnating the calcined catalyst bodies with a solution of phosphomolybdic acid and nickel nitrate.”
  • the clay mineral used is a crystalline clay mineral, as that term is used in the claims of United States patent 5,624,544, the entire disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of this patent describes "1.
  • a method for manufacturing ionized water comprising: a first step of dissolving crystalline clay minerals selected from the group consisting of montmorillonite and halloysite in water for electrolysis treatment, and a second step of further dissolving crystal clay minerals in alkaline ionized water and acidic ionized water obtained at the first step, and supplying respectively to the cathode side and anode side, and performing electrolysis treatment so as to produce strong alkaline and strong acidic ionized water maintaining a stable pH, respectively at the cathode side and anode side.”
  • an alkaline ionized water at pH 12 or more, and an acidic ionized water at pH 3 or less are produced.
  • the obtained alkaline ionized water and acidic ionized water are hardly changed in the time course, and the initial pH value is maintained stably for a long period.
  • the crystalline clay minerals are formed in a thin layer state by secondary growth by bonding of tetrahedron of silicic acid and octahedron of alumina. Structurally, crystalline clay minerals are classified into 2-1 type and 1—1 type.”
  • United States patent 5,624,544 also discloses that "The crystalline clay mineral of 2-1 type represented by montmorillonite is formed by 2: 1 bonding of a tetrahedron layer of silicic acid and an octahedron layer of alumina, and a pair of tetrahedron layers of silicic acid are placed from both sides of the octahedron layer of alumina.
  • the crystalline clay mineral of 2-1 type is higher in the content of silicic acid and lower in the content of alumina, as compared with the crystalline clay mineral of 1—1 type.”
  • United States patent 5,624,544 also discloses that "Among overlapped unit layers of crystalline clay mineral of 2-1 type such as montmorillonite, water molecules, Na ions, Ca ions and other cations are invading, and generally bonding between layers is weak, and a large amount of water molecules can be aspirated between the layers.”
  • United States patent 5,624,544 also discloses that "The crystalline clay mineral of 1--1 type is formed by 1: 1 bonding of tetrahedron layer of silicic acid and octahedron layer of alumina, and kaolinite and halloysite belong to the crystalline clay mineral of 1-1 type.
  • kaolinite the alumina plane of basic unit layer is bonded with silicic acid plane of other basic unit layer by hydrogen bond, and groups of 0.03 to 0.05 ⁇ m are formed.
  • halloysite on the other hand, one water molecule layer is present between basic unit layers, and this unit is grouped into a proper size, and the shape is varied including hollow tube, sphere, and cabbage form.”
  • United States patent 5,624,544 also discloses that "In the tetrahedron layer of silicic acid of lamellar clay mineral generally recognized, usually, one silicon ion is surrounded by four oxygen atoms, and the coordination is stable, but in the process of formation of clay mineral, its silicon ion (valence of plus 4) may be sometimes replaced by an aluminum ion (valence of plus 3). At this time, the tetrahedron layer of silicic acid comes to have one unit of negative charge (1.6xlO "19 coulombs).
  • the aluminum ion in the octahedron of alumina may be replaced by Mg ion or Fe ion, and this octahedron of alumina also possesses one unit of negative charge.
  • the permanent electric charge generated in such clay mineral continues to exist regardless of the ambient conditions.
  • the montmorillonite has this property very obviously, and its charging density is a negative charge of 10 2 units per 1 cm 3 , and in spite of its very large charge density, its structure is stably chemically.”
  • United States patent 5,624,544 also discloses that "A pair of tetrahedrons of silicic acid or a pair of octahedrons of alumina share an oxygen atom, but at the terminal end (end face), silicon or aluminum is present only at one side, and the negative charge of oxygen is not satisfied.
  • the clay mineral is very fine and large in specific surface area (for example, montmorillonite has a thickness of about 0.002 to 0.02 ⁇ m in the expanse of 0.1 ⁇ m class, and kaolinite has a length of 0.07 to 3.5 ⁇ m, width of 0.5 to 2.1 ⁇ m, and thickness of 0.03 to 0.05 ⁇ m), and even a trace diffuses sufficiently in water, and electric (electronic) effects are very large.”
  • United States patent 5,624,544 also discloses that "On the end face of the tetrahedron of silicic acid, a negative charge is exposed on the surface, and H+ ions are weakly taken in, and an electric neutrality is maintained. This bond is, however, very weak, and although it is stable when many H+ ions are present in the material water (ionized water) to be electrolyzed (acid and low in pH value), but when the pH value of the material water (ionized water) becomes large and the concentration of OH- ions is high, H+ ions pop out from the tetrahedron of silicic acid accordingly, and silicic acid is charged negatively. That is, when the pH of the material water (ionized water) is larger, it tends to charge negatively, and as the pH value is smaller, it approaches the neutrality.”
  • United States patent 5,624,544 also discloses that "By contrast, the octahedron of alumina is firmly bonded with OH- ions in the state of the positive charge of aluminum exposed on the surface, and as a result, electrically, it is minus and further attracts H+ ions to be charged positively. That is, through the intervening OH- ions, H+ is attracted. This reaction is progressed when the H+ concentration of material water becomes large (the pH value becomes lower), and it is likely to be charged positively when the pH value of the material water (ionized water) becomes lower.”
  • United States patent 5,624,544 also discloses that "Accordingly, on the end face of clay mineral, when the pH value of the water to be electrolyzed becomes higher, the negative charge (OH ' ) increases relatively, and when the pH becomes lower, the positive charge (H + ) becomes dominant.”
  • the clay mineral is selected from the group consisting of smectite clay minerals (e.g., montmorillonite, saponite, hectolite, beidellite, stevensite, nontronite), vermiculite, halloysite or fluorine mica.
  • smectite clay minerals e.g., montmorillonite, saponite, hectolite, beidellite, stevensite, nontronite
  • vermiculite e.g., to United States patent 5,936,023, the entire disclosure of which is hereby incorporated by reference into this specification.
  • the clay mineral is halloysite, a hydrated aluminosilicate that contains alumina (Al 2 O 3 ), silica (SiO 2 ), and water (H 2 O).
  • the halloysite contains abut 3 moles of silica and 2 moles of water for each mole ofalumina, it has a molecular weight of318.1, and it has a melting point above 1,500 degrees Celsius.
  • United States patent 6,401,816 the entire disclosure of which is hereby incorporated by reference into this specification, "Several naturally occurring minerals will, under appropriate hydration conditions, form tubules and other microstructures suitable for use in the present invention.
  • halloysite an inorganic aluminosilicate belonging to the kaolinite group of clay minerals. See generally, Bates et al., "Morphology and structure of endellite and halloysite", American Mineralogists 35 463-85 (1950), which remains the definitive paper on halloysite.
  • the mineral has the chemical formula Al 2 O 3 .2SiO 2 .nH 2 O. In hydrated form the mineral forms good tubules. In dehydrated form the mineral forms broken, collapsed, split, or partially unrolled tubules. "(See lines 46-57 of column 3)
  • a material selected from the group consisting of hydrated halloysite and montmorillonite As is disclosed in column 1 of such patent, "The purified and swollen inorganic gel prepared from a clay such as montmorillonite group, vermiculite, hydrated halloysite, etc., by the manner described hereinafter contains free water, bound water, and water of crystallization."
  • United States patent 6,401, 816(see lines 58-65 of column 3) "The nomenclature for this halloysite mineral is not uniform.
  • the hydrated tubule form of the mineral is called endellite, and the dehydrated form is called halloysite.
  • the hydrated tubule form of the mineral is called halloysite, and the dehydrated form is called is called meta- halloysite.
  • mineralogists will frequently refer to the hydrated mineral as halloysite 10 .A., and the dehydrated mineral as halloysite 7 .A.”
  • both hydrated and dehydrated halloysite comprise layers of single silica tetrahedral and alumina octahedral units. They differ in the presence or absence of a layer of water molecules between the silicate and alumina layers .
  • the basal spacing of the dehydrated form is about 7.2 angstroms, and the basal spacing of the hydrated form is about 10.1 angstroms (hence the names halloysite 7 .A. and halloysite 10 .A).
  • the difference, about 2.9 .A. is about the thickness of a monolayer of water molecules.”
  • the clay mineral used in applicants' composition is endellite.
  • endellite is the hydrated form of halloysite; see, e.g., column 3 of such patent.
  • the clay mineral used in applicants' composition is cylindrite.
  • Cylindrite belongs to the class of minerals known as sulfosalts. Reference may also be had, e.g., to United States patents 4,415,711, 5,561,976 (controlled release of active agents with inorganic tubules), 5,701,191 (sustained delivery of active compounds from tubules), 5,753,736 (dimensionally stable fibers), and the like. The entire disclosure of each of these United States patents is hereby incorporated by reference into this specification.
  • the clay mineral used a sulfosalt known as "Boulangerite.”
  • Reference may be had,e.g., to column 4 of United States patent 6,401,816.
  • Reference may also be had to United States patents 4,515,688; 4,626,279; 4,650,569; 5,182,014; 5,615,976 (inorganic tubules); 5,705,191 (sustained active delivery of compounds from tubules); 6,669,882 (process for making fiber having functional mineral powder), and the like.
  • the entire disclosure of each of these United States patents is hereby incorporated by reference into this specification.
  • the clay mineral used is imogolite.
  • Reference may be had,e.g.,to United States patent 6,401,816 (see column 4).
  • Reference also may be had, e.g., to United States patents 4, 152,404 (synthetic imogolite), 4,241 ,035 (synthetic imogolite), 4,252,799 (synthetic imogolite), 4,394,253 (imogolite catalyst), 4,446,244 (imogolite catalyst), and the like.
  • the entire disclosure of each of these United States patents is hereby incorporated by reference into this specification.
  • the clay mineral is comprised of hollow mineral microtubules with an inner diameter of from about 200 angstroms to about 2000 angstroms and having lengths ranging from about 0.1 microns to about 2.0 microns.
  • This patent claims (in claim 1) " L A composition for use in the delivery of an active agent at an effective rate for a selected time, comprising: hollow mineral microtubules selected from the group consisting of halloysite.
  • microtubules have inner diameters ranging from about 200 Angstroms to about 2000 .Angstroms, and have lengths ranging from about 0.1 ⁇ m to about 2.0 ⁇ m, wherein said active agent is selected from the group consisting of pesticides, antibiotics, antihelmetics, antifouling compounds, dyes, enzymes, peptides, bacterial spores, fungi, hormones, and drugs and is contained within the lumen of said microtubules, and wherein outer and end surfaces of said microtubules are essentially free of said adsorbed active agent.”
  • Capillary attraction and release occurs in tubules having inner diameters of at least about 0.2 ⁇ m.
  • Capillary attraction is relatively weak: agents in tubules having inner diameters of at least about 10 ⁇ m. typically will be released in a matter of hours, without the use of other barriers to release.”
  • United States patent 5,651,976 also discloses that "In contrast to capillary action, adsorption/desorption processes occur over much smaller distance scales, typically on the order of about 1000 .Angstroms. Thus, for tubules in this size range, adsorption/desorption is the controlling process for the release of an active agent inside the interior volume of a microtubule. For a molecule of an active agent contained within the interior volume of a microtubule to reach the end of the tubule, so that the molecule can be released into the environment, the molecule must diffuse through the interior of the tubule while repeatedly being adsorbed and then desorbed by the inner surface of the tubule. This process, which may be conceptualized as a chromatography type of process, is much slower than capillary action, by several orders of magnitude.”
  • United States patent 5,651,976 also discloses that "Several naturally occurring minerals will, under appropriate hydration conditions, form tubules and other microstructures suitable for use in the present invention.
  • the most common of these is halloysite, an inorganic aluminosilicate belonging to the kaolinite group of clay minerals. See generally, Bates et al., "Morphology and structure of endellite and halloysite", American Minerologists 35 463-85 (1950), which remains the definitive paper on halloysite.
  • the mineral has the chemical formula A12 O3.2SiO2.nH2 O. In hydrated form the mineral forms good tubules.
  • Cylindrite belongs to the class of minerals known as sulfosalts.
  • United States patent 5,651,976 also discloses that "Yet another mineral that will, under appropriate conditions, form tubules and other microstructures is boulangerite. Boulangerite also belongs to the class of minerals known as sulfosalts.”
  • United States patent 5,651 ,976 also discloses that "In preferred embodiments of the invention, an active agent is adsorbed onto the inner surface of the lumen of a mineral microstructure. Skilled practitioners will be able to employ known techniques for introducing a wide range of active agents into the lumen of a mineral microstructure according to the invention, thereby making a structure for the modulated release of the active agent. Such structures according to the invention may be used as-is, i.e., as free structures which may be dispensed as desired. Dispensing techniques include scattering, spreading, injecting, etc.”
  • Lumen size selection is governed in part by the availability of ceramic or inorganic microstructures within the suitable size range. Lumen size selection is also governed by the choice of active agent, and the choice of any carrier, coating, or matrix (see infra). The physical and chemical properties (e.g., viscosity, solubility, reactivity, resistance to wear, etc.) of the active agent, any carrier, any coating and any matrix will be considered by a skilled practitioner. Lumen size selection is also governed by the desired release profile for the active agent.”
  • United States patent 5,651,976 also discloses that "Such structures may be included in a surrounding matrix, such as a paint or a polymer. After release from the mineral microstructures, the active agent then diffuses through the surrounding matrix to interface with the use environment. If the surrounding matrix is ablative in the use environment, then the diffusion distance through the matrix is mitigated or eliminated by this ablation.” United States patent 5,651,976 also discloses that "Suitable surrounding matrices will typically be insoluble in the use environment. These matrices include paints (including marine paints), stains, lacquers, shellacs, wood treatment products, and all manner of applied coatings.”
  • the lumen of the microstructure contains both an active agent and a carrier.
  • This carrier further modulates the release of the active agent from the lumen of the microstructure.
  • the active agent may be soluble or mobile in the carrier.
  • the release rate of the active agent will depend on the solubility and diffusion rate of the active agent through the carrier and any coating or matrix.
  • the active agent may be insoluble or immobile in the carrier. Ih this case, the release rate of the active agent will depend on the release rate of the carrier from the tubule, and any coating or matrix.”
  • United States patent 5,651,976 also discloses that "In another embodiment of the invention, the microstructure is coated with a coating material. This coating further modulates the release of the active agent from the lumen of the microstructure. By carefully selecting a coating for its chemical and physical properties, very precise control of the release of the active agent from the lumen of the microstructure can be achieved.”
  • thermoset polymer may be used as a coating in a preferred embodiment of the invention.
  • degree of crosslinking in a thermoset polymer coating and thus the porosity of the thermoset polymer coating, one can obtain a precise degree of control over the release of the active agent from the lumen of the microstructure.
  • Highly crosslinked thermoset coatings will retard the release of the active agent from the lumen more effectively than less crosslinked thermoset coatings.”
  • United States patent 5,651,976 also discloses that "Likewise, the chemical properties of a coating may be used to modulate the release of an active agent from the lumen of a microstructure. For example, it may be desired to use a hydrophobic active agent in an aqueous use environment. However, if one were to load a highly hydrophobic active agent into the lumen of a microstructure according to the invention, and then place this loaded microstructure in an aqueous use environment, the active agent typically would release into the use environment unacceptably slowly, if at all.”
  • United States patent 5,651,976 also discloses that "A wide range of active agents will be suitable for use in the present invention. These suitable active agents include pesticides, antibiotics, antihelmetics, antifouling compounds, dyes, enzymes, peptides, bacterial spores, fungi, hormones, etc.” United States patent 5,651,976 also discloses that "Suitable herbicides include tri-chloro compounds (triox, ergerol), isothiazoline, and chlorothanolil (tufficide). Suitable pesticides include malathion, spectricide, androtenone.
  • Suitable antibiotics include albacilin, amforol, amoxicillin, ampicillin, amprol, ariaprime, aureomycin, aziumycin, chloratetracycline, oxytetracycline, gallimycin, fulvicin, garacin, gentocin, liquamicin, lincomix, nitrofurizone, penicillin, sulfamethazine, sulfapyridine, fulfaquinoxaline, fulfathiozole, and sulkamycin.
  • Suitable antihelmetics include ive ⁇ nictin, vetisulid, trichorofon, tribrissen, tramisol, topazone, telmin, furox, dichlorovos, anthecide, anaprime, acepromazine, pyrantel tartrate, trichlofon, fanbentel, benzimidazoles, and oxibenzidole.
  • Suitable antifouling agents include ergerol, triazine, decanolactone, angelicalactone, galactilone, any lactone compound, capsicum oil, copper sulphate, isothiazalone, organochlorine compounds, organotin compounds, tetracyclines, calcium ionophores such as 504, C23187, tetracycline.
  • Suitable hormones include estrogen, progestin, testosterone, and human growth factor.”
  • Carriers are selected in view of their viscosity and the solubility of the active agent in the carrier.
  • the carrier typically should possess a sufficiently low viscosity to fill the lumen of the microstructure.
  • a low viscosity carrier precursor may be used, and the carrier formed in situ.
  • the lumen may be filled with a low viscosity monomer, and this monomer subsequently may be polymerized inside the lumen.
  • suitable carriers include low molecular weight polymers and monomers, such as polysaccharides, polyesters, polyamides, nylons, polypeptides, polyurethanes, polyethylenes, polypropylenes, polyvinylchlorides, polystyrenes, polyphenols, polyvinyl pyrollidone, polyvinyl alcohol, ethyl cellulose, gar gum, polyvinyl formal resin, water soluble epoxy resins, quietol 651/nma/ddsa, aquon/ddsa/nsa, urea-formaldehyde, polylysine, chitosan, and polyvinylacetate and copolymers and blends thereof.”
  • polysaccharides such as polysaccharides, polyesters, polyamides, nylons, polypeptides, polyurethanes, polyethylenes, polypropylenes, polyvinylchlorides, polystyrenes, polyphenols, polyvinyl pyrollidone,
  • United States patent 5,651,976 also discloses that "Frequently, skilled practitioners may desire to select a carrier that has a very highly selective binding affinity for an active agent of interest.
  • a carrier that has a highly selective binding affinity for an active agent will tend to release that active agent very slowly.
  • very slow release rates may be achieved by the use of carriers with high binding affinities for the active agent to be released.
  • Skilled practitioners will recognize that a consequence of the extensive research that has been done on surface acoustic wave (SAW) analysis is that a large number of polymers have been identified as selective adsorbents for particular organic analytes. See generally, D. S. Ballantine, Jr., S. L. Rose, J. W. Grate, H.
  • SAW surface acoustic wave
  • Preferred carriers include polylactate, polyglycolic acid, polysaccharides (e.g., alginate or chitosan), and mixtures thereof. Each of these carriers is biodegradable. When used in combination with a naturally occurring mineral microtubule, such biodegradable carriers provide an environmentally friendly delivery system.”
  • Example 1 The halloysite was obtained as a crude sample of the lump clay deposit and was hydrated in distilled water, containing 5% by weight sodium metaphosphate. The clay was then crudely crushed by hand, using a metal hammer to break up the large lumps, and foreign material and rocks were sorted by hand. The sample was then transferred into a common kitchen blender adding 200 g of the sample to 1 liter of water. The mixture was allowed to agitate at a medium speed for a period of 30 minutes. The material in suspension was removed and fresh water containing 5% by weight Na metaphosphate was added and the process repeated until the clumps would no longer break down.
  • the suspension was allowed to stand in a 3 L graduate cylinder for 10 minutes, and then the suspended portion of the sample was removed for further processing.
  • the gravity settlement allowed further separation of quartz sand particles from the halloysite.
  • the resultant suspension was spun in an EEC Model C-6000 centrifuge in 1 L bottles and the supernatant removed and replaced with fresh distilled water, and the process was repeated an additional two cycles.
  • the resultant slurry was then filtered through a cloth paint filter cone to remove any remaining large clumps, which were then ground in a mortar and pestle and retreated as before.
  • the halloysite sample was found to be substantially free of foreign material, it was spun out of the water suspension and allowed to air dry. This yielded a white cake of halloysite that was then powdered in a mortar and pestle, to yield a friable white powder.”
  • United States patent 5,651,976 also discloses that "The powder of dry halloysite microcylinders were treated by the following scheme.
  • the active agent which is to be employed by the first method of entrapment should be a solid at or below 40 ° C. In this method both the halloysite and the agent are heated to a temperature just above the melting point of the agent. The best method should be a vacuum oven, if possible, under a partial vacuum to aid in removal of retained gasses within the core of the microcylinders.”
  • United States patent 5,651,976 also discloses that "The halloysite was observed to be "wet" with the active agent.
  • the vacuum was released and the resultant agent/microcylinders complex was suspended in a dispersant that was not a solvent for the agent, and was at the same temperature as the agent/halloysite.
  • the temperature was lowered until the agent became a solid again.
  • the agitation optionally may be stopped at this point and the suspension allowed to settle.
  • the dispersant was removed and the resultant halloysite/agent complex was then suspended in a solvent for the agent.
  • United States patent 5,651,976 also discloses that "The second method employed utilized a suspension of the halloysite and agent in solution of a suitable biodegradable polymer such as a poly- lactic/poly glycolic acid system, which was diluted in a suitable solvent such as methanol. The resultant suspension was then injected into a fluidized bed to flash off the solvent and yield a halloysite/agent mixture which had an outer coating of an environmentally benign coating of degradable polymer.”
  • a suitable biodegradable polymer such as a poly- lactic/poly glycolic acid system
  • United States patent 5,651,976 also discloses that "The third method required the active agent to be miscible with the polylactic/polyglycolic acid mixture, or that the active agent be very small particulates (nanoparticulates). This mixture was then entrapped in the central core of the microcylinders by a method similar to that in the original method, except that the agent was allowed to flash off in the vacuum at ambient temperatures.”
  • United States patent 5,651,976 also discloses that "To determine the encapsulation efficiency, the microcylinders were crushed and suspended in a suitable solvent. The suspension was agitated for several hours to ensure full dissolution of the active agent. The determination of concentration of active agents was made either by weight or by suitable chemical analysis.” United States patent 5,651,976 also discloses that "Laboratory Determination of Release Rate
  • microtubules were added to a conical 50 ml disposable centrifuge, and 50 ml of deionized H2 O was added. Concentration determinations were made based on absorption in a Perkin Elmer UV/Vis series 6000 spectrophotometer. A peristaltic pump was employed to pump the solution through a quartz flow cell where absorption measurements were made each half-hour. When necessary, the deionized H2 O was changed to prevent saturation.”
  • United States patent 5,651,976 also discloses that "Additional modification of the release characteristics has been achieved through employment of a further layer of the degradable polymeric material, where the secondary layer was free of any active agent. This provides a barrier coating to protect against short term exposure to the entrapped agent during handling. This coating then degrades in the environment at a rate that is determinable by the degree of cross-linking of the co-polymers or by employment of an additional crosslinking agent. This allows for a delayed release product. By mixing the thickness of the overcoating, the delay has been tailored to initiate release over a considerable time period.”
  • United States patent 5,651,976 also discloses that "For shorter term release profiles ( ⁇ 300 hr) polysaccharides (including alginate and chitosan) have provided a carrier and a coating that was biodegradable. Due to the open nature of the gel, the release rate has been rather fast, depending on the agent.”
  • the clay mineral used in the composition of this invention is a synthetic clay mineral, that is, a naturally occurring clay mineral that has been modified by one or more human operations.
  • the synthetic clay mineral is a 2:1 layer-type clay mineral product, as that term is defined in United States patent 3,875,288. This patent claims (in claim I) 11 I.
  • nSiO2 :A12 03 :mAB:xH2 O where the layer lattices comprise said silica, said alumina, and said B, and where n is from 1.7 to 3.0, m is from 0.2 to 0.6, A is one equivalent of an exchangeable cation chosen from the group consisting of ammonium, sodium, calcium, hydrogen, and mixtures thereof, and is external to the lattice, B is chosen from the group of anions which consists of F-, OH-, 1/2 02 --, and mixtures thereof, and is internal in the lattice, and x is from 2.0 to 3.5 at 50 percent relative humidity, said mineral being characterized by a dOOl spacing at said humidity within the range which extends from a lower limit of about 12.0 A.
  • A when A is monovalent, to about 14.7 A. when A is divalent, and to a value intermediate between 12.0 A. and 14.7 A. when A includes both monovalent and divalent cations which comprises the steps of forming a reaction mixture by bringing together a 1:1 clay chosen from the group consisting of calcined kaolinite, calcined halloysite, acid-washed calcined kaolinite, acid-washed calcined halloysite, and mixtures thereof; a cation or mixture of cations chosen from the group consisting of said A, together with an equivalent amount of an anion chosen from the group consisting of hydroxyl and fluoride and mixtures thereof; and water; the relative quantities of said reaction mixture components being selected so as to give a molar ratio of SiO2 /A12 03 of between about 1.9 and 3.2; of F-/SiO2 of between about 0.02 and 0.3; and of NH4 +/A12 03 of between about 0.1 and 2.0; and so as to give
  • United States patent 3,875,288 also discloses that "The product having been formed as described, the vessel and contents are allowed to cool until the vessel may be safely opened, and the product is recovered. Any after treatment naturally depends upon the use to be made of the product, Simple draining of excess liquid with or without drying may be adequate. Or, the solids may be washed to any desired degree of freedom from excess salts, and may be base-exchanged with any desired cation or mixture of cations, and ultimately dried and ground if desired.”
  • “An especial advantage of the present invention is that it permits the production of the Granquist-type mineral product with a wider range of silica-to-alumina ratios than originally disclosed. Thus, good syntheses may be made at SiO2 /A12 03 ratios of as small as 1.7. [It may be noted that the product in accordance with the invention generally has an SiO2 /A12 O3 ratio about 0.2 to 0.3 less than that of the reaction mixture.] When this is desired, a kaolinite of suitably low silica/alumina ratio may be selected, since there is some variation in the natural clay.
  • the quantity of reactive silica admixed may be relatively small or great, but of course should not be so great as to exceed the silica/alumina ratio for the reaction mixture already specified herein.”
  • United States patent 3,875,288 also discloses that "Alternatively, the calcined kaolinite or calcined halloysite may be acid-washed, which selectively removes alumina by dissolution, leaving a usable structure with a higher silica/alumina ratio than the starting clay. Any strong acid may be used, such as sulfuric or hydrochloric, followed by water-washing to remove the residual acid and dissolved alumina. In general it is more practical and more economical to add reactive silica.”
  • United States patent 3,875,288 also discloses that "As already stated, the lcaolinite or halloysite or the mixture of both is calcined before use in accordance with the invention. Calcination is carried out within the range 600° to 700° C, preferably about 650° C. The time is not critical, a half-hour or hour sufficing at the preferred temperature. Such calcining fundamentally changes the x-ray diffraction pattern of these clays. If the 1:1 clay is not calcined first, but used as mined, then the conversion to the unique 2:1 Granquist-type clay does not take place.”
  • United States patent 3,875,288 also discloses that "As will be evident from the examples to be given hereinbelow, the cation-anion combinations used in the reaction mixture may quite simply comprise ammonium bifluoride, NH4 F. HF, also written as NH4 HF2 ; and ammonium hydroxide, NH4 OH, in preselected proportions to give the desired ratios.
  • Calcium ion is conveniently added as calcium oxide, or, if included before calcining, as calcium carbonate.
  • Sodium may be added as the hydroxide or the fluoride. In general, we prefer a fluoride/silica ratio of about 0.1; as this ratio diminishes, the reaction time tends to be prolonged.”
  • United States patent 3,875,288 also discloses that "A variation in procedure within the broad scope of the invention comprises the formation of pellets from all or most of the reaction mixture; or from all of the 1:1 clay and most of the other ingredients, with enough water to enable pellets to be readily formed using any commercial pelletizer, as is commonplace in the catalyst industry.
  • a suitable size for the pellets is from about one-eighth to three-sixteenths inch in diameter, although this range may be exceeded. We have had excellent results at one-eighth inch. Kaolinites and halloysites from different sources tend to have different pelletizing characteristics, so that in some cases it may be desirable to include a binder in the mix fed to the pelletizer.
  • a minor quantity of the mineral product made in accordance with the invention in a previous run serves admirably; 10 to 20 percent by weight of the calcined 1:1 clay may be used, for example.
  • some of the reactive silicas have binding properties and may be included for this purpose, especially polysilicic acid.”
  • United States patent 3,875,288 also discloses that "While the pellets so produced may be used forthwith, we prefer and find best to dry the pellets at about 105° C. to 110° C. and then calcine them at about 600° C. to 700° C, and preferably at about 650° C.
  • the synthetic clay mineal is a halloysite that has a surface area greater than 85 square meters per gram, as is described in United States patent 4,098,678, the entire disclosure of which is hereby incorporated by reference into this specification.
  • This United States patent claims (in claim 1) " 1. A process for the conversion of hydrocarbons, which comprises contacting said hydrocarbons at hydrocarbon converting conditions with a synthetic, non-acid treated halloysite containing less than 0.05 wt. % iron and having a surface area greater than 85 sq. meters/gram.” Claim 2 of this patent describes "2.
  • a process for the conversion of hydrocarbons which comprises contacting said hydrocarbons and hydrocarbon converting conditions with a synthetic, non-acid treated halloysite having a surface area greater than 85 sq.
  • the hydrous alumina gel is prepared in accordance with known techniques such as by the reaction of aqueous mixtures of aluminum chloride or aluminum sulfate and an inorganic base such as NH4 OH, NaOH or NaA102, and the like.
  • Preparation of alumina gel by use of ammonium hydroxide is preferable to the use of sodium hydroxide since it is desirable to maintain the soda (Na2 O) content to a low level and because the more alkaline gels tend to form crystalline boehmite.”
  • the silica source may include those sources which are conventionally used for the preparation of crystalline aluminosilicate zeolites. These include silicic acid, silica sol, silica gel, sodium silicate, etc. Silica sols are particularly useful. These are colloidal dispersions of discrete spherical particles of surface-hydroxylated silica such as is sold by E. I. du Pont de Nemours & Company, Inc. under the trademark "Ludox".”
  • United States patent 4,098,678 also discloses that "The proportions of the reactants employed in the initial reaction mixture are determined from the following molar ratio of reactants....The pH of the reaction mixture should be adjusted to a range of about 4 to 10, preferably 6 to 8.
  • the temperature of the reaction mixture should preferably be maintained at between about 230° and 270° C, more preferably 240° to 250° C, for a period from about 2 hours to 100 hours or more.
  • the time necessary for crystallization will depend, of course, upon the temperature of the reaction mixture. By way of example, the crystallization of the synthetic halloysite occurs in about 24 hours at a temperature of about 250° C.”
  • United States patent 4,098,678 also discloses that "The catalytic activity of the synthetic halloysites of the invention can be improved by incorporating therein metals selected from Groups IIA, IIIB, VIB, and Vi ⁇ of the Periodic Table as given in "Websters Seventh New Collegiate Dictionary", (1963) published by G. C. Merriam Company.
  • metals include, among others, magnesium, lanthanum, molybdenum, cobalt, nickel, palladium, platinum and rare earths.
  • Particularly preferred metals include magnesium, nickel, cobalt and lanthanum.
  • the metals are incorporated into the synthetic halloysite structure by adding soluble salts of the metal to the reaction mixture or by coprecipitation of the metal hydroxide with Al(0H)3.
  • the metals are most conveniently added to the reaction mixture in the form of their hydroxides.
  • the synthetic halloysite of the invention particularly when substituted with the afore-described metals, is useful for catalytic cracking, hydrocracking, desulfurization, demetallization and other hydrocarbon conversion processes.
  • substituted halloysites of the invention containing metals such as magnesium, lanthanum and rare earths such as cerium, praseodymium, neodymium, gadolinium, etc. are useful in catalytic cracking of petroleum feedstocks.
  • Synthetic halloysite containing nickel, cobalt, palladium, platinum, and the like are particularly useful for hydrocracking petroleum feedstocks.”
  • the feedstocks suitable for conversion in accordance with the invention include any of the well-known feeds conventionally employed in hydrocarbon conversion processes. Usually they will be petroleum derived, although other sources such as shale oil are not to be excluded. Typical of such feeds are heavy and light virgin gas oils, heavy and light virgin naphthas, solvent extracted gas oils, coker gas oils, steam-cracked gas oils, middle distillates, steam-cracked naphthas, coker naphthas, cycle oils, deasphalted residua, etc.”
  • United States patent 4,098,678 also discloses that "The halloysite structure of the composition of this invention has been confirmed by X-ray diffraction and electron microscopy.
  • the synthetic halloysites of the invention have surface areas ranging from about 85 sq. meters/gram to about 200 sq. meters/gram (BET Method as used, for example, in U.S. Pat. No. 3,804,741) as compared to naturally occurring halloysite which has a surface area generally within the range of 40-85 sq. meters/gram (BET Method).
  • the synthetic halloysite of the invention will be substantially iron-free, i.e., less than 0.05% iron, as compared to naturally occurring halloysite which contains significant amounts of iron.
  • the synthetic and naturally occurring halloysites also differ in that the physical form of the synthetic halloysite is flakes, while the physical form of the natural halloysite has a tube-like configuration. Furthermore, it has been discovered that the synthetic halloysite has considerably better catalytic activity than natural halloysite under analogous hydrocarbon conversion conditions.
  • the synthetic halloysite has the same empirical formula as naturally occurring halloysite, the higher surface area, the elimination of iron and the presence of selective metals makes the synthetic halloysite a more effective hydrocarbon conversion catalyst."
  • the synthetic clay mineral is the synthetic halloysite described in United States patent 4,150,099, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes " 1.
  • a process for preparing halloysite which comprises forming a reaction mixture of aluminum hydroxide gel, silica sol and water having a A1(OH)3 /SiO2 molar ratio in the range of 0.5 to 1.2 and a H2 O/SiO2 molar ratio in the range of 20 to 60 and maintaining said reaction mixture at a pH in the range of 4 to 10 and a temperature of about between 230° and 270° C. for a time sufficient to permit crystallization of halloysite.”
  • the synthetic clay mineral is a chlorinated clay mineral, such as a chlorinated halloysite, as that term is defined in United States patent 4,798,630, the entire disclosure of which is hereby incorporated by reference into this specification. Claiml of United States paten t4,798,630 describes a process for chlorinating an aluminosilicate clay mineralstarting composition, describing " 1.
  • a method for chlorinating and functionalizing an aluminosilicate clay mineral starting composition comprising: reacting a said clay mineral composition selected from one or more members of the group consisting of clays of the halloysite, illite, kaolinite, montmorillonite, and polygorskite groups in substantially dry particulate form with gaseous SiC14 to activate the surface of said composition, thereby forming a reactive chloride intermediate, said reaction being conducted at temperatures in the range of from about 56° C.
  • the synthetic clay mineral is a layered kaolinitic mineral (such as halloysite)that has undergone cation exchange with a specified cation.
  • a "cation halloysite” is described, e.g., in claims 22, 28, and 29 of United States patent 5,530,052, the entire disclosure of which is hereby incorporated by reference into this specification; reference also may be had, e.g., to United States patent 5,707,439. .
  • "Efforts have been disclosed for preparing polymeric nanocomposites.
  • the instant invention is directed to novel compositions prepared from low viscosity macrocyclic oligomers.
  • the synthetic clay mineral is the organophilic phylosilicate described by the claims of United States patent 6,197,849, the entire disclosure of which is hereby incorporated by reference into this specification.Claim 1 of this patent describes "1. An organophilic phyllosilicate which has been prepared by treating a naturally occurring or synthetic phyllosilicate, or a mixture of such silicates, with a salt of a quaternary or other cyclic amidine compound or with a mixture of such salts.” Claim 2 describes "2.
  • An organophilic phyllosilicate according to claim 1 whose preparation uses naturally occurring or synthetic smectite clay minerals, bentonite, vermiculite and/or halloysite, and preferably montmorillonite, saponite, beidelite, nontronite, hectorite, sauconite or stevensite, and particularly preferably montmorillonite and/or hectorite.”
  • Claim 3 describes "3.
  • An organophilic phyllosilicate according to claim 1 which has a distance between layers of from about 0.7 nm-1.2 nm (nanometers) and a cation-exchange capacity in the range from 50-200 meq/100 g.”
  • organophylosilicates of these claims are further described in column 1 of United States patent 6,197,849, wherein it is disclosed that " It is known that organophilic phyllosilicates prepared, for example, by ion exchange, can be used as fillers for thermoplastic materials and also for thermosets, giving nanocomposites. When suitable organophilic phyllosilicates are used as fillers, the physical and mechanical properties of the mouldings thus produced are considerably improved. A particular interesting feature is the increase in stiffness with no decrease in toughness. Nanocomposites which comprise the phyllosilicate in exfoliated form have particularly good properties.”
  • United States patent 6,197,849 also discloses that "U.S. Pat. No. 4,810,734 has disclosed that phyllosilicates can be treated with a quaternary or other ammonium salt of a primary, secondary or tertiary linear organic amine in the presence of a dispersing medium. During this there is ion exchange or cation exchange, where the cation of the ammonium salt becomes embedded into the space between the layers of the phyllosilicate.
  • the organic radical of the absorbed amine makes phyllosilicates modified in this way organophilic. When this organic radical comprises functional groups the organophilic phyllosilicate is able to enter into chemical bonding with a suitable monomer or polymer.
  • thermosets When the amidinium compounds according to the invention are used in thermosets there is no change in the stoichiometry of the reactive components, in contrast to the use of linear ammonium salts, and this allows addition to the thermosetting materials of an increased proportion of tillers.
  • the cyclic amidines used contain reactive groups the organophilic phyllosilicates prepared therewith and used as fillers can be covalently linked to the matrix by grafting.
  • Amidinium ions derived, for example, from hydroxystearic acid or hydroxyoleic acid have surprisingly good layer separation combined with excellent adhesion to a wide variety of polymers and fillers.
  • alkyl groups with nonterminal hydroxyl groups in particular are useful, as well as alkyl substituents with terminal hydroxyl groups.
  • the hydroxyl groups in the alkyl side chain may easily be derivatized in order to tailor a system-specific property spectrum.
  • the compounds also create excellent dispersing effect and interfacial adhesion.
  • the heterocyclic amidine salts according to the invention with long substituted or unsubstituted alkyl radicals, exchange cations efficiently within the spaces between the layers of the phyllosilicates.
  • the synthetic clay mineral is an acidified calcined halloysite, as that term is defined in United States patent 6,294,108, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent refers to " 1.
  • a dry solid composition for generating chlorine dioxide gas consisting essentially of a combination of at least one dry metal chlorite and at least one dry solid hydrophilic material comprising at least one inorganic material selected from the group consisting of hydrous clays, calcined clays, acidified clays and acidified calcined clays, wherein said combination is one which passes both the Dry Air and Humid Air Tests.”
  • Claim 6 of this patent refers to a "hydrous halloysite,” stating "6.
  • the composition of claim 1 wherein the hydrous clay is selected from the group consisting of bentonite, kaolin, attapulgite and halloysite.”
  • Claim 7 refers to "calcined halloysite,” stating "7.
  • composition of claim 1 wherein the calcined clay is selected from the group consisting of metakaolin, spinel phase kaolin, calcined bentonite, calcined halloysite and calcined attapulgite.”
  • Claim 8 refers to "acidified halloysite,” stating "8.
  • composition of claim 1 wherein the acidified clay is selected from the group consisting of bentonite, kaolin, attapulgite and halloysite that have been contacted with one or more acidic solutions containing sulfuric acid, hydrochloric acid, nitric acid or other acidic compounds so that the pH of the resulting liquid phase of the mixture is below 10.5.”
  • Claim 9 refers to "acidified, calcined halloysite," stating " 9.
  • composition of claim 1 wherein the acidified calcined clay is selected from the group consisting of metakaolin, spinel phase kaolin, calcined bentonite, calcined halloysite and calcined attapulgite that have been contacted with one or more acidic solutions containing sulfuric acid, hydrochloric acid, nitric acid or other acidic compounds so that the pH of the resulting liquid phase of the mixture is below 10.5.” Any of these forms of halloysite may be used in the composition of this invention.
  • the synthetic clay mineral is selected from the group conisisting of organosilicate clay and organophilic clay, as these terms are defined by United States patent 6,501,934, the entire disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of this patent describes "An electrophotographic transfer member having a substrate comprising a nanosize polymer filler material wherein said nanosize polymer material is selected from the group consisting of particulate organosilicate clay filler material and organophilic clays, wherein the amount of said filler in said substrate is lower than about 10% by weight.”
  • the "...organosilicate clay filler material is an organically modified talc-type silica (OMTS) in nanosize particulate form.”
  • OMTS organically modified talc-type silica
  • said organophilic clay is an organically modified particulate organically modified mica, bentonite; allophane; kaolinite; halloysite; illite; chlorite; vermiculite; sepiolite; attapulgite; palygorskite; and mixed-layer clay minerals in nanosize particulate form.”
  • the organophilic clay is described at column 3 of United States patent 6,501,934, wherein it is disclosed that "The nanosize polymer material may be an organophilic clay.
  • Organic clay includes layered minerals such as particulate organically modified mica, e.g., muscovite, lepidolite, phlogopite or glauconite; or organically modified bentonite, e.g., montmorillonite; allophane; kaolinite; halloysite; illite; chlorite; vermiculite; sepiolite; attapulgite; palygorskite; and mixed-layer clay minerals in nanosize particulate form which have been intercalated with organic cations.
  • Exemplary cations include onium cations, e.g., higher (including C4 to C20 alkyl) alkylammonium ions like laurylammonium, palmitylammonium, and stearylammonium.
  • the clay from which the organophilic clays are prepared have a cation exchange capacity from 50 to 300 milliequivalents per 100 grams of clay.”
  • United States patent 6,501,934 also discloses that "The intercalation of the layered minerals in the substrate is a consequence of replacing inorganic ions intercalated between mineral layers of the clay with organic ions.
  • the presence of the intercalated organic cations is believed to advantageously finely disperse the mineral in the material from which the substrate material of the invention may be made, e.g., a solution of polyamic acid, which is a polyimide prepolymer.
  • the small size, packing and orientation of the organophilic clay in the film is believed to increase the film strength and the films ability to act as a heat, gas and moisture barrier, which is not feasible with ordinary filler materials.”
  • organophilic clay is also described in the claims of United States patent 6,617,020, the entire disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of United States patent 6,617,020 describes "L A composition comprising: at least one elastomer; organophilic clay plate-like particles; and at least one non-volatile organophilic exfoliating agent; wherein the composition is a hot melt processable pressure sensitive adhesive.”
  • Claim 5 describes the "organophilic clay plate-like particles” as comprising " ...organophilically modified versions of hydrated aluminum silicate, kaolinite, atapulgite, illite, bentonite, halloysite, beidelite, nontronite, hectorite, hectite, saponite, montmorillonite, and combinations thereof.”
  • Claim 6 describes the "organophilic exfoliating agent” as comprising "...a resin having a number average molecular weight of less than about 20,000 g/mol. "
  • organophilic clay isdefined at column 2 of United States patent 6,617,020 as including "...a clay that has been surface-modified to convert at least a portion of its surface nature from an organophobic state to an organophilic state (preferably to a hydrophobic state).
  • a clay may initially have both organophobic and organophilic sites. However, upon modification according to the present invention, at least a portion of the organophobic sites are converted to organophilic sites.
  • a clay initially contains essentially only organophobic sites and, upon modification according to the present invention, at least a portion of the organophobic sites are converted to organophilic sites. Preferably, at least about 50% of exchangeable cations on the unmodified organophilic clay are exchanged with organophilic modifying cations.”
  • organophilic exfoliating agent is defined in column 2 of United States patent6,617,020 as inlucindg "...an organophilic material capable of separating an organophilic clay sheet into plate-like particles and maintaining the clay in plate-like particles at the use temperature (typically room temperature, i.e., about 21° C)."
  • Organic clays and "organophilic exfoliating agents” are also described at columns 5-6 of United States patent 6,617,020, wherein it is disclosed that "Organophilic clay is obtainable by modifying a hydrophilic clay such that the clay is organophilic. Conventional hydrophilic clays are generally not able to be adequately exfoliated according to the present invention. Thus, the present invention utilizes organophilic clays to achieve a higher degree of exfoliation in the clay.”
  • the hydrophilic clay to be modified can be any phyllosilicate or other clay that has a sheet-like structure. Examples thereof include, but are not limited to, hydrated aluminum silicate, kaolinite, atapulgite, illite, halloysite, beidelite, nontronite, hectorite, hectite, bentonite, saponite, and montmorillonite.
  • the smectite clays such as, for example, beidelite, nontronite, hectorite, hectite, bentonite, saponite, and montmorillonite are preferred.”
  • the organophilic clays useful for the invention may be prepared from commercially available hydrophilic clays.
  • the following is an example of a method of preparing organophilic clay:
  • the hydrophilic clay is stirred and dissolved in water to form an exfoliated hydrophilic clay solution.
  • exchangeable ions e.g., sodium or calcium ions
  • organophilic modifying cations comprise onium cations.
  • such cations include, but are not limited to, C2 to C60 alkyl primary, secondary, tertiary, and quaternary ammonium cations and quaternary phosphonium cations.
  • examples thereof include, but are not limited to, (meth)acrylate ammonium cations, such as 2-(dimethylammonium)ethyl methacrylate cations, octadecylammonium cations, dimethyl dihydrogenated tallow ammonium cations, thiol group functionalized alkyl ammonium cations, and combinations thereof.
  • Exchange of the hydrophilic clay ions with organophlic modifying cations causes the modified clay to precipitate from the water solution.
  • organophilically-modified montmorillonite is available as SCPX CLOISITE 2OA, SCPX CLOISITE 15 A, SCPX CLOISITE 1OA, SCPX CLOISITE 6A, SCPX CLOISITE 30b, and SCPX CLOISITE 2398 from Southern Clay Products; Gonzalez, Tex., and under the trade designation, NANOMER, from Nanocor Inc.; Arlington Heights, 111.”
  • the composition of the invention typically comprises any suitable amount of organophilic clay.
  • the amount of organophilic clay present is such that the overall composition is a pressure sensitive adhesive.
  • the composition includes about 1 to about 40 weight percent of the organophilic clay plate-like particles, more preferably about 1 to about 20 weight percent, and most preferably 1 to about 10 weight percent based on the total weight of the composition.
  • composition of the invention typically comprises about 1 to about 75 weight percent of a non-volatile organophilic exfoliating agent based on the total weight of the composition.
  • a non-volatile organophilic exfoliating agent is used to exfoliate the organophilic clay. It has been found that the organophilic clay can be easily exfoliated by exfoliating agents, that are low molecular weight resins.
  • useful low molecular weight resins include, but are not limited to, tackifying agents and low molecular weight block copolymers such as styrene-isoprene block copolymers, styrene-butadiene block copolymers, and hydrogenated block copolymers.
  • exfoliating agents typically have a number average molecular weight of less than about 20,000 g/mol, preferably less than about 10,000 g/mol, and most preferably less than about 5,000 g/mol.”
  • United States patent 6,617,020 also discloses that "Tackifying agents are the preferred exfoliating agents. However, not all tackifying agents will act as an exfoliating agent in any given system.
  • a tackifying agent to function as an exfoliating agent according to the present invention, it generally needs to be viscous enough to impart shear forces in the composition upon exfoliation in order to effectively exfoliate the organophilic clay. It is also preferred that such a tackifying agent would minimize or prevent substantial agglomeration of the exfoliated particles. Selecting a tackifying agent in which the organophilic clay is compatible helps to accomplish this preferred embodiment. Suitable tackifying agents can be found in the following groups: aliphatic, aromatic-modified aliphatic, aromatic, and at least partially hydrogenated versions and derivatives thereof.”
  • tackifying agents that are useful as exfoliating agents include, but are not limited to, rosins, such as wood rosins and their hydrogenated derivatives; derivatives of rosins, such as FORAL 85, a stabilized rosin ester from Hercules Chemical Co.; Wilmington, Del., the SNOWTACK series of gum rosins from Tenneco Corp.; Greenwich, Conn., and the AQUATAC series of tall oil rosins from Arizona Chemical Co.; Panama City, FIa.; terpene resins of various softening points, such as .alpha.-pinene and ⁇ -pinene, available as PICCOLYTE A-115 and ZONAREZ B-100 from Arizona Chemical Co.; Panama City, FIa.; petroleum- based resins, such as the ESCOREZ 1300 series of aliphatic olefin-derived resins and the ESCOREZ 2000 series of
  • United States patent 6,617,020 also discloses that "Particularly preferred are resins derived by polymerization of C5 to C9 unsaturated hydrocarbon monomers, polyterpenes, synthetic polyterpenes and the like. Examples of such commercially available resins of this type are WlNGTACK PLUS tackifying agents, available from Goodyear Tire and Rubber Co.; Akron, Ohio; REGALREZ 1126 tackifying agents, available from Hercules Chemical Co.; Wilmington, Del.; and ESCOREZ 180, ESCOREZ 1310, and ESCOREZ 2393 tackifying agents, all available from Exxon Chemical Co.; Houston, Tex.”
  • the synthetic clay mineral is clay bridged with a metal compound, as that term is defined in United States patent 6,674,009, the entire disclosure of which is hereby incorporated by reference into this specification.
  • the bridged clay may be selected from the group consisting of "...
  • the synthetic clay mineral used in the process of this invention is an organophilic layer silicate as that term is defined in United States patent 6,683,122, the entire disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of this patent describes " 1.
  • a filler mixture comprising an (a) organophilic layer silicate obtainable by treatment of a natural or synthetic layer silicate with a swelling agent selected from the group consisting of sulfonium, phosphonium and ammonium compounds (salts of melamine compounds and cyclic amidine compounds being excluded as ammonium compounds); and (b) a mineral filler different from component (a).
  • a swelling agent selected from the group consisting of sulfonium, phosphonium and ammonium compounds (salts of melamine compounds and cyclic amidine compounds being excluded as ammonium compounds)
  • a mineral filler different from component (a). Claim 2 of this patent " 2.
  • This filler mixture is described at columns 1-3 of United States patent 6,683,122, wherein it is disclosed that "The preparation of organophilic layer silicates by treatment of layer silicates with onium salts, e.g. quaternary ammonium salts, in the presence of a dispersion medium is known from U.S. Pat. No. 4,810,734.
  • the present invention relates to a filler mixture comprising an organophilic layer silicate obtainable by treatment of a natural or synthetic layer silicate with a swelling agent selected from sulfonium, phosphonium and ammonium compounds (salts of melamine compounds and cyclic amidine compounds being excluded as ammonium compounds) and a mineral filler different therefrom.”
  • a swelling agent selected from sulfonium, phosphonium and ammonium compounds (salts of melamine compounds and cyclic amidine compounds being excluded as ammonium compounds) and a mineral filler different therefrom.
  • As layer silicates for the preparation of the organophilic layer silicates of the filler mixtures according to the invention there come into consideration especially natural and synthetic smectite clay minerals, more especially bentonite, vermiculite, halloysite, saponite, beidellite, nontronite, hectorite, sauconite, stevensite and montmorillonite. Montmorillonite and hectorite are preferred.”
  • the layer silicate montmorillonite corresponds generally to the formula A12 [(OH)2 /Si4 Ol 0 ].nH2 O, it being possible for some of the aluminium to have been replaced by magnesium.
  • the composition varies according to the silicate deposit.
  • a preferred composition of the layer silicate corresponds to the formula (A13.15 MgO.85)Si8.OO O20 (OH)4 Xl 1.8.nH2 O, wherein X is an exchangeable cation, generally sodium or potassium, and some of the hydroxyl groups may have been replaced by fluoride ions.
  • Suitable ammonium salts can be prepared, for example, by protonation or quaternisation of corresponding aliphatic, cycloaliphatic or aromatic amines, diamines, polyamines or aminated polyethylene or polypropylene glycols (Jeffamine® M series, D series or T series)."
  • United States patent 6,683,122 also discloses that "Special preference is given to layer silicates in which the layers have a layer spacing of about from 0.7 nm to 1.2 nm and which have a cation exchange capacity in the region of 50 to 200 meq./100 g (milliequivalents per 100 grams).
  • the layer spacing in the organophilic layer silicates so obtained is preferably at least 1.2 nm.
  • Such layer silicates are described, for example, in A. D. Wilson, H. T. Posser, Developments in Ionic Polymers, London, Applied Science Publishers, Chapter 2, 1986.
  • Synthetic layer silicates can be obtained, for example, by reaction of natural layer silicates with sodium hexafluorosilicate and are commercially available inter alia from the CO-OP Chemical Company, Ltd., Tokyo, Japan.”
  • United States patent 6,683,122 also discloses that "For the preparation of the organophilic layer silicates, the swelling agent is first advantageously dispersed or dissolved, with stirring, in a dispersion medium, preferably at elevated temperature of about from 40° C. to 90° C. The layer silicate is then added and dispersed, with stirring. The organophilic layer silicate so obtained is filtered off, washed with water and dried.It is, of course, also possible to prepare the dispersion of the layer silicate as initial batch and then to add the solution or dispersion of the swelling agent.”
  • Suitable dispersion media are water, methanol, ethanol, propanol, isopropanol, ethylene glycol, 1 ,4-butanediol, glycerol, dimethyl sulfoxide, N,N-dimethylformamide, acetic acid, formic acid, pyridine, aniline, phenol, nitrobenzene, acetonitrile, acetone, 2-butanone, chloroform, carbon disulfide, propylene carbonate, 2-methoxyethanol, diethyl ether, tetrachloromethane and n-hexane.
  • Preferred dispersion media are methanol, ethanol and especially water.”
  • United States patent 6,683,122 also discloses that "The swelling agent brings about a widening of the interlayer spacing of the layer silicate, so that the layer silicate is able to take up monomers into the interlayer space. The subsequent polymerisation, polyaddition or polycondensation of the monomer or monomer mixture results in the formation of a composite material, a nanocomposite.”
  • United States patent 6,683,122 also discloses that "In the filler mixtures according to the invention it is preferable to use layer silicates that have been pre-treated with a polymerisable monomer prior to swelling. When the swelling is complete, the compositions are polymerised.
  • Such monomers are, for example, acrylate monomers, methacrylate monomers, caprolactam, laurinlactam, aminoundecanoic acid, aminocaproic acid or aminododecanoic acid.
  • Suitable mineral fillers that can be used in the filler mixtures according to the invention are, for example, glass powder, glass beads, semi-metal and metal oxides, e.g. SiO2 (aerosils, quartz, quartz powder, fused silica), corundum and titanium oxide, semi-metal and metal nitrides, e.g.
  • silicon nitride silicon nitride, boron nitride and aluminium nitride, semi- metal and metal carbides (SiC), metal carbonates (dolomite, chalk, CaCO3), metal sulfates (barite, gypsum), powdered minerals and natural or synthetic minerals primarily from the silicate series, e.g. talcum, mica, kaolin, wollastonite etc. It is also possible to use the untreated layer silicates that are used for the preparation of organophilic layer silicates.”
  • United States patent 6,683,122 also discloses that "Preferred mineral fillers are quartz powder, mica, kaolin, wollastonite, chalk and talcum.”
  • United States patent 6,683,122 also discloses that "In one embodiment, the synthetic clay mineral used is an organoclay, as that term is described in United States patent 6,831,123, the entire disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of this patent describes "A composition comprising at least one ionomeric polyester resin and at least one organoclay, wherein the organoclay is not preswollen before combination with ionomeric polyester resin.” The organoclay is further described in claim 10, which recites that "10.
  • the composition of claim 1 wherein the organoclay comprises at least one member selected from the group consisting of kaolinite, halloysite, dickite, nacrite, montmorillonite, nontronite, beidellite, hectorite, saponite, hydromicas, phengite, brammallite, glaucomite, celadonite, kenyaite, magadite, bentonite, stevensite, muscovite, sauconite, vermiculite, volkonskoite, laponite, mica, fluoromica, and smectite.”
  • organoclays are further described in column 1 of such United States patent, wherein it is disclosed that "Organoclays typically consist of particles comprised of several layers of alumino-silicate plates held together by electrostatic interactions with organic moieties containing metal cations or alkyl ammonium ions intercalated between the plates. Such clays have been used as fillers in resinous composition
  • United States patent 6,831,122 also discloses that "The benefit of organoclays over other mineral fillers in resinous compositions is obtained when the alumino-silicate plates comprising the clay are separated from one another and dispersed in the polymer matrix. Since these plates have a very high aspect ratio, they may provide property enhancement such as reinforcement and improvement in modulus compared to traditional mineral fillers on a per weight of total inorganic content. In order to separate the layers of the clay and obtain maximum reinforcement in a resinous composition, it is typically necessary that polymer adsorb between the layers of the clay causing exfoliation (separation) of the layers.
  • hydrophilic polymers such as polyamides or water-soluble polymers have been used in compositions with organoclays since they may have an affinity for the clay surface promoting exfoliation. It has been found, however, that intimately mixing typically hydrophobic polyester resins and organoclays does not allow for full exfoliation of the clay. Thus properties of the compositions such as modulus may be only marginally better than those properties obtained when traditional fillers are used in typical polyester resins. There is a need to prepare compositions of normally hydrophobic polyester resins with organoclay fillers which achieve optimum beneficial property improvement.”
  • United States patent 6,831,123 also discloses that "PCT Patent Application WO 99/32403 suggests the preparation of an expanded organoclay using a sulfonated polyester as an expanding agent. Following the expansion step, the expanded organoclay is combined in a separate step with a non- ionomeric polyester resin to form a composition with up to 30 weight % expanded organoclay, the clay containing 20 to 80 weight % expanding agent.”
  • organoclay comprises a layered clay, usually a silicate clay, typically derived from a layered mineral and in which organic moieties have been chemically incorporated, ordinarily by ion exchange and especially cation exchange with organic-containing ions and/or onium compounds.
  • Illustrative organic ions are mono- and polyammonium cations such as trimethyldodecylammonium and N,N'-didodecylimidazolium.”
  • United States patent 6,831,123 also discloses that "There is no particular limitation with respect to the layered clays that may be employed in this invention other than that they are capable of undergoing cation exchange with cations and/or onium compounds comprising organic moieties to produce organoclays, and in the form of organoclays they are capable of producing an increase in modulus in a composition containing an ionomeric polyester resin compared to a similar composition containing essentially the same non-ionomeric polyester resin.
  • Illustrative of such layered clays that may be employed in this invention include, for instance, smectite and those of the kaolinite group such as kaolinite, halloysite, dickite, nacrite and the like.”
  • the layered clays are preferably natural or synthetic phyllosilicates, particularly smectic clays.
  • Illustrative examples include, for instance, halloysite, montmorillonite, nontronite, beidellite, saponite, volkonskoite, laponite, sauconite, magadite, kenyaite, bentonite, stevensite, and the like.
  • organoclays comprising minerals of the illite group, including hydromicas, phengite, brammallite, glaucomite, celadonite and the like.
  • the preferred layered minerals include those often referred to as 2:1 layered silicate minerals, including muscovite, vermiculite, saponite, hectorite and montmorillonite, the latter often being most preferred.
  • the clays may be synthetically produced, but most often they comprise naturally occurring minerals and are commercially available. Mixtures of clays for example as described above are also suitable. A more detailed description of suitable clays can be found in U.S. Pat. No.
  • United States patent 6,831,123 also discloses that "It is also within the scope of the instant invention to include layered minerals which are classified as layered double hydroxides, as well as layered minerals having little or no charge on their layers provided that they are capable of undergoing cation exchange with cations and/or onium compounds comprising organic moieties to produce organoclays, and in the form of organoclays they are capable of producing an increase in modulus in a composition containing an ionomeric polyester resin compared to a similar composition containing essentially the same non-ionomeric polyester resin.”
  • United States patent 6,831,123 also discloses that "In addition to the clays mentioned above, admixtures prepared therefrom may also be employed as well as accessory minerals including, for instance, quartz, biotite, limonite, hydrous micas, fluoromicas, feldspar and the like.” United States patent 6,831,123 also discloses that "Preferred layered clays comprise particles containing a plurality of silicate platelets having a thickness of about 7-15 .Angstroms, bound together at interlayer spacings of about 4 .Angstroms, or less, and containing exchangeable cations such as Na+, Ca+2, K+, Al+3, and/or Mg+2 present at the interlayer surfaces.
  • United States patent 6,831,123 also discloses that "The layered clay is cation exchanged with organic-containing ions and/or onium compounds to produce organoclay.
  • Suitable organic-containing ions and/or onium compounds include ammonium cations, pyridinium cations, phosphonium cations, or sulfonium cation represented, respectively, by the general formulas NHx Ry+, PyR+, PyR+, and SR2+, wherein R is an aromatic group, an alkyl group, an aralkyl group, or a mixture thereof, and the sum of x and y is 4; preferably R is an alkyl group.
  • Other suitable organic-containing ions and/or onium compounds include protonated amino acids and salts thereof containing about 2-30 carbon atoms.
  • suitable organic-containing ions and/or onium compounds and processes for employing them are disclosed in U.S. Pat. Nos. 4,810,734; 4,889,885; and 5,530,052 which are incorporated herein by reference.”
  • United States patent 6,831,123 also discloses that "Suitable specific commercially available or easily prepared organoclays which are illustrative of those which may be employed include CLAYTONE HY, a montmorillonite which has been cation exchanged with dimethyldi(hydrogenated tallow)ammonium ion available from Southern Clay Products, and montmorillonite which has been cation exchanged with such ions as dodecylammonium, trimethyldodecylammonium, N,N'- didodecylimidazolium, N,N'-ditetradecylbenzimidazolium, methyl bis(hydroxyethyl)(hydrogenated tallow)amrnoniurn, or methyl bis(2-hydroxyethyl)octadecylammonium.” United States patent 6,831,123 also discloses that "The compositions of the invention may also contain conventional additives.
  • Suitable additives include flame retardants, anti-drip agents, stabilizers, resinous impact modifiers, other fillers such as extending fillers, pigments, dyes, antistatic agents, crystallization aids and mold release agents. Since these are well known in the art, they will not be dealt with in detail herein.” Preparation of a composite containing nanomagnetic material and mineral material
  • Figure 24 is a schematic illustration of a nanocomposite assembly 1100 comprised of tubules 1102 and granular material 1104. These tubules 1102, and their properties, are described elsewhere in this specification and in United States patents 4,877,501 (process for fabrication of lipid microstrucutres), 4,911,981 (metal clad lipid microstrucutres), 5,049,382 (eating and composition contaiing lipid microstructure toxin dispenses), 5,492,696 (controlled relase microstructures), 5,651 ,976 (controlled release of active agents using inorganic tubules), 5,705,191 (sustained delivery of active compounds from tubules, with rational control), 5,744,337 (internal gelation method for forming multilayer microspheres), 6,013,206 (formation of high aspect ratio lipid microtubules), 6,280,759 (method of controlled release and controlled release microstructures), and the like. The entire disclosure of each of these United States patent is hereby incorporated by
  • the tubules 1102 are inorganic tubules, and the granular material 1104 is inorganic granular material.
  • the inorganic tubules are halloysite tubules.
  • Figure 25 is a sectional view of the nancomposite assembly 1100 of Figure 24, showing the granular material 1104 disposed both between the tubules 1102 as well as within the tubules 1102.
  • the granular material 1104 is disposed between the tubules 1102 but not within the tubules 1102.
  • the granular material 1104 is disposed within the tubules 1102 but not between the tubules 1102.
  • tubular material 1100 When the tubular material 1100 is mined (such as, e.g., when halloysite is ined), it generally contains from about 5 to about 95 weight of tubular material 1102; and it often contains from about 5 to about 50 weight percent of tubular material 1102.
  • the as-mined mineral such as, e.g., as mined halloysite
  • the as-mined mineral matter be purified by conventional means to concentrate the long tubules 1102.
  • conventional means may include, e.g., electrostatic means, ultrasonic means, centrifugal means, and/or sieving.
  • the composition 1100 (see Figures 24 and 25) contain at least 80 weight percent of the tubules 1102 and, more preferably, at least 90 weight percent of the tubules 1102. In one aspect of this embodiment, the composition 1100 contains at least 95 weight percent of tubules 1102.
  • Figure 26 is a schematic illustration of a composition 1101 that is comprised of such tubules 1102 and, coated on the outer surfaces 1105 thereof, a multiplicity of particles of nanomagnetic material 1106; this nanomagnetic material 1106, and means for its preparation and coating onto the tubules 1102, are described elsewhere in this specification.
  • the tubules 1102 are halloysite microtubules.
  • Figure 27 is a schematic illustration of a tubule assembly 1103 comrpising a tubules 1102 onto which and into which nanomagnetic material 1106 has been incorporated. Such incorporation of the nanomagnetic material into the microtubule 1102 may be done by conventional means.
  • the tubule 1102 is coated with a multiplicity of nano- sized particles 1106 (such as, e.g., nanomagnetic particles that are smaller than about 100 nanometers and, more preferably, smaller than about 50 nanometers).
  • nanor ⁇ agnetic particles 1106 adhere to both themselves and to the tubules 1102, thereby forming a continuous film 1108 on the outer surface of the tubule 1102.
  • the continuous film 1108 on the outer surface 1105 of the tubule 1102 provides several distinct advantages. In addition to providing adaptive shielding (discussed later in this specification) and potentially modifying the thermal characteristics of such tubule 1102, it also improves the mechanical properties of such tubule 1102.
  • the film 1108 of nanomagnetic particles 1106 preferably has a surface roughness of less than about 50 nanometers and, more preferably, less than about 10 nanometers.
  • the average surface roughness of a thin film is preferably measured by an atomic force microscope (AFM).
  • AFM atomic force microscope
  • a the coated tubules 1107 comprised of a continuous film 1108 of nanomagnetic particles 1106 on outer surface 1105 have improved compressive strength and flexural strength properties.
  • a compositon comprised of at least 80 weight percent of such coated tubules 1107 (and, preferably, at least about 90 weight percent of such coated tubules 1107) is tested in accordance with the procedure described in United States patent 6,290,771, the compressive strength obtained is at least 2,000 kilograms per square centimeter, and the flexural strength obtained is at least about 200 kilograms per square centimeter.
  • Example 1 of United States patent 6,290,771 appears at column 7 of such patent. It discloses that "Cement of 450 g, activated kaolin of 50 g, sands of 1,500 g, water of 250 g and superplasticizer of 5 g were mixed together. Specimens of mortar of 40x40x160 mm were prepared from the mixture. The specimens were wet-cured in a 3-in-l mold for 24 hours, and water-cured for 28 days. Three specimens (Specimens I, II and III) were prepared.”
  • Example 1 has an increase of 14.9% of the conventional mortar (Comparative Example 1) in flexural strength.
  • Example 2 shows a decrease of 27.3% of the conventional mortar (Comparative Example 1) in flexural strength.”
  • United States patent 6,290,771 also discloses that (in column 7) "Compressive strengths were measured according to KS L 5105. The applied force was 80 kg.multidot.force per second. After measurement of the flexural strength, six specimens per Example were tested. The compressive strengths of the specimens were shown in Table 1....As shown in Table 7, the mortar according to the present invention (Example 1) has an increase of 25.8% of the conventional mortar (Comparative Example 1) in compressive strength. The mortar using unactivated kaolin (Comparative Example 2) shows a decrease of 8.9% of the conventional mortar (Comparative Example 1) in compressive strength.” The best flexural strength obtainable in the experiments reported in United States patent
  • the best compressive strength obtainable in the experiments reported in United States patent 6,290,771 was 958 kilograms per square centimeter (see Table 7, Example 1).
  • the compressive strength obtained is at least 2,000 kilograms per square centimeter.
  • the flexural strength so obtained is at least 3,000 kilograms per square centimeter.
  • the term "compressive strength,” as used in this specification (and in the claims of this case), refers to the value obtained when 50 grams of the composition in question is used in the test specified in United States patent 6,290,771.
  • the coating/film 1108 also improves the shielding properties of a composition that contains at least 80 weight percent of the tubules 1107.
  • a composition has shielding factor of at least 0.5 and, preferably, at least about 0.9.
  • a film 104 is adapted to reduce the magnetic field strength at point 108 (which is disposed less than 1 centimeter above film 104) by at least about 50 percent.
  • the film 104 has a magnetic shielding factor of at least about 0.5.
  • the film 1108 (see Figure 28) has a magnetic shielding factor of at least about 0.9, i.e., the magnetic field strength at "point 110" is no greater than about 10 percent of the magnetic field strength at "point 108".
  • the film 1108 engages in "adaptive shielding,” i.e., it changes its electrical properties as it senses electromagnetic radiation.
  • Figures 29 and 30 illustrate why this "adaptive shielding" occurs.
  • Figure 29 illustrates the response of a coating 1108 in response to an alternating current electromagnetic field.
  • Figure 30 illustrates the response of such coating 1108 to both an alternating current electromagnetic field and a direct current magnetic field 1138.
  • the electromagnetic properties of the coating 1108 will depend, at least in part, on the properties and intensity of the a.c. fields and/or d.c. fields to which it is exposed. It will also depend, in part, on the concentrations of the "A", "B”, and “C” moieties discussed elsewhere in this specification and with reference to United States patent 6,765,144 (see Figure 37), the entire disclosure of which is hereby incorporated by reference into this specification.
  • a composition comprised of magnetic material and polymeric material
  • composition comprised of both the nanomagnetic material of this invention and polymeric material.
  • polymer refers to a member of a series of polymeric compounds that are composed of very large molecules which consist essentially of recurring, long-chain structural units; these structural units distinguish polymers from other types of organic molecules and confer on them tensile strength, deformability, elasticity, and hardness. See, e.g., page 534 of Julius Grant's "Haclch's Chemical Dictionary,” Fourth Edition (McGraw-Hill Book Company, New York, New York, 1972) .
  • the composition of this invention is comprised of such nanomagnetic material, such polymeric material, and one or more of the mineral materials described hereinabove.
  • various polymeric materials that may be used in such "magnetic mineral composition” will be described by way of illustration and not limitation.
  • the polymeric material used in the magnetic mineral composition of the instant invention may be comprised of one or more resins such as, e.g., the phenol-formaldehyde resin disclosed in United States patent 3,467,618, the entire disclosure of which is hereby incorporated by reference into this specification.
  • the polymeric material used in the magnetic mineral composition of the instant invention may be a polyamide-containing resin, such as the polyamide material described in United States patent 4,894,411 , the entire disclosure of which is hereby incorporated by reference into this specification.
  • This polyamide resin is described in column 1 of such patent, wherein it is disclosed that "Various attempts have been made so far to incorporate an organic polymeric material with an inorganic material such as calcium carbonate, clay mineral, and mica for the improvement of its mechanical properties.
  • the present inventors developed a composite material composed of a resin containing a polyamide and a layered silicate having a layer thickness of 7-12 .ANG. uniformly dispersed therein, with the polymer chain of said polyamide being partly connected to said silicate through ionic bond.
  • This composite material has a high elastic modulus and heat resistance because of its unique structure; that is, silicate having an extremely high aspect ratio are unifo ⁇ nly dispersed in and connected to a polyamide resin through ionic bond.
  • the amorphous polyamide resin having the aromatic skeleton structure is transparent.
  • An example of the amorphous polyamide resin is "Trogamid” made by Dynamit Nobel Co., Ltd.
  • Terogamid made by Dynamit Nobel Co., Ltd.
  • it is extremely expensive and cannot be a substitute for aliphatic nylons such as nylon-6 and nylon-66.
  • the aliphatic nylon extremely decreases in strength and heat resistance when it is made amorphous. Under these circumstances, there has been a demand for a polyamide resin which has high clarity without decrease in crystallinity.”
  • a polyamide resin composition comprising (A) at least one polyamide resin component selected from the group consisting of a polyamide resin and a resin composition comprising (i) at least 80 weight % of a polyamide resin and (ii) the remainder being another thermoplastic resin selected from the group consisting of polypropylene, an ABS resin, polycarbonate, polyethyleneterephthalate and polybutyleneterephthalate;(B) a layered silicate having a thickness of 6 to 20.ANG., a length of one side of 0.002 to 1 ⁇ m and being uniformly dispersed in the component (A) with a weight ratio of 0.05 to 30 parts by weight of (B) per 100 parts by weight of (A); and respective layers of silicate being positioned apart from each other by 20.ANG.
  • an impact resistance improving material selected from the group consisting ofrimpact resistance improving materials comprising copolymers obtained from ethylene, unsaturated carboxylic acid and unsaturated carboxylic acid metal salt;impact resistance improving materials comprising olefin copolymers containing 0.01 to 10 mole % of acid groups; and mpact resistance improving materials comprising block copolymers, containing 0.01 to 10 mole % of acid groups, obtained from vinyl aromatic compounds and conjugated diene compounds, hydrogenated products of said block copolymers or mixtures thereof, wherein there are 5 to 70 parts by weight (c) per 100 parts by weight of (A)."
  • the polymeric material used in the magnetic mineral composition of this invention may be a polyimide such as, e.g., the polyimide disclosed in United States patent 6,164,660, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes "1.
  • a polyimide composite material which comprises a polyimide-containing resin, organic monoonium ions and a layered clay mineral, said layered clay mineral being intercalated with the organic monoonium ions not bonding with said polyimide and uniformly dispersed in said polyimide.
  • the preparation of the polyimide material of this patent is described, e.g., in column 4 of such patent, wherein it is disclosed that "The polyimide in the present invention is produced from any dianhydride and diamine which are known as monomers for polyimide.
  • Examples of the dianhydride include pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, and 3,3', 4,4'- benzophenonetetracarboxylic dianhydride.
  • Examples of the diamine include4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and p-phenylenediamine. They may be used alone for homopolymerization or in combination with one another for copolymerization. They may be copolymerized with a dicarboxylic acid and a diol or their respective derivatives to give polyamideimide, polyesteramideimide, or polyesterimide.”
  • the polyimide in the present invention is also produced from a prepolymer which is exemplified by poly(amic acid). Usually, a polyimide resin cannot be mixed in its molten state with the intercalated clay mineral because it decomposes at a temperature lower than the temperature at which it begins to flow. But, if the temperature of fluidization is lower than that of decomposition, the polyimide composite material can be produced by this melt-mixing method.”
  • the polymeric material used in the magnetic mineral composition of this invention may be a polypropylene material such as, e.g., the polypropylene thermoplastic resin composition disclosed in United States patent 5,206,284, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes "1.
  • a polypropylene thermoplastic resin composition comprising:
  • a modified polypropylene obtained by grafting a polypropylene with an unsaturated carboxylic acid or a derivative of an unsaturated carboxylic acid (Japanese Patent Publication No. 30945/1970).
  • This approach makes a polypropylene and a polyamide to be compatible with each other and can improve the heat resistance of polypropylene without reducing the impact resistance of polypropylene.”
  • United States patent 5,206,284 also discloses that "However, even in the above improvement of polypropylene by addition of polyamide, the improvement effect is not satisfactory as long as there is used, as the polyamide, an ordinary polyamide such as nylon-6, nylon-6,6, nylon-112 or the like. Recently there has been made a proposal of adding ar aromatic polyamide and a glass fiber to a polypropylene to obtain a material of high strength and low water absorbability [Japanese Patent
  • the polymeric material used in the magnetic mineral composition of this invention may be a polyester, such as poly(ethylene terephthalate), as is disclosed in United States patent 5,876,812, the entire disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of such patent describes " 1.A transparent container for a flowable food product having a decreased permeability for gases, the transparent container consisting essentially of a layer of polyethylene terephthalate integrated with a plurality of synthetic smectite particles between 0.1% and 10% weight of the layer of polyethylene terephthalate, each of the plurality of smectite particles having a thickness of between 9 Angstroms and 100 nanometers, and an aspect ratio of between 100 and 2000, the layer of polyethylene terephthalate having a thickness range of approximately 100 microns to approximately 2000 microns.”
  • the polymeric material used in the magnetic mineral composition of this invention may be a melt processable polymer, as that term is defined in United States patent 5,962,53, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of United States patent 5,962,553 describes " 1.
  • a method of making a composite comprising the steps of: (a) providing 100 parts by weight of melt processable polymer which is a fluoroplastic selected from the group consisting of ethylene-tetrafluoroethylene copolymer, perfluorinated ethylene-propylene copolymer, and tetrafluoroethylene-perfluoro(propyl vinyl ether) copolymer; (b) providing between 1 and 80 parts by weight of a modified layered clay, the modified layered clay being a layered clay having negatively charged layers and modified so as to have organophosphonium cations intercalated between the negatively charged layers, the organophosphonium cations having the structure Rl P+ (R2)3 wherein Rl is a C8 to C24 allcyl or arylalkyl group and each R2, which may be the same or different, is an aryl, arylalkyl, or a Cl to C6 allcyl group; and (c) melt-blending together the melt processable polymer and
  • melt processable polymers that may be used in the process of United States patent 5,962,553 are described at columns 4-5 of such patent, wherein it is disclosed that "Suitable melt processable polymers preferably have a melt processing temperature of at least about 250° C, preferably at least about 270° C.
  • a melt processable polymer is melt processed at a temperature which is at least about 20 to 30° C. above a relevant transition temperature, which can be either a Tm or a Tg, in order to attain complete melting (or softening) of the polymer and to lower its viscosity.
  • melt processable polymer having a melt processing temperature of at least about 250° C. will have a Tm or Tg of at least about 220° C.”
  • melt processable polymers which can be used are crystalline thermoplastics having a crystalline melting temperature (Tm) of at least about 220° C, preferably at least about 250° C, and most preferably at least about 270° C. Tm may be measured by the procedure of ASTM standard E794-85 (Reapproved 1989). For the purposes of this specification, Tm is the melting peak Tm as defined at page 541 of the standard. Either a differential scanning calorimeter (DSC) or a differential thermal analyzer (DTA) may be used, as permitted under the standard, the two techniques yielding similar results.”
  • DSC differential scanning calorimeter
  • DTA differential thermal analyzer
  • Tg may be measured according to ASTM E 1356-91 (Reapproved 1995), again using either DSC or DTA.”
  • United States patent 5,962,553 also discloses that "Turning now to specific types of melt processable polymers which can be used, these include fluoroplastics, poly(phenylene ether ketones), aliphatic polyketones, polyesters, poly(phenylene sulfides) (PPS), poly(phenylene ether sulfones) (PES), poly(ether imides), poly(imides), polycarbonate, and the like. Fluoroplastics are preferred.
  • the organophosphonium modified clays of this invention can also be used to make nanocomposites with polymers having lower melting temperatures, such as aliphatic polyamides (nylons), but since the conventional quaternary ammonium salts can also be used, no special advantage is obtained in such instance."
  • United States patent 5,962,553 also discloses that "A preferred fluoroplastic is ethylene- tetrafluoroethylene copolymer, by which is meant a crystalline copolymer of ethylene, tetrafluoroethylene and optionally additional monomers.
  • Ethylene-tetrafluoroethylene copolymer is also known as ETFE or poly(ethylene-tetrafluoroethylene), and herein the acronym ETFE may be used synonymously for convenience.
  • the mole ratio of ethylene to tetrafluoroethylene can be about 35- 60:65-40.
  • a third monomer may be present in an amount such that the mole ratio of ethylene to tetrafluoroethylene to third monomer is about 40-60:15-50:0-35.
  • the third monomer if present, is so in an amount of about 5 to about 30 mole %.
  • the third monomer may be, e.g., hexafluoropropylene; 3,3,3-trifluoropropylene-l; 2-trifluoromethyl-3,3,3-trifiuoropropylene-l; or perfluoro(alkyl vinyl ether).
  • the melting point varies depending on the mole ratio of ethylene and tetrafluoroethylene and the presence or not of a third monomer.
  • Commercially available ETFE's have melting points between 220 and 270° C, with the grades having melting points above 250° C. being most appropriate for this invention.”
  • EFE for use in this invention is available from various suppliers, including from E.I. du Pont de Nemours under the tradename Tefzel (e.g., grades 280, 2181 and 2129) and from Daikin Industries under the tradename Neoflon (e.g., grades 540, 610 and 620)."
  • Another fluoroplastic suitable for use in this invention is perfluorinated ethylenepropylene copolymer (also known as FEP), by which is meant a copolymer of tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and optionally additional monomers.
  • FEP perfluorinated ethylenepropylene copolymer
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • FEP is predominantly random and has a relatively low HFP content, between about 1 and about 15 weight % based on the total weight of TFE and HFP.
  • the molecular weight is between about 100,000 and about 600,000.
  • a preferred FEP is available from E.I. du Pont de Nemours under the trade name Teflon FEP.
  • FEP The melting point of FEP is about 260° C.
  • United States patent 5,962,553 also discloses that "Yet another suitable fluoroplastic is tetrafluoroethylene-perfluoro(propyl vinyl ether) copolymer (also known as PFA), by which is meant a copolymer of tetrafluoroethylene, perfluoro(propyl vinyl ether), and optionally a third monomer.
  • the third monomer where present, is typically present in an amount of 5 % or less by weight of the polymer and may be, for example, perfluoro(methyl vinyl ether), ⁇ erfluoro(ethyl vinyl ether), perfluoro(butyl vinyl ether), or any other suitable monomer.
  • a representative PFA has about 90 to 99 (preferably 96 to 98) weight % tetrafluoroethylene derived repeat units and about 1 to 10 (preferably 2 to 4) weight % perfluoro(propyl vinyl ether) derived repeat units.
  • a representative crystalline melting point is about 302 to 305° C.
  • PFA is available from E.I. du Pont de Nemours under the tradename Teflon PFA.”
  • PET poly(ethylene terephthalate)
  • Figure PET is available commercially from a variety of suppliers. It is believed to be crystalline, with a Tm in the range of about 250 to about 265° C.”
  • a suitable polyimide is a thermoplastic supplied under the tradename Aurumby Mitsui Toatsu Chemical, Inc. It has a Tg of about 250° C. and a Tm of about 388° C.”
  • the polymeric material used in the magnetic mineral composition of this invention may be a mixture of two or more polymers such as, e.g., the mixture disclosed in United States patent 6,117,932, the entire disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of this patent describes " 1.
  • a resin composite comprising, an organophilic clay and a polymer, wherein said polymer comprises: component (a) two or more polymers, at least one of which is poly(phenylene oxide), or component (b) a copolymer comprising at least one oxazoline functional group.”
  • the polymeric material used in the magnetic mineral composition of this invention may be a polymerized aminoaryl lactam monomer, as is described in United States patent 6,136,908, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes " 1.
  • thermoplastic nanocomposite comprising the steps of: contacting a swellable layered silicate with a polymerizable N-aminoaryl substituted lactam monomer to achieve intercalation of said lactam monomer between adjacent layers of said layered silicate; and .”admixing the intercalated layered silicate with a thermoplastic polymer, and heating the admixture to provide for flow of said polymer and polymerization of the intercalated lactam monomer to cause exfoliation of the layered silicate, thereby forming a thermoplastic nanocomposite having exfoliated silicate layers dispersed in a thermoplastic polymer matrix.”
  • Thelactam monomer used in such process is described in column 2 of the patent as being " ...an N-aminoaryl substituted lactam monomer, which can be prepared via a one-step synthesis by coupling an aromatic amino acid with a lactam having a cyclic ring system containing 1 to 12 carbon atoms.
  • aminoaryl lactams are N-(p-aminobenzoyl)caprolactam, N-(p-aminobenzoyl)butyrolactam, N-(p-aminobenzoyl)valerolactam, and N-(p-aminobenzoyl)dodecanelactam.”
  • the polymeric material used in the magnetic mineral composition may be a conducting polymer, as that term is described in United States patent 6,136,909, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes a process for preparing a conductive polymeric nanocomposite, disclosing " 1.
  • a method for producing a conductive polymeric nanocomposite comprising the steps of: (a) forming a reaction mixture comprising water, an aniline monomer, a protonic acid, an oxidizing agent, and a layered silicate which has been subjected to an acid treatment or is intercalated with polyethylene glycol; and (b) subjecting said reaction mixture to oxidative polymerization to form a conducive polymeric nanocomposite having said layered silicate dispersed in a polymeric matrix of polyaniline, wherein said nanocomposite has a conductivity of greater than 10 '1 S/cm.”
  • Conducting polymers are discussed in column 1 of United States patent 6,136,909, wherein it is disclosed that " In the past decade, conducting polymers have been used in many fields, such as batteries, displays, optics, EMI shielding, LEDs, sensors, and the aeronautical industry.
  • High molecular weight polyaniline has emerged as one of the more promising conducting polymers because of its excellent chemical stability combined with respectable levels of electrical conductivity of the doped or protonated material. Processing of polyaniline high polymers into useful objects and devices, however, has been problematic. Melt processing is not possible, since the polymer decomposes at temperatures below a softening or melting point. In addition, major difficulties have been encountered in attempts to dissolve the high molecular weight polymer.”
  • United States patent 6,136,909 also discloses that "One known method to improve the processibility of polyaniline is by employing a protonic acid dopant containing a long-chain sulfonic group in the polymerization of aniline to form an emulsified colloidal dispersion.
  • this method requires a large quantity of long-chain dopants, which decrease the conductivity and mechanical properties of polyaniline. Ih addition, high aspect ratios of polyaniline are unavailable through this method.
  • aniline monomers are interposed between layered hosts, and then subjected to oxidative polymerization to form composites with highly ordered polymer matrices.
  • the polyaniline composite thus obtained commonly has a conductivity lower than 10-2 S/cm. Moreover, they do not give nanoscale structures.
  • the interlayer spacing (d-spacing) of the inorganic layers is less than 15 .Angstroms,"
  • the polymeric material used in the magnetic mineral composition of this invention may be a benzoaxazine polymer as described, e.g., in claim 1 of United States patent 6,323,270, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes "1. A nanocomposite composition comprising clay and a benzoxazine monomer, oligomer, and/or polymer in amount effective to form nanocomposite. " The preparation of these polymers is described in column 5 of the patent, wherein it is disclosed that "Benzoxazines are prepared by reacting a phenolic compound with an aldehyde and an amine, desirably an aromatic amine.
  • the conventional phenolic reactants for benzoxazines include, for instance, mono and polyphenolic compounds having one or more phenolic groups of the formula [ Figure] in which Rl through R5 can independently be H; OH; halogen; linear or branched aliphatic groups having from 1 to 10 carbon atoms; mono, di, or polyvalent aromatic groups having from 6 to 12 carbon atoms; or a combination of said aliphatic groups and said aromatic groups having from 7 to 12 carbon atoms; mono and divalent phosphine groups having up to 6 carbon atoms; or mono, di and polyvalent amines having up to 6 carbon atoms.
  • at least one of the ortho positions to the OH is unsubstituted, i.e.
  • Rl to R5 is hydrogen.
  • one or more of the Rl through R5 can be an oxygen, an alkylene such as methylene or other hydrocarbon connecting molecule, etc.
  • Example of mono-functional phenols include phenol; cresol; 2-bromo-4-methylphenol; 2- allyphenol; 1,4-aminophenol; and the like.
  • difunctional phenols include phenolphthalane; biphenol; 4-4'-methylene-di-phenol; 4-4'- dihydroxybenzophenone; bisphenol-A; 1,8-dihydroxyanthraquinone; 1,6-dihydroxnaphthalene; 2,2'- dihydroxyazobenzene; resorcinol; fluorene bisphenol; and the like.
  • trifunctional phenols comprise 1,3,5-trihydroxy benzene and the like.
  • Polyvinyl phenol is also a suitable component for the benzoxazine compounds that constitute the subject of the invention.”
  • the polymeric material used in the magnetic mineral composition may be a polyphenylene ether resin as is disclosed, e.g., in United States patent 6,350,804, the entire disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of this patent describes " L A composition comprising: about 30 to about 70 parts by weight of a polyphenylene ether resin; about 20 to about 60 parts by weight of an alkenylaromatic compound, wherein the alkenylaromatic compound is a high impact polystyrene; and about 1 to about 10 parts by weight of an organoclay; wherein the parts by weight of the polyphenylene ether, the alkenylaromatic compound, and the organoclay sum to 100."
  • the polymeric material used in the magnetic mineral composition may be a syndiotactic polystyrene, as that term is defined in the claims of United States patent 6,410,142, the entire disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of this patent describes "A syndiotactic polystyrene/clay nanocomposite comprising: a polymer matrix comprising syndiotactic polystyrene (sPS); and a layered clay material uniformly dispersed in the polymer matrix, said layered clay material being intercalated with an organic onium cation, and the interlayer distances of said layered clay material being at least 20 angstroms.”
  • the nanocomposite described in such claim 1 is further described at columns 2-3 of United States patent 6,410,142, wherein it is disclosed that " The sPS/clay nanocomposite of this invention comprises a polymer matrix containing syndiotactic polystyrene (sPS), and a layered clay material uniformly dispersed in the polymer matrix, said layered clay material being intercalated with an organic onium cation, and the interlayer distances of said layered clay material being at least 20 .ANG..
  • the layered clay material may be intercalated with a polymer or oligomer which is compatible or partially compatible with sPS.
  • the amount of the optionally intercalated polymer or oligomer is preferably in the range from 0.5 to 50 parts by weight per 100 parts by weight of the clay material.”
  • the polymer matrix in the composite material of this invention is a resin containing sPS, namely, a sPS or a mixture thereof with other polymers.
  • the molecular weight of the sPS to be used in the present invention is not specifically limited, but is preferably within the range from about of 15,000 to 800,000 in terms of weight-average molecular weight (Mw).
  • United States patent 6,410,142 also discloses that "The layers of clay material in the composite material of this invention, which are intended to impart the polymeric material with high mechanical strength, have a thickness of about 7 to 12 .Angstroms.. Also, it has been found that the nano-dispersed clay material unexpectedly increases the crystallization rate and crystallization temperature of sPS. The greater the proportion of the clay material in the sPS matrix, the more marked the effects achieved.”
  • United States patent 6,410,142 also discloses that "The amount of the clay material dispersed in the composite material of this invention is preferably in the range from about 0.1 to 40 parts by weight per 100 parts by weight of the polymer matrix. If this amount is less than 0.1 parts, a sufficient reinforcing effect cannot be expected. If the amount exceeds 40 parts, on the other hand, the resulting product is powdery interlayer compound which cannot be used as moldings. In addition, it is also preferable that the composite material of this invention be such that the interlayer distance is at least 30 Angstroms. . The greater the interlayer distance is, the better the mechanical strength will be.” United States patent 6,410,142 also discloses that "Next, the process for manufacturing composite material of this invention is described below.
  • the first step is to bring a cation-type surfactant into contact with a clay material having a cation-exchange capacity of about 50 to 200 meq/100 g, thereby adsorbing the surfactant on the clay material. This can be accomplished by immersing the clay material in an aqueous solution containing the surfactant, followed by washing the treated clay material with water to remove excess ions, thereby effecting ion-exchange operation.”
  • the clay material used in this invention can be any clay material (both natural and synthesized) having a cation exchange capacity of about 50 to 200 meq/100 g.
  • Typical examples include smectite clays (e.g., montmorillonite, saponite, beidellite, nontronite, hectorite, and stevensite), vermiculite, halloysite, sericite, and mica.
  • smectite clays e.g., montmorillonite, saponite, beidellite, nontronite, hectorite, and stevensite
  • vermiculite halloysite
  • sericite and mica.
  • United States patent 6,410,142 also discloses that "The cation-type surfactant serves to expand the interlayer distance in a clay material, thus facilitating the formation of polymer between the silicate layers.
  • the surfactants used in the present invention are organic compounds containing onium ions which-are capable of forming a firm chemical bond with silicates through ion-exchange reaction.
  • Particularly preferred surfactants are ammonium salts containing at least 12 carbon atoms, such as n- hexadecyl trimethylammonium bromide and cetyl pyridinium chloride.”
  • the surface modified clay material may be intercalated with a polymer or oligomer, which is compatible or partially compatible with sPS, as a subsequent modification.
  • aPS atactic polystyrene
  • PPO poly(2,6-dimethyl-l,4-phenylenen oxide)
  • Suitable polymerization time varies with the surfactant adopted, but is usually in the range from 15 to 40 minutes for reaching a weight-average molecular weight of 15,000 to 800,000.
  • the composite material of this invention can be obtained by directly blending the modified clay material with a syndiotactic polystyrene, wherein the clay material may be intercalated with a polymer or oligomer which is compatible or partially compatible with sPS.
  • the blending can be accomplished by a variety of methods which are well-known in the art, such as melt blending or solution blending.
  • the blending can be accomplished by melt blending in a closed system. For example, this can be carried out in a single- or multi-screw extruder, a Banbury mill, or a kneader at a temperature sufficient to cause the polymer blend to melt flow.
  • the blending is preferably carried out at a temperature ranging from about 290° to 310° C.
  • Solution blending can be carried out by dispersing the modified clay in an organic solution of sPS, and thoroughly mixing the dispersion.
  • the intended composite material of this invention can be therefore obtained after evaporation of the organic solvent.”
  • United States patent 6,410,142 also discloses that "The composite materials obtained according to the procedure detailed above may be directly injection-molded, extrusion-molded or compression- molded, or may be mixed with other types of polymers before molding.”
  • the polymeric material used in the magnetic mineral composition of this invention may be an epoxy resin such as, e.g., the epoxy resin described in United States patent 6,548,159, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes" 1.
  • An epoxy/clay nanocomposite comprising: a polymer matrix comprising an epoxy resin; and an exfoliated layered clay material uniformly dispersed in the polymer matrix, wherein the exfoliated layered clay material is present in an amount ranging from about 0.1% to 10% by weight based on the total weight of the nanocomposite and has been modified by ion exchange with (1) benzalkoniurn chloride and (2) dicyandiamide or tetraethylenepentamine.”
  • the polymeric material used in the magnetic mineral composition of this invention may be almost any kind of thermoplastic or thermosetting polymer, as is disclosed in United States patent 6,562,891, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes " 1.
  • a method for producing a polymer/clay composite comprising a polymer matrix selected from the group consisting of polyethylene terephthalate (PET), epoxy resins and polyaniline and a layered clay mineral uniformly dispersed in said polymer matrix, said method comprising the steps of: (a) intercalating a layered clay mineral with a polymerization catalyst in a polar solvent selected from the group consisting of ethylene glycol and water; (b) admixing the intercalated clay mineral with monomers or oligomers of said polymer matrix; and (c) polymerizing said monomers or oligomers under the catalysis of said polymerization catalyst.”
  • Some of the polymers that may be used in the process of such United States patent6,562,891 are described in column3 of the patent, wherein it is disclosed that "The modified clay mineral of the present invention can be admixed with almost any kind of thermoplastic or thermosetting polymers by way of melt blending or oligomer intercalating, followed by polymerization to form polymer
  • the matrix polymer suitable for use in the present invention includes, for example; conductive polymers such as polyaniline, polypyrrole, polythiphene; polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycarbonate (PC); silicones such as polydimethyl siloxane, silicone rubber, silicone resin; acrylic resins such as polymethylmethacrylate, polyacrylate; epoxy resins such as bisphenol-epoxy, phenolic-epoxy; and styrene polymers such as polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer.”
  • conductive polymers such as polyaniline, polypyrrole, polythiphene
  • polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycarbonate (PC)
  • silicones such as polydimethyl siloxane, silicone rubber
  • the polymeric material used in the magnetic mineral composition of this invention may be one of more of the polyamides described in United States patent 6,627,324, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes "1.
  • the polymeric material used in the magnetic mineral composition of this invention may be one or more of the epoxy resins disclosed in United States patent 6,683,122, the entire disclosure of which is hereby incorporated by reference into this specification.
  • suitable epoxy resins include "I) Polyglycidyl and poly( ⁇ -methylglycidyl) esters, obtainable by reaction of a compound having at least two carboxyl groups in the molecule with epichlorohydrin and ⁇ -methyl-epichlorohydrin, respectively. The reaction is advantageously carried out in the presence of bases.
  • Aliphatic polycarboxylic acids can be used as the compound having at least two carboxyl groups in the molecule.
  • polycarboxylic acids examples include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, suberic acid, azelaic acid and dimerised or trimerised linoleic acid. It is also possible, however, to use cycloaliphatic polycarboxylic acids, for example tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4- methylhexahydrophthalic acid. Aromatic polycarboxylic acids, for example phthalic acid, isophthalic acid or terephthalic acid, may also be used.” As is also disclosed in United States patent 6,683,122, to illustrate suitable epoxy resins, "II)
  • Polyglycidyl or poly( ⁇ -methylglycidyl) ethers obtainable by reaction of a compound having at least two free alcoholic hydroxy groups and/or phenolic hydroxy groups with epichlorohydrin or ⁇ - methylepichlorohydrin under alkaline conditions, or in the presence of an acidic catalyst and subsequent alkali treatment.
  • the glycidyl ethers of this kind may be derived, for example, from acyclic alcohols, such as from ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycols, propane- 1,2-diol or poly(oxypropylene) glycols, propane- 1, 3 -diol, butane- 1,4-diol, poly(oxytetramethylene) glycols, pentane-l,5-diol, hexane-l,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1- trimethylolpropane, pentaerythritol, sorbitol and also from polyepichlorohydrins, but they may also be derived, for example, from cycloaliphatic alcohols, such as 1,4-cyclohexanedimethanol, bis(4- hydroxycyclohexyl)methane or 2,2-bis(4
  • the glycidyl ethers may also be derived from mononuclear phenols, for example from resorcinol or hydroquinone, or they may be based on polynuclear phenols, for example bis(4- hydroxyphenyl)methane, 4,4'-di-hydroxybiphenyl, bis(4-hydroxyphenyl)sulfone, l,l,2,2-tetrakis(4- hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4- hydroxyphenyl)propane and also on novolaks, obtainable by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfuraldehyde, with phenols, such as phenol, or with phenols substituted in the nucleus by chlorine atoms or Cl -C9 alkyl groups, for example 4-chlorophenol
  • Poly(N-glycidyl) compounds also include, however, triglycidyl isocyanurate, N,N'-diglycidyl derivatives of cycloalkyleneureas, such as ethyleneurea or 1,3- propyleneurea, and diglycidyl derivatives of hydantoins, such as of 5,5-dimethylhydantoin.
  • V Cycloaliphatic epoxy resins for example bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclo- pentylglycidyl ether, l,2-bis(2,3-epoxycyclopentyloxy)ethane or 3,4-epoxycyclohexylmethyl 3 ',4'- epoxycyclohexanecarboxylate .
  • Epoxy resins in which the 1,2-epoxy groups are bonded to different hetero atoms or functional groups for example the N,N,O-triglycidyl derivative of 4-aminophenol, the glycidyl ether glycidyl ester of salicylic acid, N-glycidyl-N'-(2-glycidyloxypro ⁇ yl)-5,5-dimethyhydantoin or 2-glycidyloxy- l,3-bis(5,5-dimethyl-l-glycidylhydantoin-3-yl)propane.”
  • the 1,2-epoxy groups are bonded to different hetero atoms or functional groups, for example the N,N,O-triglycidyl derivative of 4-aminophenol, the glycidyl ether glycidyl ester of salicylic acid, N-glycidyl-N'-(2-glycidyloxypro ⁇ yl)-5,5-dimethyhy
  • suitable epoxy resins Epoxidation products of unsaturated synthetic or natural oils or derivatives thereof;
  • suitable natural oils are, for example, soybean oil, linseed oil, perilla oil, tung oil, oiticica oil, saffiower oil, poppyseed oil, hemp oil, cottonseed oil, sunflower oil, rapeseed oil, walnut oil, beet oil, high oleic triglycerides, triglycerides from euphorbia plants, groundnut oil, olive oil, olive kernel oil, almond oil, kapok oil, hazelnut oil, apricot kernel oil, beechnut oil, lupin oil, maize oil, sesame oil, grapeseed oil, lallemantia oil, castor oil, herring oil, sardine oil, menhaden oil, whale oil, tall oil, palm oil, palm kernel oil, coconut oil, cashew oil and tallow oil and derivatives derived there
  • suitable natural oils are, for example, soybean oil, linseed
  • United States patent 6,683,122 also discloses that "It is preferable to use as epoxy resin in the curable mixtures according to the invention a fluid or viscous polyglycidyl ether or ester, especially a fluid or viscous bisphenol diglycidyl ether. Especially preferred are bisphenol diglycidyl ethers, especially bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.”
  • United States patent 6,683,122 also discloses that "The above-mentioned epoxy compounds are known and some of them are commercially available. It is also possible to use mixtures of epoxy resins. For example, cured products having a high tensile strength and a high modulus of elasticity can be obtained when the epoxy resin used is a mixture of a bisphenol diglycidyl ether and an epoxidised oil or an epoxidised rubber.”
  • United States patent 6,683,122 also discloses that "All customary hardeners for epoxides can be used; preferred hardeners are amines, carboxylic acids, carboxylic acid anhydrides and phenols. It is also possible to use catalytic hardeners, for example imidazoles. Such hardeners are described, for example, in H. Lee, K. Neville, Handbook of Epoxy Resins, McGraw Hill Book Company, 1982.” United States patent 6,683,122 also discloses that "In a special embodiment of the invention the hardener is an amine, a carboxylic acid, a carboxylic acid anhydride or a phenol and additionally contains a maleinated oil, a maleinated rubber or an alkenyl succinate.
  • Suitable maleinated oils are, for example, the reaction products of the above-mentioned synthetic or natural oils or rubbers with maleic acid anhydride.
  • alkenyl succinate is dodecenyl succinate.
  • the amount of maleinated oil or rubber or of alkenyl succinate is preferably from 0.5 to 30% by weight, more especially from 1 to 20% by weight, based on the total amount of hardener.
  • United States patent 6,683,122 also discloses that "The amount of hardening agent used is governed by the chemical nature of the hardening agent and by the desired properties of the curable mixture and of the cured product. The maximum amount can readily be determined by a person skilled in the art. The preparation of the mixtures can be carried out in customary manner by mixing the components together by manual stirring or with the aid of known mixing apparatus, for example by means of stirrers, kneaders or rollers.
  • United States patent 6,683,122 also discloses that the polymeric material that may be mixed with the layer silicate material may be a polyurethane. United States patent 6,683,122 also discloses that "Further preferred components A are polyurethane precursors. Structural components for crosslinked polyurethanes are polyisocyanates, polyols and optionally polyamines, in each case having two or more of the respective functional groups per molecule.”
  • United States patent 6,683,122 also discloses that "Aromatic and also aliphatic and cycloaliphatic polyisocyanates are suitable building blocks for polyurethane chemistry.
  • Examples of frequently used polyisocyanates are 2,4- and 2,6-diisocyanatotoluene (TDI) and mixtures thereof, especially the mixture of 80% by weight 2,4-isomer and 20% by weight 2,6-isomer; 4,4'- and 2,4'- and 2,2'-methylenediisocyanate (MDI) and mixtures thereof and technical grades that, in addition to containing the above-mentioned simple forms having two aromatic nuclei, may also contain polynuclear forms (polymer MDI); naphthalene- 1, 5 -diisocyanate (NDI); 4,4',4"- triisocyanatotriphenylmethane and l,l-bis(3,5-diisocyanato-2-methyl)-l-phenylmethane; 1,
  • Suitable low molecular weight polyols are, for example, glycols, glycerol, butanediol, trimethylolpropane, erythritol, pentaerythritol; pentitols, such as arabitol, adonitol or xylitol; hexitols, such as sorbitol, mannitol or dulcitol, various sugars, for example saccharose, or sugar and starch derivatives.
  • Low molecular weight reaction products of polyhydroxyl compounds, such as those mentioned, with ethylene oxide and/or propylene oxide are also frequently used as polyurethane components, as well as the low molecular weight reaction products of other compounds that contain sufficient numbers of groups capable of reaction with ethylene oxide and/or propylene oxide, for example the corresponding reaction products of amines, such as especially ammonia, ethylenediamine, 1 ,4-diaminobenzene, 2,4-diaminotoluene, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, l-methyl-3,5-diethyl-2,4-diaminobenzene and/or l-methyl-3,5-diethyl-2,6-diaminobenzene.
  • amines such as especially ammonia, ethylenediamine, 1 ,4-diaminobenzene, 2,4-diaminotol
  • polyester polyols including polylactones, for example polycaprolactones, and polyether polyols.
  • the polyester polyols are generally linear hydroxyl polyesters having molar masses of approximately from 1000 to 3000, preferably up to 2000.
  • Suitable polyether polyols preferably have a molecular weight of about from 300 to 8000 and can be obtained, for example, by reaction of a starter with alkylene oxides, for example with ethylene, propylene or butylene oxides or tetrahydrofuran (polyalkylene glycols).
  • Starters that come into consideration are, for example, water, aliphatic, cycloaliphatic or aromatic polyhydroxyl compounds having generally 2, 3 or 4 hydroxyl groups, such as ethylene glycol, propylene glycol, butanediols, hexanediols, octanediols, dihydroxybenzenes or bisphenols, e.g. bisphenol A, trimethylolpropane or glycerol, or amines (see Ullmanns Encyclopadie der ischen Chemie, 4th edition, Vol. 19, Verlag Chemie GmbH, Weinheim 1980, pages 31-38 and pages 304, 305).
  • aliphatic, cycloaliphatic or aromatic polyhydroxyl compounds having generally 2, 3 or 4 hydroxyl groups such as ethylene glycol, propylene glycol, butanediols, hexanediols, octanediols, dihydroxybenzenes or bisphenol
  • polyalkylene glycols are polyether polyols based on ethylene oxide and polyether polyols based on propylene oxide, and also corresponding ethylene oxide/propylene oxide copolymers, it being possible for such polymers to be statistical or block copolymers.
  • the ratio of ethylene oxide to propylene oxide in such copolymers may vary within wide limits. For example, only the terminal hydroxyl groups of the polyether polyols may have been reacted with ethylene oxide (end capping).
  • the content of ethylene oxide units in the polyether polyols may also, however, have values of e.g. up to 75 or 80% by weight.
  • polyether polyols it will frequently be advantageous for the polyether polyols to be at least end-capped with ethylene oxide, since in that case they will have terminal primary hydroxyl groups which are more reactive than the secondary hydroxyl groups originating from the reaction with propylene oxide.
  • polytetrahydrofurans which, like the polyalkylene glycols already mentioned above, are commercially available (trade name e.g. POLYMEG®). The preparation and properties of such polytetrahydrofurans are described in greater detail, for example, in Ullmanns Encyclopadie der ischen Chemie, 4th edition, Vol. 19, Verlag Chemie GmbH, Weinheim 1980, pages 297-299.”
  • Also suitable as components of polyurethanes are polyether polyols that contain solid organic fillers in disperse distribution and chemically partially bonded to the polyether, such as polymer polyols and polyurea polyols.
  • Polymer polyols are, as is known, polymer dispersions that can be prepared by free-radical polymerisation of suitable olefinic monomers, especially acrylonitrile or styrene or mixtures of the two, in a polyether serving as graft base.
  • Polyurea polyols which can be prepared by reaction of polyisocyanates with polyamines in the presence of polyether polyols, are dispersions of polyureas in polyether polyols, there likewise taking place a partially chemical linkage of the polyurea material to the polyether polyols by way of the hydroxyl groups on the polyether chains.
  • Polyols such as those mentioned in this section are described in greater detail, for example, in Becker/Braun "Kunststoffhandbuch", Vol. 7 (Polyurethanes), 2nd edition, Carl Hanser Verlag, Kunststoff, Vienna (1983), pages 76, 77.”
  • United States patent 6,683,122 also discloses that "Polyamines also play an important role as components in the preparation of polyurethanes, especially because they exhibit greater reactivity than comparable polyols.
  • both low molecular weight polyamines e.g. aliphatic or aromatic di- and polyamines
  • polymeric polyamines e.g. poly(oxyalkylene)polyamines
  • Suitable poly(oxyalkylene)poryamines which, for example, in accordance with U.S. Pat. No. 3,267,050 are obtainable from polyether polyols, preferably have a molecular weight of from 1000 to 4000 and are also commercially available, e.g.
  • JEFF AMINE® such as JEFF AMINE® D2000, an amino-terminated polypropylene glycol of the general formula H2 NCH(CH3)CH2 -[OCH2 CH(CH3)]x --NH2, wherein x has on average the value 33, resulting in a total molecular weight of about 2000; JEFF AMINE® D2001 having the formula H2 NCH(CH3)CH2 --[OCH2 CH(CH3)]a -- [OCH2 CH2 ]b - ⁇ [OCH2 CH(CH3)]c --NH2, wherein b is on average about 40.5 and a+c is about 2.5; JEFFAMINE® BUD 2000, a urea-terminated polypropylene ether of formula H2 N(CO)NH--
  • United States patent 6,683,122 also discloses that "For the preparation of polyurethanes there are often used mixtures of one or more polyols and/or one or more polyamines, as described, for example, in EP-A-O 512 947, EP-A-O 581 739 or the prior art cited in those documents.”
  • United States patent 6,683,122 also discloses that "It is also possible, however, firstly to adduct the swelling agent with a portion of the monomer or monomer mixture, insert the resulting product into the layer silicate and then process that mass with the remaining portion of the resin mixture and the mineral filler to form a moulding material.”
  • the quantity ratio of components A and B in the compositions according to the invention may vary within wide limits.
  • the proportion of component A is preferably from 30 to 95% by weight, more especially from 40 to 92% by weight, and the proportion of component B is preferably from 5 to 70% by weight, more especially from 8 to 60% by weight, based on the sum of components A and B.”
  • compositions according to the invention may contain further customary additives, for example catalysts, stabilisers, propellants, parting agents, fireproofmg agents, fillers and pigments, etc.
  • United States patent 6,683,122 also discloses that "The invention relates also to a process for the preparation of a nanocomposite, wherein a composition comprising components A and B is solidified by curing or polymerisation of component A. Special preference is given to nanocomposites that contain the layer silicate in exfoliated form.” United States patent 6,683,122 also discloses that "By virtue of the very good property profile of the nanocomposites, the compositions according to the invention have a wide variety of uses, inter alia as coatings, paints/vamishes or adhesives.”
  • the polymeric material used in the magnetic mineral composition of this invention may be one or more of the polymers used in the "high molecular substrate" of United States patent 6,710,111, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes "1.
  • a polymer nanocomposite comprising: 60 ⁇ 99 wt % of high molecular substrate; 0.5-30 wt % of layer structured inorganic, well dispersed, coated evenly on the high molecular substrate; and 0.5 ⁇ 30 wt % of polyelectrolyte, which carries the opposite charge of the layer-structured inorganic material and it is attached onto the layer-structured inorganic material.”
  • Claim 2 of this patent describes the "high molecular substrate” as being “...selected from the group consisting of styrene-butadiene rubber, isopiperylene rubber, butadiene rubber, acrylonitrile-butadiene rubber, natural rubber, PVC, PS, PMMA, PU and combinations thereof.”
  • composition of United States patent 6,710,111 is a "polymer nanocomposite," and this type of material is discussed at columns 1-2 of United States patent 6,710,111, wherein it is disclosed that "Nanocomposites are the composites that the diameter of its dispersed particles are in the range of 1-100 nm.
  • the nanocomposites contain layered inorganic material, such as clay, which has the characteristics of nanoscale layer thickness, a high aspect ratio, and ionic bonding between layers.
  • the material has high strength, high rigidity, high resistance to heat, low moisture absorption, low gas permeability and can be multiple recycled for reuse.
  • Nylon 6/clay from Ube Company, Japan, which is used in vehicle parts and air-blocking wrapping films (1990); and from Unitika Company, Japan, which is used in vehicle parts and as an engineering plastic (1996).”
  • United States patent 6,710,111 also discloses that "Conventional methods to produce nanocomposites are: (1) in-situ polymerization, (2) kneading and (3) coagulation and sedimentation.
  • Nylon 6 nanocomposite has been successfully commercialized by in-situ polymerization. However, this method is successful for Nylon 6 nanocomposites only until to now.
  • kneading is convenient, the equipment is considerably expensive and the relative techniques are very complex. It has not been commercialized.
  • coagulation and sedimentation most research, such as Applied Clay Science volume 15 (1999), pages 1 ⁇ 9, has shown that it is hard to avoid the re-coagulate of the layered inorganic material.
  • Butadiene Rubber as disclosed in the journal of Special Rubber Products, issued by Beijing- Univ-Chem-Technol in China, volume 19 (2), pages 6 ⁇ 9, 1997, include: (1) Latex 'method: Vigorously stirring the aqueous to allow clay dispersed in water, SBR latex and antioxidant are then added and uniformly mixed. The mixture is coagulated with the addition of diluted hydrochloric acid. After it is washed with water and dried, clay/SBR nanocomposite is obtained. The lattice spacing of the clay is expanded from 0.98 nm of pure clay to 1.46 nm. This indicates that SBR molecules inserted between layers of clay to form intercalated nanocomposites.
  • the polymeric material used in the magnetic mineral composition of this invention may be a polymeric foam as is described, e.g., United States patent 6,750,264, the entire disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of this patent describes " l. A polymeric foam comprising a polymer having multiple cells defined therein and at least one absorbent clay dispersed within said polymer; wherein said foam has a multimodal cell size distribution and contains less than 0.2 parts by weight of bentonite based on 100 parts by weight of polymer.” Processes for the preparation of such foams are described in columns 3-5 of this patent, wherein it is disclosed that "Polymer resins useful for preparing polymeric foams of the present invention are desirably thermoplastic polymer resins.
  • Suitable thermoplastic polymer resins include any extrudable polymer (including copolymers) including semi-crystalline, amorphous, and ionomeric polymers and blends thereof.
  • Suitable semi-crystalline thermoplastic polymers include polyethylene (PE), such as high- density polyethylene (HDPE), and low-density polyethylene (LDPE); polyesters such as polyethylene terephthalate (PET); polypropylene (PP) including linear, branched and syndiotactic PP; polylactic acid (PLA); syndiotactic polystyrene (SPS); ethylene copolymers including ethylene/styrene copolymers (also known as ethylene/styrene interpolymers), ethylene/alpha-olefm copolymers such as ethylene/octene copolymers including linear low density polyethylene (LLDPE), and ethylene/propylene copolymers.
  • PE polyethylene
  • HDPE high- density polyethylene
  • LDPE
  • Suitable amorphous polymers include polystyrene (PS), polycarbonate (PC), thermoplastic polyurethanes (TPU), polyacrylates (e.g., polymethyl-methacrylate), and polyether sulfone.
  • Preferred thermoplastic polymers include those selected from a group consisting of polymers and copolymers of PS, PP, PE, PC and polyester.
  • Suitable polymer resins include coupled polymers such as coupled PP (see, for example, U.S. Pat. No.
  • Lightly crosslinked polyolefms desirably have a composition content of 0.01% or more, preferably 0.1% or more, and 5% or less, preferably 1% or less according to American Society for Testing and Materials (ASTM) method D2765-84.”
  • United States patent 6,750,264 also discloses that "Foams and processes of the present invention include at least one absorbent clay.
  • An absorbent clay absorbs water into interlayer spacings and, when present in a foamable composition, releases at least a portion of that water as a polymer expands into a foam during foam manufacturing.”
  • An absorbent clay for use in the present invention also desirably has a plasticity index (PI) of less than 500, preferably less than 200, more preferably less than 100, still more preferably less than 75, and greater than zero.
  • PI plasticity index
  • a PI is the difference between the wt % of absorbed water necessary for a clay to change to a near liquid state (liquid limit) and the wt % of absorbed water necessary for a clay to become plastic (plastic limit).
  • a PI is a measure of a clay's plastic range breadth.
  • a clay has a large PI (greater than 500), it can develop an undesirably high viscosity in the presence of water and hinder foam manufacturing.”
  • United States patent 6,750,264 also discloses that "Absorbent clays are distinct from clays that adsorb water. Clays that adsorb water only take up water onto their surface. Clays for use in the present invention absorb water by taking it up into interlayer spacings in the clay. Release of water absorbed into a clay can be controlled more ways than release of water adsorbed on the surface of a clay, providing absorbent clays an advantage over adsorbing clays. Controlling water release allows control over multimodal cell formation.
  • Examples of clays that are not considered absorbent clays because they tend to adsorb rather than absorb water include mica-illite group three-layer-minerals such as pyrophylite, muskovite, dioktaedric illite, glaukonite, talc, biotite, and dioktaedric illite.”
  • Examples of suitable absorbent clays for use in the present invention include two-layer-minerals of the kaolinite-group such as kaolinite, dickite, halloysite, nakrite, serpentine, greenalithe, berthrierine, cronstedtite, and amesite.
  • Halloysite is a particularly desirable absorbent clay for use in the present invention.
  • Two-layer minerals of the kaolinite group tend to absorb water into interlayer spacings without swelling the clay.
  • Smectite-group three-layer minerals can also fall within the scope of an absorbent clay.
  • Smectite-group three-layer minerals include dioktaedric vermiculite, dioktaedric smectite, montmorillonite, beidellite, nontronite, volkonskoite, trioctaedric vermiculite, trioctaedric smectite, saponite, hectorite, and saukonite.
  • Smectite-group three-layer minerals tend to swell as they absorb water between their interlayer spaces.”
  • United States patent 6,750,264 also discloses that "Salt forms of minerals are also included within the scope of absorbent clays.
  • Absorbent clay salts generally have potassium, calcium or magnesium counterions but can also have organic counterions.
  • Certain salt forms of smectite-group three-layer minerals have a plasticity index outside the desired scope of an absorbent clay. For example, sodium montmorillonite has a plastic limit of 97, liquid limit of 700, and a PI of 603. "
  • WO 01/51551 Al discloses a process for forming bimodal polymeric foam using bentonite at a concentration of 0.2 to 10 parts by weight in 100 parts by weight of a thermoplastic resin.
  • Bentonite is a rock whose principle components are montomorillonite salts, particularly sodium montmorillonite.
  • WO 01/51551 Al (incorporated herein by reference) includes in the definition of bentonite natural bentonite, purified bentonite, organic bentonite, modified montmorillonite such as montorillonite modified with an anionic polymer, montmorillonite treated with a silane, and montmorillonite containing a high polarity organic solvent.
  • bentonite refers to the broad definition used in WO 01/51551 Al. In contrast to teachings in WO
  • multimodal foams of the present invention can be made using less than 0.2 weight parts, preferably less than 0.1 weight parts, more preferably less than 0.05 weight parts of bentonite, based on 100 weight parts of polymer. Foams and process for preparing foams of the present invention can be free of bentonite.”
  • United States patent 6,750,264 also discloses that "Polymeric foams of the present invention contain absorbent clays at a concentration of 0.01 wt % or more, preferably 0.1 wt % or more, more preferably 0.2 wt % or more and generally 10 wt % or less, preferably 5 wt % or less, and more preferably 3 wt % or less based on polymer resin weight.
  • suitable absorbent clays have a particle size of 100 micrometers or less, preferably 50 micrometers or less, more preferably 20 micrometers or less. There is no known limit as to how small absorbent clay particles can be for use in the present invention, however the particles typically have a size of one micrometer or more, often 5 micrometers or more. Typically, particle clays having a particle size of 20 micrometers or less are useful for preparing close-celled foams while clays having a particle size of 50 micrometers or greater are useful for preparing open-celled foams. If an absorbent clay swells with water, determine particle size prior to swelling.”
  • Cell-controlling agents also known as nucleating agents
  • Nucleating agents are often useful for controlling cell sizes of smaller cells of a bimodal foam.
  • typical nucleating agents include talc powder and calcium carbonate powder.
  • Foams and processes of the present invention can be substantially free of nucleating agents apart from the absorbent clay. “Substantially free” means having less than 0.05 weight parts per 100 weight parts of polymer resin. Foams and foam preparation process of the present invention can include 0.02 weight parts or less, even 0.01 weight parts or less of nucleating agents other than the absorbent clay. Foams and foam preparation processes of the present invention can be free of nucleating agents other than the absorbent clay.”
  • United States patent 6,750,264 also discloses that "Prepare multimodal foams of the present invention, in general, by preparing a foamable polymer composition at an initial pressure and then expanding the foamable polymer composition at a foaming pressure, which is lower than the initial pressure, into a polymeric foam having a multimodal cell size distribution.
  • the foamable polymer composition comprises a mixture of plasticized polymer resin, a blowing agent composition and an absorbent clay that is capable of expanding into a multimodal polymer foam when upon lowering the initial pressure to the foaming pressure.
  • the initial pressure is a pressure sufficient to liquefy the blowing agent composition and to preclude foaming of the foamable polymer composition.”
  • United States patent 6,750,264 also discloses that "Prepare a foamable polymer composition by blending together components comprising foamable polymer composition in any order. Typically, prepare a foamable polymer composition by plasticizing a polymer resin, blending in an absorbent clay, and then blending in components of a blowing agent composition at an initial pressure.
  • a common process of plasticizing a polymer resin is heat plasticization, which involves heating a polymer resin enough to soften it sufficiently to blend in a blowing agent composition, an absorbent clay, or both.
  • thermoplastic polymer resin to or near to its glass transition temperature (Tg), or melt temperature (Tm) for crystalline polymers.
  • Tg glass transition temperature
  • Tm melt temperature
  • United States patent 6,750,264 also discloses that "Addition of an absorbent clay can occur at any point prior to foaming the foamable polymer composition. For example, an artisan can blend polymer resin and an absorbent clay together while polymerizing the polymer resin, during a melt- blending procedure with a polymer resin but prior to initiating a foaming process (e.g., making polymer pellets containing an absorbent clay), or during a foaming process.”
  • Blowing agent compositions for use in the present invention comprise CO2 and water, and can contain additional blowing agent components.
  • CO2 is present at a concentration of 0.5 wt % or more, preferably 10 wt % or more, more preferably 20 wt % or more and 99.5 wt % or less, preferably 98 wt % or less, and more preferably 95 wt % or less based on blowing agent composition weight.
  • Water is present at a concentration of 0.5 wt % or more, preferably 3 wt % or more, and 80 wt % or less, more preferably 50 wt % or less, and more preferably 20 wt % or less based on blowing agent composition weight.”
  • Additional blowing agents can be present at a concentration ranging from 0 wt % to 80 wt %, based on blowing agent composition weight. Preferably, less than 40 wt % of the blowing agent composition is selected from a group consisting of dimethyl ether, methyl ether, and diethyl ether. Suitable additional blowing agents include physical and chemical blowing agents.
  • Suitable physical blowing agents include HFCs such as methyl fluoride, difluoromethane (HFC-32), perfluoromethane, ethyl fluoride (HFC-161), 1,1-difiuoroethane (HFC- 152a), l,l,l-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2- tetrafluoroethane (HFC- 134a), pentafluoroethane (HFC- 125), perfluoroethane, 2,2-difluoropropane (HFC-272fb), 1,1,1-trifluoropropane (HFC-263fb), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea); liquid hydrofluorocarbons such as 1,1,1,3,3-pentafluoropropane (HFC-245fa), and 1,
  • Suitable chemical blowing agents include azodicarbonamide, azodiisobutyronitrile, benzenesulfo-hydrazide, 4,4-oxybenzene sulfonyl semi-carbazide, p-toluene sulfonyl semi-carbazide, barium azodicarboxylate, N,N'-dimethyl- N,N'-dinitrosoterephthalamide, trihydrazino triazine and sodium bicarbonate.”
  • United States patent 6,750,264 also discloses that "CO2, water, and any additional blowing agents account for 100 wt % of a blowing agent composition for use in the present invention.
  • a blowing agent composition is typically present at a concentration of 3 parts per hundred (pph) or more, preferably 4 pph or more, more preferably 5 pph or more and typically 18 pph or less, preferably 15 pph or less, and more preferably 12 pph or less based on polymer resin weight.”
  • United States patent 6,750,264 also discloses that "One desirable blowing agent composition for use in the present invention contains CO2 and water, and is essentially free of additional blowing agents, meaning that the blowing agent composition comprises 1 wt % or less, preferably 0.5 wt % or less, more preferably 0.1 wt % or less, still more preferably zero wt % of additional blowing agent based on blowing agent composition weight.”
  • United States patent 6,750,264 also discloses that "Another desirable blowing agent composition consists essentially of carbon dioxide, water, and ethanol.
  • Ethanol is useful to reduce foam density and increase foam cell sizes over foams prepared with blowing agents without ethanol.
  • Still another desirable blowing agent composition consists essentially of CO2, water, a Cl -C5 hydrocarbon, and, optionally, ethanol.
  • the hydrocarbon in this particular blowing agent composition can be halogen- free or can be a hydrofluorocarbon.
  • select the hydrocarbon from a group consisting of isobutane, cyclopentane, n-pentane, isopentane, HFC- 134a, HFC-235fa, and HFC-365mfc.
  • the hydrocarbon serves to reduce the thermal conductivity of a resulting foam over a foam prepared without such a hydrofluorocarbon.
  • blowing agent compositions include CO2, water, and at least one of cyclopentane, n-pentane, and isopentane, HFC-134a, HFC-245fa, and HFC-365mfc; and CO2, water, ethanol and at least one of isobutane, cyclopentane, n-pentane, isopentane, HFC-134a, HFC-245fa, and HFC-365mfc.”
  • a foamable polymer composition can contain additional additives such as pigments, fillers, antioxidants, extrusion aids, stabilizing agents, antistatic agents, fire retardants, acid scavengers, and thermally insulating additives.
  • additional additives such as pigments, fillers, antioxidants, extrusion aids, stabilizing agents, antistatic agents, fire retardants, acid scavengers, and thermally insulating additives.
  • One desirable embodiment includes thermally insulating additives such as carbon black, graphite, silicon dioxide, metal flake or powder, or a combination thereof in the foamable polymer composition and foam of the present invention. Add additional additives to a polymer, polymer composition, or foamable polymer composition at any point in the foaming process prior to reducing a foamable polymer composition from an initial pressure to a foaming pressure, preferably after plasticizing a polymer and prior to adding a blowing agent.”
  • Foam preparation processes of the present invention include batch, semi-batch, and continuous processes.
  • Batch processes involve preparation of at least one portion of the foamable polymer composition in a storable state and then using that portion of foamable polymer composition at some future point in time to prepare a foam.
  • prepare a portion of a foamable polymer composition containing an absorbent clay and polymer resin by heat plasticizing a polymer resin, blending in an absorbent clay to form a polymer/clay blend, and then cooling and extruding the polymer/clay blend into pellets.
  • United States patent 6,750,264 also discloses that "A semi-batch process involves preparing at least a portion of a foamable polymer composition and intermittently expanding that foamable polymer composition into a foam all in a single process.
  • U.S. Pat. No. 4,323,528, herein incorporated by reference discloses a process for making polyolefin foams via an accumulating extrusion process.
  • the process comprises: 1) mixing a thermoplastic material and a blowing agent composition to form a foamable polymer composition; 2) extruding the foamable polymer composition into a holding zone maintained at a temperature and pressure which does not allow the foamable polymer composition to foam; the holding zone has a die defining an orifice opening into a zone of lower pressure at which the foamable polymer composition foams and an openable gate closing the die orifice; 3) periodically opening the gate while substantially concurrently applying mechanical pressure by means of a movable ram on the foamable polymer composition to eject it from the holding zone through the die orifice into the zone of lower pressure, and 4) allowing the ejected foamable polymer composition to expand to form the foam.”
  • United States patent 6,750,264 also discloses that "A continuous process involves forming a foamable polymer composition and then expanding that foamable polymer composition in a non-stop manner. For example, prepare a foamable polymer composition in an extruder by heating a polymer resin to form a molten resin, blending into the molten resin an absorbent clay and blowing agent composition at an initial pressure to form a foamable polymer composition, and then extruding that foamable polymer composition through a die into a zone at a foaming pressure and allowing the foamable polymer composition to expand into a multimodal foam. Desirably, cool the foamable polymer composition after addition of the blowing agent and prior to extruding through the die in order to optimize foam properties. Cool the foamable polymer composition, for example, with heat exchangers.”
  • Fibers of the present invention can be of any form imaginable including sheet, plank, rod, tube, beads, or any combination thereof. Included in the present invention are laminate foams that comprise multiple distinguishable longitudinal foam members that are bound to one another. Laminate foams include coalesced foams that comprise multiple coalesced longitudinal foam members. Longitudinal foam members typically extend the length (extrusion direction) of a coalesced polymeric foam. Longitudinal foam members are strands, sheets, or a combination of strands and sheets. Sheets extend the full width or height of a coalesced polymeric foam while strands extend less than the full width and/or height.
  • Width and height are orthogonal dimensions mutually perpendicular to the extrusion direction (length) of a foam.
  • Strands can be of any cross-sectional shape including circular, oval, square, rectangular, hexagonal, or star-shaped. Strands in a single foam can have the same or different cross-sectional shapes.
  • Longitudinal foam members can be solid foam or can be hollow, such as hollow foam tubes (see, for example, U.S. Pat. No. 4,755,408; incorporated herein by reference).
  • the foam of one preferred embodiment of the present invention comprises multiple coalesced foam strands.
  • United States patent 6,750,264 also discloses that "Preparing coalesced polymeric foams typically involves extruding a foamable polymer composition containing polymer resin and a blowing agent formulation through a die defining multiple holes, such as orifices or slits. The foamable polymer composition flows through the holes, forming multiple streams of foamable polymer composition. Each stream expands into a foam member. "Skins" form around each foam member. A skin can be a film of polymer resin or polymer foam having a density higher than an average density of a foam member it is around. Skins extend the full length of each foam member, thereby retaining distinguishability of each foam member within a coalesced polymeric foam. Foam streams contact one another and their skins join together during expansion, thereby forming a coalesced polymeric foam.”
  • United States patent 6,750,264 also discloses that "Other methods are available for joining longitudinal foam members together to form a foam including use of an adhesive between foam members and coalescing foam members together after they are formed by orienting the members and then applying sufficient heat, pressure, or both to coalesce them together. Similar processes are suitable for forming bead foam, which comprises multiple foam beads partially coalesced together. Bead foam is also within the scope of the present invention.” United States patent 6,750,264 also discloses that "Foams of the present invention contain residual blowing agents, including CO2 and water, when fresh. Fresh, herein, means within one day, preferably within one hour, more preferably immediately after manufacturing. Foams of the present invention can also contain residuals of additional blowing agents if they were present during foam preparation.”
  • United States patent 6,750,264 also discloses that "Foams of the present invention typically have a density of 16 kilograms per cubic meter (kg/m3) or more, more typically 20 kg/m3 or more, and still more typically 24 kg/m3 or more and 64 kg/m3 or less, preferably 52 kg/m3 or less, and more preferably 48 kg/m3 or less. Determine foam density according to ASTM method D- 1622.”
  • United States patent 6,750,264 also discloses that "Foams of the present invention can be open- celled or close-celled. Open-celled foams have an open cell content of 20% or more while close-celled foams have an open cell content of less than 20%. Determine open cell content according to ASTM method D-6226. Desirably, the present foams are close-celled foams.”
  • Foams of the present invention are particularly useful as thermal insulating materials and desirably have a thermal conductivity of 30 milliwatts per meter-Kelvin (mW/m-K) or less, preferably 25 mW/m-K or less (according to ASTM method C-518 at 24° C). Foams of the present invention also preferably include a thermally insulating additive. Articles, such as thermally insulating containers, that contain foams of the present invention "
  • the polymeric material used in the magnetic mineral composition of this invention may be,e.g., one or more of the copolymers disclosed in United States patent 6,767,951, the entire disclosure of which is hereby incorporated by reference into this specification.
  • polymers can be built of one, two, or even three different monomers and termed homopolymers, copolymers, and terpolymers, respectively.
  • the "....hydrophilic block comprises poly(vinyl pyrrolidone).
  • the "...hydrophilic block comprises poly(vinyl acetate).
  • the polymeric material used in the magnetic mineral composition of this invention may be the polyamide material of United States patent 6,780,522 that has non-scale nucleating particles dispersed therein; the entire disclosure of this United States patent is hereby incorporated by reference into this specification. Claim 1 of this patent describes "1.
  • Multi-layer film having at least one layer (I) of polyamide with nano-scale nucleating particles dispersed therein, wherein said nano-scale nucleating particles have an aspect ratio of at least 10 in two randomly selectable directions, and, as a number- weighted average, a dimension no greater than 100 nm in at least one direction that is randomly selectable for each consent, having crystalline structures that emanate from the surface of the particles, the amount by weight of the particles, based on the total weight of the polyamide forming the layer (I), is from 10 ppm to 2000 ppm, the polyamide forming the layer (I) contains at least 90% polyamide 6, based on the total mass of the polyamide in that layer and comprising further polyamide-containing layers (II) containing no or less than 10 ppm nano-scale nucleating agent.”
  • the polymeric material used in the magnetic mineral composition of this invention may be an ionomeric polyester as described, e.g., in United States patent 6,831,123, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes "1. A composition comprising at least one ionomeric polyester resin and at least one organoclay, wherein the organoclay is not preswollen before combination with ionomeric polyester resin.” A .composition that contains ceramic material and nanomagnetic material.
  • compositions that contain nanomagnetic material, polymeric material, and (optionally) one or more mineral materials.
  • polymeric material is replaced by a ceramic material.
  • ceramic refers to any of a class of inorganic, nonmetallic products which are subjected to a temperature of 540 degrees Celsius and above during manufacture or use, including metallic oxides, borides, carbides, or nitrides, and mixtures or compounds of such materials. Reference may be had, e.g., to page 54 of Loran S. O'Bannon's "Dictionary of Ceramic Science and Engineering” (Plenum Press, New York, New York, 1984).
  • the ceramic material used in the magnetic mineral composition of this invention may be a calcined diatomaceous earth, as described, e.g., in United States patent 3,793,042, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes " 1.
  • the calcined diatomaceous earth is also described at column 1 of this patent, which discloses that "The calcined diatomaceous earth is a coarse graded calcined diatomaceous silica aggregate that has been converted to the crystobalite form by calcining at not lower than 2,100 0 F. This calcining gives the diatomaceous earth maximum volume stability which prevents swelling during the heating cycles.”
  • the ceramic material used in the magnetic mineral composition of this invention may be a porous ceramic composition such as, e.g., the porous ceramic composition of matter described in United States patent 4,358,400, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes
  • a porous composition of matter comprising: dispersed rods of halloysite, and 0-15 percent by weight of a binder oxide, based on the total weight of said halloysite and binder oxide having a pore volume of at least 0.35 cc/gm of which at least 70 percent of the pore volume is present as pores having a diameter of between 200-700 Angstroms and at least 70 percent of said pores have a diameter of 300- 700 Angstroms.”
  • the preparation of the "dispersed rods of halloysite” is discussed at columns 2-4 of this patent, wherein it is disclosed that "The tubular or rod form of halloysite is readily available from natural deposits.
  • inorganic binder oxides are defined as refractory inorganic oxide such as, silica and oxides of elements in Group 2a, 3b and 3 a of the Periodic Table as defined in Handbook of Chemistry and Physics, 45th Edition.
  • Preferable binder oxides include: silica, alumina, magnesia, zirconia, titania, boria and the like.
  • An especially preferred binder oxide is alumina. It has been discovered that the amount of asphaltene adsorbed onto a catalyst support of dispersed rods of halloysite is related to the amount of binder oxide used.
  • binder oxide When the amount of binder oxide exceeds about 15 percent of the total weight of halloysite and binder oxide, the amount of asphaltenes adsorbed is severely reduced. It has been found that an especially preferable amount of binder oxide is about 5 percent. As more binder oxide is added to the catalyst support, the pore sizes tend to cluster around smaller distributions. A catalyst support with 25 percent alumina has substantially all of its pores less than 100 Angstroms in diameter.”
  • a catalyst support made from halloysite can contain any catalytic reactive transition metal.
  • the catalytic metal component can be added during any stage of preparation.
  • Catalytic metals can be added as powdered salts or oxides during the agitation stage or by impregnation of the catalyst body by adding a metal containing solution after the catalyst bodies have been formed.
  • Preferred catalytic metals are those of Groups VI-B and VIII of the Periodic Table.
  • the composition include at least one metal of the group of chromium, molybdenum, tungsten and vanadium, and at least one metal of the group of iron, nickel and cobalt, such as cobalt-molybdenum, nickel -tungsten or nickel- molybdenum.” It should be noted that, in addition to the means described elsewhere in this specifiation, one may add the nanomagnetic material of this invention to thedispersed rods of halloysite by the means taught in United States patent 4,358,400.
  • United States patent 4,358,400 also discloses that "Preparation of the catalyst with dispersed rods is accomplished by creating a mixture of tubular halloysite and if desired, binder oxide and enough water to form a slurry of about 20 weight percent solid content. As the mixture is violently agitated the slurry is observed to thicken. Agitation is continued until the slurry stops getting thicker with continued agitation. This takes about 10 minutes of agitation. This thickening is indicative of dispersal of the rods. Excess water in the slurry is removed by evaporation until a moldable plastic mass is formed. The bodies are then shaped by spheridizing, pelletizing and similar procedures and then calcined.
  • a catalyst body made of dispersed rods of halloysite tends not to extrude well.
  • the rods tend to realign on the surface of the extruded mass, and this skin effect decreases the average pore diameter at the surface of the extruded mass.
  • the halloysite mass can be dried and calcined; and the calcined mass broken up to produce catalyst bodies.
  • the final product is a catalyst body with the characteristics of dispersed rods of halloysite.
  • the binder oxide be added to the halloysite as the gel or the sol precursor to the gel at the agitation stage of the slurry.” This means may also be used to add nanomagnetic material to thedispersed rods of halloysite.
  • United States patent 4,358,400 also discloses that "Referring to Table I, the pore size distribution for unprocessed halloysite and pore size distribution for halloysite with dispersed rods are compared. It will be noted that in unprocessed halloysite most of the pore size is in the 200-400 Angstrom range. On the other hand, halloysite with dispersed rods has most of it pores distributed from 400-600 Angstroms. In halloysite with dispersed rods there is a substantial amount of pore volume provided by pores having diameters in the range of 100-300 Angstroms. It is believed that these pores are from the central hole present in halloysite rods.
  • Example II of United States patent 4,358,400 discloses the preparation of halloysite with a binder support. As will be apparent to those skilled in the art, one may use the procedure of this Example to prepare a mixture of halloysite and magnetic material.
  • Example II used naturally occurring halloysite from the Dragon Iron Mine in Utah;#13 powder was used.
  • This example illustrates preparation of a catalyst support containing halloysite and a binder oxide.
  • Dragon Halloysite #13 powder is placed in a blender.
  • Enough 5 percent alumina by weight alumina hydrogel is added to form a mixture that is 5 percent by dry weight alumina.
  • the alumina hydrogel is prepared conventionally, as by peptizing a commercially available alumina by a vigorous agitation with a peptizing agent such a nitric acid or formic acid, or by precipitation of the hydrogel from an aluminum nitrate solution with a base such as ammonium hydroxide.
  • Enough water is then added to make a slurry that is no more than about 20 percent solid content.
  • the mixture is then vigorously agitated in a Waring blender until the slurry no longer visibly thickens. Once the halloysite rods are adequately dispersed, the slurry will not get any thicker. Normally this takes about 10 minutes of agitation. Excess water is evaporated from the slurry to form a plastic, workable mass. The mixture is heated to 500° C. for three hours and the calcined mass is broken up into catalyst particles.”
  • the ceramic material used in the magnetic mineral composition of this invention may be cordierite as described, e.g., in United States patent 4,421,699, the entire disclosure of which is hereby incorporated by reference into this specification.. Claiml of this patent describes " 1. A method of producing a cordierite body having a coefficient of thermal expansion of less than 10.5xl0 "7 / 0 C.
  • United States patent 4,421,699 also discloses that "The important points of the present invention are that plate-shaped talc particles contained within the batch raw material impart a low thermal expansion property to the obtained cordierite body, and that halloysite contained within the batch raw material promotes the sintering of the cordierite body.”
  • United States patent 4,421,699 also discloses that "Namely, when talc (3MgO.4SiO2.H2 O) is broken, it is generally delaminated into plate-shaped particles along the (001) plane perpendicular to the C-ciystal axis thereof. And when the batch raw material containing these plate-shaped talc particles is extruded by means of an extrusion die, the plate-shaped talc particles 1 align themselves while the batch raw material passes thin slits of the extrusion die, and the plate-shaped talc particles 1 are oriented in the plane along the surface of the sheet-shaped extruded green body 2.”
  • United States patent 4, 421, 699 also discloses that " In the present invention, halloysite includes metahalloysite and endellite, allophane and the like all of which are formed in the process that the halloysite crystals grow.” It should be noted that each of these clay minerals, or mixtures thereof, or different forms thereof, may be used in the magnetic mineral composition of the instant invention. By way of yet further illustration, one may use a ceramic susceptor material in the magnetic mineral composition of this invention, as that term is described, e.g., in United States patent 4,818,831, the entire disclosure of which is hereby incorporated by reference into this specification. Claim 1 of this patent describes " 1.
  • a package article for food to be heated by microwave energy in a microwave oven comprising: a tray for holding a food item having a top and bottom surface, a substantially planar microwave heating susceptor disposed within said tray, said microwave heating susceptor fabricated from a ceramic composition, comprising: a ceramic binder; and a ceramic susceptor material which absorbs energy and having a residual lattice charge, wherein the compound is unverified, and wherein the susceptor is in intimate physical contact with the food item and ranges in thickness from about 0.5 to 8 mm.”
  • Similar ceramic susceptor compositions are described in United States patents 4,965,423; 4,965,427; and 5,183,787, the entire disclosure of each of which is hereby incorporated by reference into this specification
  • Claim 1 of United States patent 6,290,771 describes "A method of preparing an activated kaolin powder compound for mixing with cement, which comprises: heating natural kaolin to 480° C. for a time period up to one hour, wherein the natural kaolin is primarily composed of halloysite; calcinating the heated natural kaolin in the range of 800°-950° C. over at least 15 minutes; quenching the calcinated kaolin; and pulverizing the quenched activated kaolin to form powder having particle sizes of 2 ⁇ m or less.”
  • the halloysite described in this claim is referred to as "natural kaolin" in the specification ofUnited States patent 6,290,771.
  • the present invention utilizes natural kaolin which is buried under the ground in an tremendous amount.
  • the natural kaolin is activated for use mixing with cement in this invention.
  • the natural kaolin has been used for manufacturing pottery, porcelain, china, etc.
  • an activated kaolin powder has been developed from the natural kaolin, which is capable of being used as one of composite materials for mortar or concrete.
  • the activated kaolin powder is prepared by heating natural kaolin to a certain temperature, calcinating the heated kaolin at high temperature, quenching the calcinated kaolin with water or air, and pulverizing the quenched activated kaolin in a form of powder.”
  • activation of a mineral compound means a state wherein a large amount of crystallization energy is reserved in the molecular structure of the mineral compound when energy is applied to the mineral compound and then the mineral material is quenched, and wherein the mineral compound is in a free state having a strong chemical bonding ability due to the reserved crystallization energy when an external force is applied to the mineral compound.”
  • the natural kaolin is calcinated at high temperature and then quenched, the kaolin reserves a large amount of crystallization energy in the molecular structure and has a latent hydraulicity, because the kaolin molecules are in a free state.
  • the activated kaolin has a high reaction activity and does not cause a hydration when the kaolin contacts with water
  • the kaolin shows a significant water-setting under a certain circumstance, for instance, in an alkali state.
  • Such water-setting is called as "latent hydraulicity”.
  • the present invention is to provide a natural kaolin with the latent hydraulicity by activation, and to cause a mechanism for hydration and pozzolan reaction of the activated kaolin under a certain circumstance such as in mortar or in concrete.”
  • the reactions intended to derive in the present invention are pozzolan reaction and straetlingite reaction, and the pozzolan reaction shown in the following reaction formula (I) is that a silica and Ca(OH)2 are reacted each other, and the straetlingite reaction shown in the following formula (II) is that a silica, a alumina and Ca(OH)2 are reacted each other.
  • the activated kaolin according to the present invention and Ca(OH)2 from cement cause a pozzolan reaction, and the mortar or concrete using the activated kaolin has excellent strength and water permeability due to the latent hydraulicity.”
  • the activated kaolin material is mixed with nanomagnetic material, and this mixture is then formed into cement building blocks that, because of the presence of nanomagnetic material, provides shielding against electromagnetic radiation.
  • a bleeding or segregation phenomenon can be improved when a fine particle component is added to a mortar or concrete, which is called as "stabilizing effect”.
  • the activated kaolin powder causes the stabilizing effect.
  • the activated kaolin powder of this invention can cause an excellent stabilizing effect when the activated kaolin powder is together used with mortar or cement. This is believed because the activated kaolin powder fills the porosities of cement particles or reduces the porosity sizes, and because the activated kaolin powder increases the surface of cement paste and aggregate thereby increasing the bonding force of mortar or cement. " As will be apparent to those skilled in the art, when the activated kaolin also contains nanomagnetic particles, not only is the bonding force of the mortar or cement increased, but also the mortar or cement objects formed are capable of shielding against electromagnetic radiation.
  • the activated kaolin powder compound is prepared from natural kaolin.
  • the activated kaolin powder compound is prepared by heating natural kaolin to 480° C. (for a time period up to one hour, calcinating the heated natural kaolin at 800-950° C. over at least 15 minutes, quenching the calcinated kaolin with water or air, and pulverizing the quenched activated kaolin to give powder having particle sizes of 2 ⁇ m or less.”
  • the kaolin without any treatment can be used in the present invention.
  • a method of pulverizing the quenched activated kaolin comprises crushing by Crusher, and pulverizing by Air Jet Mill. The maximum particle size is 2 ⁇ m, and the average particle size is 0.1-1.0 ⁇ m.”
  • FIG. 1 is a schematic graph showing the relationship of temperature with heating and calcinating time in the process of preparing an activated kaolin powder compound according to the present invention.
  • the natural kaolin which is dried at ambient temperature is heated to 480° C. It is preferable to heat the natural kaolin for a time period up to one hour in aspect of heat efficiency and energy consumption.”
  • the heated natural kaolin is calcinated in the range of 800-950° C.
  • this calcinating step it is preferable to calcinate the heated kaolin over at least 15 minutes.
  • the calcinating step should be conducted for more than 15 minutes in consideration of the heat efficiency and amount of energy used.
  • the temperature should be lower than 950° C, because the physical properties can be adversely affected at the higher temperature than 950° C.
  • the starting temperature for activation of kaolin is in the range of 450-500° C, and the terminating temperature for that is 980° C.
  • the optimum temperature to improve the compressive strength is in the range of 800-950° C.”
  • the calcinated kaolin is quenched with water or air.
  • a water-cooling method is more effective in cost than an air-cooling method.
  • the air- cooling method is that the calcinated kaolin is quenched by using an air spray in the range of 20-60° C, and the water-cooling method is that the calcinated kaolin is immersed in water ranging from 15 to 40° C. Through the quenching step, the kaolin is in an activation state which reserves crystallization energy therein.”
  • the quenched kaolin is pulverized in a form of powder to give particle sizes of 2 ⁇ m or less. Kaolin particles having about 1 ⁇ m are preferably used. The pulverized kaolin powder has a specific gravity of 1.5 to 3.0.”
  • the activated kaolin powder compound is employed in an amount of about 5 to 15% by weight of cement for preparing mortar or cement. It is preferable to employ the activated kaolin powder compound in an amount of about 10% by weight of the cement.
  • a magnetic mineral compositon comprised of an elastomer
  • the magnetic mineral composition of this invention in addition to containing magnetic material (such as nanomagnetic material), also contains an elastomer.
  • an elastomer One may use any of the elastomers that have been used together with clay minerals in the prior art.
  • a gasket comprising a sheet of a composition consisting essentially of a fibrillated polytetrafluoroethylene resin and a fine inorganic powder having an average particle size of not larger than 100 ⁇ m and containing at least 30% by weight of a clay mineral, based on the total weight of the fine inorganic powder, said composition characterized in that the polytetrafluoroethylene resin is at least 5% by weight and the fine inorganic powder is at least 40% by weight, based on the total amount of the polytetrafluoroethylene resin and the fine inorganic powder, the polytetrafluoroethylene resin and the fine inorganic powder are mutually uniformly dispersed and mixed with each other, and further comprising a metal support for said sheet.”
  • the elastomer may, e.g., be an adhesive composition, as described in United States patent 5,686,099, the entire disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of this patent describes "A dermal composition comprising a mixture of 0.1 to 50 by dry weight of a drug, a pressure sensitive adhesive, a liquid solvent for one or more of the components of the composition and about 0.1 to about 10% by dry/weight of the total composition of clay to increase the adhesiveness of the composition.
  • pressure sensitive adhesive is also described at columns 5-6 of the patent, wherein it is disclosed that "The term “pressure sensitive adhesive” as used herein means and refers to polymers, including but not limited to homopolymers, copolymers and mixtures of polymers, which are adhesive in the sense that they can adhere to the skin of an animal and which are pressure sensitive in the sense that adherence can be effected by the application of pressure.
  • the pressure sensitive adhesive can function as a matrix for the drug.
  • the adhesive is sufficiently resistant to chemical and/or physical attack by the environment of use so that it remains substantially intact throughout the period of use.
  • the adhesive is biocompatible in the environment of use, plastically deformable and with limited water solubility solubility.
  • water as used herein includes water containing biological fluids such as saline and buffers.”
  • a wide variety of polymers are known to be suitable for use in pressure sensitive adhesives. Suitable polymers include a natural or synthetic rubber, acryates, polycarboxylic acids or anhydrides thereof, vinyl acetate polymers and the like.
  • a pressure sensitive adhesive can be composed of a single polymer or mixtures thereof. It is generally found that the preferred polymers for pressure sensitive applications have a glass transition temperature of between about -50 to +10 degrees Celsius ( 0 C). The glass transition temperature is related to the molecular weight of the adhesive.
  • a preferred dermal composition of this invention comprises a drug; a multipolymer comprising an ethylene/vinyl acetate polymer and an acrylate polymer; a rubber, a clay and, optionally, a tackifying agent.
  • the multipolymer and rubber are preferably in a ratio by weight respectively from about 1 : 10 to about 30:1, more desirably about 1:5 to 20:1 and preferably about 1:2 to 15:1.
  • the ratio of ethylene/vinyl acetate polymer to acrylate polymer is preferably about 20:1 to about 1:20 by weight.
  • the clay is present in the composition in an amount by dry weight of less than about 50% and preferably from 0.1 to 20%.
  • the elastomer may be rubber as is described, e.g., in United States patent 5,936,023, the entire disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of this patent describes "1.
  • a method of manufacturing a composite material comprising a rubber and a clay mineral comprising the steps of: exchanging an inorganic ion of a clay mineral with an organic onium ion to organize the clay mineral; mixing the organized clay mineral and a process oil and/or a plasticizer; and mixing a rubber material with the mixture of the organized clay mineral and the process oil and/or the plasticizer and dispersing the clay mineral uniformly in the rubber material.”
  • the rubber material is described at column 3 of this patent as comprising "...at least one rubber selected from natural rubber, isoprene rubber, chloroprene rubber, styrene rubber, nitrile rubber, ethylene-propylene rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, epich
  • compositions comprised of the natural mineral and/or a synthetic mineral and/or a nanomagnetic material with a material other than such polymeric material, such resin material, such elastomer material, or such ceramic material.
  • the other material may be an adhesive material, as is described in United States patent 5,686,099, the entire disclosure of which is hereby incorporated by reference into this specification.
  • Claim 1 of such patent describes "A dermal composition comprising a mixture of 0.1 to 50 by dry weight of a drug, a pressure sensitive adhesive, a liquid solvent for one or more of the components of the composition and about 0.1 to about 10% by dry/weight of the total composition of clay to increase the adhesiveness of the composition.”
  • the pressure sensistive adhesive described in the such claim 1 of United States patent 5,686,099 is further described at columns 5-6 of such patent, wherein it is disclosed that "The term "pressure sensitive adhesive” as used herein means and refers to polymers, including but not limited to homopolymers, copolymers and mixtures of polymers, which are adhesive in the sense that they can adhere to the skin of an animal and which are pressure sensitive in the sense that adherence can be effected by the application of pressure.
  • the pressure sensitive adhesive can function as a matrix for the drug.
  • the adhesive is sufficiently resistant to chemical and/or physical attack by the environment of use so that it remains substantially intact throughout the period of use.
  • the adhesive is biocompatible in the environment of use, plastically deformable and with limited water solubility solubility.
  • water as used herein includes water containing biological fluids such as saline and buffers.
  • United States patent 5,686,099 also discloses that "A wide variety of polymers are known to be suitable for use in pressure sensitive adhesives. Suitable polymers include a natural or synthetic rubber, acryates, polycarboxylic acids or anhydrides thereof, vinyl acetate polymers and the like.
  • a pressure sensitive adhesive can be composed of a single polymer or mixtures thereof. It is generally found that the preferred polymers for pressure sensitive applications have a glass transition temperature of between about -50 to +10 degrees Celsius ( 0 C). The glass transition temperature is related to the molecular weight of the adhesive.”
  • a preferred dermal composition of this invention comprises a drug; a multipolymer comprising an ethylene/vinyl acetate polymer and an acrylate polymer; a rubber, a clay and, optionally, a tackifying agent.
  • the multipolymer and rubber are preferably in a ratio by weight respectively from about 1 : 10 to about 30:1, more desirably about 1 :5 to 20:1 and preferably about 1:2 to 15:1.
  • the ratio of ethylene/vinyl acetate polymer to acrylate polymer is preferably about 20:1 to about 1:20 by weight.
  • the clay is present in the composition in an amount by dry weight of less than about 50% and preferably from 0.1 to 20%.
  • Certain nanomcomposite materials comprised of mineral matter and/or nanomagetic material.
  • magnetic mineral compositons that contain mineral matter and/or nanomagentic material and/or one or more other materials that may be, e.g., polymeric material, resinous material, elastomeric material, ceramic material, mixtures thereof, and the like.
  • certain particular nanomcomposite materials are described by way of further illustration.
  • the halloysite nanotubules described elsewhere in this specification are used as a structural component in a composite material.
  • a composite material may comprise a polymer, a polymer blend, or a copolymer into which the nanotubules are dispersed and blended.
  • An additional embodiment is an article comprising a matrix polymer and clay wherein said clay is intercalated with a block copolymer, wherein said block copolymer comprises a hydrophilic block capable of intercalating said clay and a matrix compatible block compatible with said matrix polymer.
  • the clay material suitable for this invention can comprise any inorganic phase desirably comprising layered materials in the shape of plates with significantly high aspect ratio. However, other shapes with high aspect ratio will also be advantageous, as per the invention. ...
  • Preferred clays for the present invention include smectite clay such as montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, sobockite, stevensite, svinfordite, halloysite, magadiite, kenyaite and vermiculite as well as layered double hydroxides or hydrotalcites.”
  • smectite clay such as montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, sobockite, stevensite, svinfordite, halloysite, magadiite, kenyaite and vermiculite as well as layered double hydroxides or hydrotalcites.”

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Abstract

La présente invention concerne une matière nanocomposite contenant une matière minérale argileuse disposée dans une matrice sélectionnée dans le groupe qui comprend un matière polymère, une matière résineuse, une matière élastomère, une matière céramique, et des mélanges de celles-ci. La matière minérale argileuse a une résistance à la flexion d'au moins environ 200 kilogrammes par centimètre-carré, et une résistance à la compression d'au moins environ 2000 kilogrammes par centimètre-carré.
PCT/US2006/003570 2006-02-01 2006-02-01 Nouvelle composition WO2007089230A2 (fr)

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US9027765B2 (en) 2010-12-17 2015-05-12 Hollingsworth & Vose Company Filter media with fibrillated fibers
US9352267B2 (en) 2012-06-20 2016-05-31 Hollingsworth & Vose Company Absorbent and/or adsorptive filter media
US9511330B2 (en) 2012-06-20 2016-12-06 Hollingsworth & Vose Company Fibrillated fibers for liquid filtration media
US9828294B2 (en) 2014-01-17 2017-11-28 National University Of Singapore Sintered clay mineral matrix doped with rare earth metals, transition metals, or post-transition metals
US10137392B2 (en) 2012-12-14 2018-11-27 Hollingsworth & Vose Company Fiber webs coated with fiber-containing resins
CN110165156A (zh) * 2019-04-12 2019-08-23 淮阴工学院 碳限域空间内FeP/FeC双层异质界面电极材料及其制备方法和应用
CN112403450A (zh) * 2020-09-08 2021-02-26 苏州市相城环保技术有限公司 一种磁性农田重金属吸附剂制备方法
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CN116640456A (zh) * 2023-06-14 2023-08-25 广州大学 一种负载型埃洛石纳米管改性沥青及其制备方法
EP4004097A4 (fr) * 2019-07-31 2024-05-29 Univ Northeastern Films de nitrure de bore thermiquement conducteurs et composites multicouches en contenant

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CN110165156A (zh) * 2019-04-12 2019-08-23 淮阴工学院 碳限域空间内FeP/FeC双层异质界面电极材料及其制备方法和应用
EP4004097A4 (fr) * 2019-07-31 2024-05-29 Univ Northeastern Films de nitrure de bore thermiquement conducteurs et composites multicouches en contenant
WO2021058880A1 (fr) * 2019-09-26 2021-04-01 Aalto University Foundation Sr Système de refroidissement
CN112403450A (zh) * 2020-09-08 2021-02-26 苏州市相城环保技术有限公司 一种磁性农田重金属吸附剂制备方法
CN114683663A (zh) * 2022-04-16 2022-07-01 南通纳科达聚氨酯科技有限公司 一种抗老化tpu膜及其加工工艺
CN114956787A (zh) * 2022-06-22 2022-08-30 景德镇玉玺陶瓷有限公司 一种低温瓷的配方及工艺
CN114956787B (zh) * 2022-06-22 2023-03-14 景德镇玉玺陶瓷有限公司 一种低温瓷的配方及工艺
CN116640456A (zh) * 2023-06-14 2023-08-25 广州大学 一种负载型埃洛石纳米管改性沥青及其制备方法
CN116640456B (zh) * 2023-06-14 2024-05-24 广州大学 一种负载型埃洛石纳米管改性沥青及其制备方法

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