US20050014851A1 - Colloidal core-shell assemblies and methods of preparation - Google Patents

Colloidal core-shell assemblies and methods of preparation Download PDF

Info

Publication number
US20050014851A1
US20050014851A1 US10/622,354 US62235403A US2005014851A1 US 20050014851 A1 US20050014851 A1 US 20050014851A1 US 62235403 A US62235403 A US 62235403A US 2005014851 A1 US2005014851 A1 US 2005014851A1
Authority
US
United States
Prior art keywords
core
shell
particles
dispersion
silica
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/622,354
Other languages
English (en)
Inventor
Joseph Bringley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US10/622,354 priority Critical patent/US20050014851A1/en
Assigned to EASTMAN KODAK COMPANY reassignment EASTMAN KODAK COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BRINGLEY, JOSEPH F.
Priority to PCT/US2004/022666 priority patent/WO2005009603A1/fr
Priority to US11/036,752 priority patent/US8287952B2/en
Priority to US11/036,814 priority patent/US7541017B2/en
Publication of US20050014851A1 publication Critical patent/US20050014851A1/en
Assigned to CREDIT SUISSE, CAYMAN ISLANDS BRANCH, AS ADMINISTRATIVE AGENT reassignment CREDIT SUISSE, CAYMAN ISLANDS BRANCH, AS ADMINISTRATIVE AGENT SECOND LIEN INTELLECTUAL PROPERTY SECURITY AGREEME Assignors: CARESTREAM HEALTH, INC.
Assigned to CREDIT SUISSE, CAYMAN ISLANDS BRANCH, AS ADMINISTRATIVE AGENT reassignment CREDIT SUISSE, CAYMAN ISLANDS BRANCH, AS ADMINISTRATIVE AGENT FIRST LIEN OF INTELLECTUAL PROPERTY SECURITY AGREEMENT Assignors: CARESTREAM HEALTH, INC.
Assigned to CARESTREAM HEALTH, INC. reassignment CARESTREAM HEALTH, INC. RELEASE OF SECURITY INTEREST IN INTELLECTUAL PROPERTY (FIRST LIEN) Assignors: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH
Abandoned legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0004—Preparation of sols
    • B01J13/0008—Sols of inorganic materials in water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0086—Preparation of sols by physical processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

  • the invention relates to colloidal dispersions comprising core-shell particles and to methods of forming colloidal core-shell dispersions.
  • the invention relates to nanoparticles, having either a positive or negative charge, assembled onto the surface of larger colloidal particles, which possess the opposite charge.
  • One, two or more layers of nanoparticles are assembled onto the surface, each layer having a charge opposite that of its adjacent layers.
  • a dispersion consists of a mixture of small solid particulates in a solvent, such as water.
  • the dispersion is said to be a stable colloid if the solid particulates are sufficiently small and homogeneous such that they do not rapidly aggregate and settle from suspension, usually for a period of many days.
  • Such suspensions are often referred to as “colloids” and are useful in many applications.
  • It is the surface properties of the particulates, such as their electrostatic charge, which is responsible for the stability of colloids. Typically the surfaces are significantly charged, positive or negative, so as to provide electrostatic repulsion to overcome forces which would lead to the aggregation and settling of the colloid.
  • Homola et al. in U.S. Pat. No. 4,280,918 claim “a method of manufacturing a magnetic dispersion containing magnetic particles” whereby a slurry of negatively charged colloidal particles is mixed with a slurry of positively charged magnetic particles, causing the colloidal particles to be attracted to and irreversibly bound to the magnetic particles.
  • the method does not employ simultaneous addition and typically a sonication step is required to homogenize the product. There is no indication of whether the resulting dispersion is a stable colloid.
  • a cationic polymer-modified silica dispersion and a method for its preparation which comprises (1) making a preliminary mixed solution of the silica and cationic polymer and (2) treating this solution with a high pressure homogenizer at a treating pressure of 300 kgf/cm 2 or more.
  • the method does not employ simultaneous addition of the colloid and surface modifying species.
  • Caruso et al. J. Amer. Chem Soc. 120, 8523 (1998) describe a method for preparing nanoparticle-shell multilayers upon larger polystyrene core-particles. A layer-by-layer technique is described in which oppositely charged nanoparticles or polymeric species are sequentially absorbed to the core particle.
  • the technique requires that the core particles be added to a large excess of the shelling polymer or particles and that the unabsorbed fraction (or excess) be removed be repeated centrifugation and wash cycles. Only then is a second shell-layer applied and centrifugation and washing repeated. This method is tedious, requires considerable time and is typically only applicable to dilute ( ⁇ 5 wt %) systems.
  • previous methods of forming core-shell colloids require purification methods to remove unshelled core particles, or to remove shell particles unassociated (not bound) to the core particles. These methods are time consuming and are not cost effective.
  • the invention provides a method of forming a colloidal dispersion comprising simultaneously bringing together core particles and shell material in a high shear mixing zone within a dispersion medium to form core-shell particles.
  • the invention provides a colloidal aqueous dispersion comprising core-shell particles dispersed in an aqueous medium, wherein said aqueous dispersion has a percent solids of greater than 5 weight percent; wherein the solid consists of core-shell particles wherein the surface of said core-shell particles comprises a particulate material and the particulate material is present in an amount sufficient, and only sufficient, to cover the surfaces of all core particles, and the ratio of the average particle diameter of the core particles to the average particle diameter of the particulate material is greater than 4 and wherein said core-shell particle has a zeta potential of greater than ⁇ 30 millivolts.
  • the invention provides core-shell colloids at a high production rate and at a low cost, and readily provides colloidally stable dispersions of said core-shell particles.
  • the invention further provides well-ordered, homogeneous core-shell colloidal particles in which substantially all of the core particles are shelled, and the colloid is substantially free of unshelled core particles, and is substantially free of shell particles unassociated with the core particles.
  • FIG. 1 shows the experimentally determined (points) and theoretically calculated (line) weight fractions of shell particles necessary to cover the surface of a 100 nm core particle as a function of shell particle size. The figure indicates that the core to shell weight ratios can be accurately described using geometrical relationships.
  • the invention has numerous advantages, providing core-shell colloids at a high production rate and at a low cost, and readily provides colloidally stable dispersions of said core-shell particles.
  • the invention further provides well-ordered, homogeneous core-shell colloidal particles in which substantially all of the core particles are shelled, and the colloid is substantially free of unshelled core particles, and is substantially free of shell particles unassociated with the core particles.
  • Colloidal particles find use in a broad variety applications such as pigments for paints, as thickeners and coating aids, in cosmetic products, in paper products, as polishing media in semiconductor electronics, to name only a few.
  • An application of particular importance is the use of colloids in the production of inkjet paper and media. It is often desired to modify the surfaces of colloidal particles to obtain a specific chemical function or to impart a desired physical property to the colloidal particles. Because the surface area of colloidal particles is generally very high, the surface properties play an important role in the application of colloidal particles. Surface modification of colloidal particles may be achieved through the preparation of core-shell particles. Because the shelling species is at the surface, the chemical and physical properties of the core-shell are determined by the nature of the shell species.
  • core particles may chosen based upon availability and low cost and can serve as carriers for more expensive and chemically complex shell materials. This approach greatly lowers the cost of the material, since it may be difficult or even impossible to obtain colloidally stable shell materials of desired particle size. It is desired that the core-shell colloid be inexpensive, homogeneous and colloidally stable to facilitate its application in products and devices.
  • Core particle materials may be selected from inorganic materials such as metals, metal oxides, metal oxyhydroxides and insoluble salts; and from organic particulates such as latexes, polystyrene, and insoluble polymers.
  • Preferred core particle materials are inorganic colloidal particles, such as alumina, silica, boehmite, zinc oxide, calcium carbonate, titanium dioxide, and zirconia. These materials are preferred because of their low cost and general availability.
  • Preferred organic core particle materials are selected from aqueous latexes and polystyrene.
  • the core particles are silica or aqueous latex particles.
  • the core particles are silica particles having a diameter between about 50 and 500 nm. These are preferred because of their low-cost and because they are suited to application in inkjet media.
  • Shell materials useful for the invention may be selected from organic or inorganic materials including covalently-bonded molecules, polymers, bio-polymers, oxides and particulate materials.
  • the shell material may be chosen to impart a particular property or function to the core-shell particles depending upon the intended use of the core-shell dispersion.
  • the shell material comprises a bio-molecule or bio-polymer. These are preferred because of their ability to function as biomedical tools such as in drug-delivery and in bio-recognition.
  • the shell material comprises a hydrolyzable organosilane, which are preferred because of their ability to attach themselves to a wide variety of materials, and because they may impart a specific chemical function to the core-shell particles.
  • said shell material comprises at least one member selected from the group consisting of silica, alumina, zirconia, tin oxide and titania. These oxides are preferred because of their availability and low cost.
  • the shell material comprises a particulate, it is preferred that the average size of the shell particles be less than about 100 nm, and more preferably less than about 50 nm.
  • the dispersion medium for carrying out the invention may be either aqueous or non-aqueous.
  • solvents suitable for carrying out the method of the invention include water, methanol, ethanol, iso-propanol, butanol, acetone, methylene chloride, chloroform, benzene or toluene.
  • the dispersion medium comprises water. Water is preferred because it is inexpensive and environmentally safe.
  • the core and shell dispersions are brought together simultaneously into a high shear mixing zone within a dispersion medium.
  • the high shear mixing zone may be provided by a propeller-like mixer, a static mixer, in-line mixers, dispersators, or other high shear mixing apparatus.
  • the mixing efficiency of the apparatus is dependent upon the type of mixing method chosen and the precise geometry and design of the mixer.
  • the mixing efficiency may be approximated by the turnover rate, where the turnover rate is the stir rate (rev/sec.) times the turnover volume (ml/rev)) divided by the aqueous volume.
  • the mixing efficiency may be approximated by multiplying the sum of the addition rates of the colloidal dispersions by the turnover volume of the mixer.
  • the mixing efficiency has units of turnovers/sec. It is preferred that the mixing efficiency be greater than about 0.10 turnovers/sec, and preferably greater than 0.5 turnovers/sec and most preferably greater than 1 turnover/sec.
  • Complete mixing of the two particle dispersion streams is preferably accomplished in less than about 10 seconds; and is more preferably accomplished substantially instantaneously. High turnover rates and fast mixing are preferred because they result in more complete shelling and more stable core-shell colloids.
  • the core-shell dispersion of the invention is a stable colloid and hence should remain in suspension for a period of greater than a few hours, and more preferably greater than a few days; and most preferably greater than a few weeks. This is preferred because it increases the shelf-life of the colloid.
  • the zeta potential of the dispersion should have a maximum value greater than about ⁇ 20 mV, and more preferably greater than about ⁇ 30 mV. A high zeta potential is preferred because it increases the colloidal stability of the colloid.
  • the pH of the dispersion may be adjusted as is necessary to obtain a stable colloid.
  • the pH of the core-shell, colloidal dispersion is substantially the same as the pH of the aqueous shell material dispersion used to prepare it. This is preferred because it typically maximizes the colloidal stability of the resulting core-shell dispersion.
  • the colloid stability may also be enhanced through the addition of dispersing aids, surfactants, or peptizers.
  • the core and shell material may be brought together into the high shear mixing zone as dry solids, or be carried in a suspending medium such as a liquid or gas.
  • the core and shell materials are suspended in water and thereafter brought together into the mixing zone.
  • Aqueous suspensions are preferred because they are readily available and inexpensive.
  • the solids concentration of the suspensions may varying from about 0.1% to about 50%, but is preferably greater than 1% and more preferably greater than 5% and most preferably greater than 10%. Colloids with higher solids concentrations are preferred because they lower the cost of the resulting core-shell dispersion.
  • the core-shell dispersion is recovered in the medium, and thereafter is simultaneously brought together with a second layer shell material in a high shear mixing zone within a dispersion medium to form core-shell particles having two layers. This process may be repeated many times until three or more shell layers are assembled onto the core particle surfaces.
  • the shell materials are brought together with the core particles in an amount sufficient, and only sufficient, to substantially cover all the surfaces of said core particles. This is preferred because when there is insufficient coverage, stable core-shell colloids are not obtained. It is furthermore preferred that the shell material should not be supplied into the mixing zone in an excess of that required to substantially cover all the surfaces of said core particles. In this case, excess shell materials are not strongly bound by the core and may reside as distinct particles in the dispersion. These particles are harmful since they may have properties distinct from the core-shell particles; and purification and separation of these particles from the core-shell may be difficult. A measure of the degree of shelling is approximated by comparing the total projected surface area of the shelling particles to the total surface area of the core particles.
  • the invention comprises a colloidal aqueous dispersion comprising core-shell particles dispersed in an aqueous medium, wherein said aqueous dispersion has a percent solids of greater than 5 weight percent; wherein the solid consists of core-shell particles, wherein the surface of said core-shell particles comprises a particulate material and the particulate material is present in an amount sufficient to cover the surfaces of all core particles, and the ratio of the average particle diameter of the core particles to the average particle diameter of the particulate material is greater than 4. It is preferred that the diameter of the core be at least 4 times greater than the diameter of the shell particle, since stable core-shell colloids are not obtained for diameter ratios less than four.
  • a stable colloid as referenced in the examples is defined as a particulate suspension in which there is no evidence for aggregation of core particles as determined by particle size measurement, and that there is not visible flocculation or settling of the colloid for at least one week after its preparation. Significant growth of average particle size to diameters greater than about three times the core diameter, and visible settling of the colloid within one week of its preparation is indicative of an unstable colloid.
  • Silica colloids of varying size were obtained from Nalco Chemical Company and nanoparticle Zirconia from Nyacol. Fumed silica and fumed alumina were obtained from Cabot Corporation.
  • Core/shell colloidal dispersions were prepared by the simultaneous addition of the core and the shell colloidal dispersions into a highly efficient mixing apparatus.
  • the colloidal dispersions were introduced via calibrated peristaltic pumps at known flow rates.
  • the mixing efficiencies and flow rates were varied to obtain stable core/shell colloidal dispersions.
  • the details of the preparation and the characteristics of the dispersions are given below.
  • the mixing efficiency typically was kept constant for each example and was about 25 turnovers/min, or 0.4 turnovers/sec.
  • the resulting dispersion had a bimodal particle size distribution with populations centered at about 0.250 microns and about 4.0 microns; and settled after standing, indicating that the dispersion was not a stable colloid.
  • the properties of the resulting mixture are summarized in Table 2.
  • I-1 This was prepared in an identical manner to that of I-1, except that the 1% silica colloid was added at a rate of 8.9 ml/min. The weight ratio of the resulting colloid was 93.0% boehmite and 7.0% silica. The resulting dispersion had a particle size of 110 nm and did not settle after standing, indicating that the dispersion was a stable colloid.
  • Table 2 The properties of the resulting colloidal assembly are summarized in Table 2.
  • I-2 This was prepared in an identical manner to that of I-1, except that the 1% silica colloid was added at a rate of 11.8 ml/min. The weight ratio of the resulting colloid was 90.9% boehmite and 9.1% silica. The resulting dispersion had a particle size of 110 nm and did not settle after standing, indicating that the dispersion was a stable colloid. The zeta potential of the colloidal particles was found to be about ⁇ 40 mV at a pH of about 7.0, indicating that the particles were negatively charged. The properties of the resulting colloidal assembly are summarized in Table 2.
  • I-3 This was prepared in an identical manner to that of I-1, except that the 1% silica colloid was added at a rate of 13.2 ml/min. The weight ratio of the resulting colloid was 89.0% boehmite and 11.0% silica. The resulting dispersion had a particle size of 120 nm and did not settle after standing, indicating that the dispersion was a stable colloid. The zeta potential of the colloidal particles was found to be about ⁇ 35 mV at a pH of 8.0 indicating that the particles were negatively charged. The properties of the resulting colloidal assembly are summarized in Table 2.
  • I-4 This was prepared in an identical manner to that of I-1, except that the 1% silica colloid was added at a rate of 21.0 ml/min. The weight ratio of the resulting colloid was 84.4% boehmite and 15.6% silica. The resulting dispersion had a particle size of 130 nm and did not settle after standing, indicating that the dispersion was a stable colloid.
  • the properties of the resulting colloidal assembly are summarized in Table 2.
  • I-5 This was prepared in an identical manner to that of I-1, except that the 1% silica colloid was added at a rate of 29.8 ml/min. The weight ratio of the resulting colloid was 80.6% boehmite and 19.4% silica. The resulting dispersion had a particle size of 120 nm and did not settle after standing, indicating that the dispersion was a stable colloid.
  • the properties of the resulting colloidal assembly are summarized in Table 2.
  • the zeta potential of the colloidal particles was found to be about ⁇ 30 mV at a pH of 8.0 indicating that the particles were negatively charged.
  • the properties of the resulting colloidal assembly are summarized in Table 2.
  • the resulting dispersion had a bimodal particle size distribution with populations centered at about 0.40 microns and about 4.0 microns; and settled after standing, indicating that the dispersion was not a stable colloid.
  • the properties of the resulting mixture are summarized in Table 2.
  • the data of Table 2 show that the standard mixing method is unable to provide stable core-shell colloidal assemblies even when the shell is present at a level to sufficiently cover the surface of the core.
  • the data further show that the successful preparation of stable core/shell assemblies is dependent upon the ratio of shell to core particles and is dependent upon the size of the shell particles. The relationship between these factors is shown more clearly in FIG. 1 in which we plot the experimentally determined weight % shell/(core+shell) necessary to achieve a stable core-shell colloid (from Table 2 above) versus that calculated from simple geometrical considerations (see below).
  • the geometrical considerations simply account for the fact that a given number of shell particles are required to completely cover the surface of the core particle; and that for larger shell particles this requires a greater weight fraction since the thickness of the shell increases.
  • FIG. 1 It can be seen in FIG. 1 that the experimentally determined (points) and theoretically calculated (line) weight fractions of shell particles necessary to cover the surface of a 100 nm core particle as a function of shell particle size.
  • the figure indicates that the core to shell weight ratios can be accurately described using geometrical relationships.
  • FIG. 1 clearly show that the core-shell assembly process closely follows the geometrical relationships assumed for packing of the shell around the spherical core. These data indicate that stable core/shell assemblies cannot be prepared unless a sufficient number of shell particles are present. From Table 2, once the core is “saturated” with shell particles the particle size no longer increases, or only very slightly, indicating that excess shell particles do not assemble into a second shell layer.
  • An alternative method of expressing the geometrical relation is arrived at by comparing the total projected surface area of the shelling particles to the total surface area of the core particles.
  • the ratio may vary from about 0.8 and 1.2, or may be from about 0.7 to 1.5 if the particles are significantly non-spherical.
  • the resulting dispersion had an average particle size of 131 nm, and did not settle after standing, indicating that the dispersion was a stable colloid.
  • the zeta potential of the colloidal particles was found to be about +25 mV at a pH of 4.0, indicating that the particles were positively charged and that the sign of the particles had been reversed by the shelling process.
  • the properties of the resulting colloidal assembly are summarized in Table 5.
  • the resulting dispersion had an average particle size of 125 nm, and did not settle after standing, indicating that the dispersion was a stable colloid.
  • the zeta potential of the colloidal particles was found to be about +35 mV at a pH of 4.0, indicating that the particles were positively charged and that the sign of the particles had been reversed by the shelling process.
  • the properties of the resulting colloidal assembly are summarized in Table 5.
  • the weight ratio of the resulting colloid was 74.2% boehmite, 6.7% silica (1st shell) and 19.1% siloxyl(propyl-3-ammonium) acetate (2 nd shell).
  • the resulting dispersion had an average particle size of 490 nm, and did not settle after standing, indicating that the dispersion was a stable colloid.
  • the resulting dispersion was then coated and tested as described above and the results shown in Table 5 below. TABLE 5 Ex. or Comp. 1 st shell 2 nd Shell Core/Shell/shell Particle Stable Ex.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Colloid Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Silicon Compounds (AREA)
  • Medicinal Preparation (AREA)
US10/622,354 2003-07-18 2003-07-18 Colloidal core-shell assemblies and methods of preparation Abandoned US20050014851A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US10/622,354 US20050014851A1 (en) 2003-07-18 2003-07-18 Colloidal core-shell assemblies and methods of preparation
PCT/US2004/022666 WO2005009603A1 (fr) 2003-07-18 2004-07-14 Ensembles coques-noyaux colloidaux et procedes d'elaboration
US11/036,752 US8287952B2 (en) 2003-07-18 2005-01-14 Colloidal core-shell assemblies and methods of preparation
US11/036,814 US7541017B2 (en) 2003-07-18 2005-01-14 Amine polymer-modified nanoparticulate carriers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US10/622,354 US20050014851A1 (en) 2003-07-18 2003-07-18 Colloidal core-shell assemblies and methods of preparation

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US11/036,814 Continuation-In-Part US7541017B2 (en) 2003-07-18 2005-01-14 Amine polymer-modified nanoparticulate carriers
US11/036,752 Continuation-In-Part US8287952B2 (en) 2003-07-18 2005-01-14 Colloidal core-shell assemblies and methods of preparation

Publications (1)

Publication Number Publication Date
US20050014851A1 true US20050014851A1 (en) 2005-01-20

Family

ID=34063200

Family Applications (3)

Application Number Title Priority Date Filing Date
US10/622,354 Abandoned US20050014851A1 (en) 2003-07-18 2003-07-18 Colloidal core-shell assemblies and methods of preparation
US11/036,814 Expired - Fee Related US7541017B2 (en) 2003-07-18 2005-01-14 Amine polymer-modified nanoparticulate carriers
US11/036,752 Active 2028-09-23 US8287952B2 (en) 2003-07-18 2005-01-14 Colloidal core-shell assemblies and methods of preparation

Family Applications After (2)

Application Number Title Priority Date Filing Date
US11/036,814 Expired - Fee Related US7541017B2 (en) 2003-07-18 2005-01-14 Amine polymer-modified nanoparticulate carriers
US11/036,752 Active 2028-09-23 US8287952B2 (en) 2003-07-18 2005-01-14 Colloidal core-shell assemblies and methods of preparation

Country Status (2)

Country Link
US (3) US20050014851A1 (fr)
WO (1) WO2005009603A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070219291A1 (en) * 2006-03-20 2007-09-20 Fuji Xerox Co., Ltd. Inkjet ink, and inkjet ink set, inkjet ink tank, inkjet-recording method and inkjet-recording apparatus using the same
US20080011441A1 (en) * 2004-07-28 2008-01-17 Degussa Gmbh Highly-Filled, Aqueous Metal Oxide Dispersion
WO2010093909A1 (fr) * 2009-02-12 2010-08-19 The Regents Of The University Of California Sphères creuses d'oxyde métallique et nanoparticules y étant encapsulées
WO2014100380A2 (fr) * 2012-12-19 2014-06-26 Sloan-Kettering Institute For Cancer Research Particules multimodales, procédés et utilisations associées
CN105645418A (zh) * 2016-01-15 2016-06-08 东南大学 一种黑色素掺杂单分散二氧化硅胶体粒子的量产制备方法
EP2944609A4 (fr) * 2013-01-08 2016-08-17 Kmtr Co Ltd Procédé de préparation d'une composition produisant des superoxydes et composition produisant des superoxydes préparée par le procédé
US10322194B2 (en) 2012-08-31 2019-06-18 Sloan-Kettering Institute For Cancer Research Particles, methods and uses thereof
US10688202B2 (en) 2014-07-28 2020-06-23 Memorial Sloan-Kettering Cancer Center Metal(loid) chalcogen nanoparticles as universal binders for medical isotopes
US10888227B2 (en) 2013-02-20 2021-01-12 Memorial Sloan Kettering Cancer Center Raman-triggered ablation/resection systems and methods
US10912947B2 (en) 2014-03-04 2021-02-09 Memorial Sloan Kettering Cancer Center Systems and methods for treatment of disease via application of mechanical force by controlled rotation of nanoparticles inside cells
US10919089B2 (en) 2015-07-01 2021-02-16 Memorial Sloan Kettering Cancer Center Anisotropic particles, methods and uses thereof
US11560487B2 (en) 2020-09-22 2023-01-24 Swimc Llc Coating compositions containing low molecular weight chitosan composition

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050014851A1 (en) 2003-07-18 2005-01-20 Eastman Kodak Company Colloidal core-shell assemblies and methods of preparation
FR2872061B1 (fr) * 2004-06-23 2007-04-27 Toulouse Inst Nat Polytech Composition solide divisee formee de grains a depot metallique atomique continu et son procede d'obtention
US20060293396A1 (en) * 2005-01-14 2006-12-28 Eastman Kodak Company Amine polymer-modified nanoparticulate carriers
US20090252965A1 (en) * 2005-04-29 2009-10-08 Eidgenössische Technische Hochschule Zürich Surface functionalization and coating of flame-generated nanoparticles
US20090014682A1 (en) * 2005-05-20 2009-01-15 Jsr Corporation Carrier Polymer Particle, Process for Producing the Same, Magnetic Particle for Specific Trapping, and Process for Producing the Same
US7402506B2 (en) * 2005-06-16 2008-07-22 Eastman Kodak Company Methods of making thin film transistors comprising zinc-oxide-based semiconductor materials and transistors made thereby
US20070292688A1 (en) * 2005-08-18 2007-12-20 Eastman Kodak Company Silylamine modified nanoparticulate carriers
CN100393408C (zh) * 2006-04-11 2008-06-11 陕西师范大学 表面图案化二氧化硅高分子复合微球的制备方法
US20080206562A1 (en) * 2007-01-12 2008-08-28 The Regents Of The University Of California Methods of generating supported nanocatalysts and compositions thereof
US7604924B2 (en) * 2007-10-24 2009-10-20 Eastman Kodak Company Negative-working imageable elements and methods of use
EP2237311A4 (fr) * 2008-02-01 2011-11-30 Fujimi Inc Composition de polissage et procédé de polissage l'utilisant
US9474769B2 (en) * 2008-02-08 2016-10-25 Yeu-Kuang Hwu Methods of treating cancers
US20100047559A1 (en) * 2008-06-20 2010-02-25 Washington, University Of Core-shell particles and their use in toughening polymer composites
JP5341049B2 (ja) * 2010-10-29 2013-11-13 日本発條株式会社 セラミックス焼結体の製造方法、セラミックス焼結体およびセラミックスヒータ
WO2013010446A2 (fr) * 2011-07-15 2013-01-24 北京格加纳米技术有限公司 Matériau à base de métal et d'oxyde métallique présentant une modification de surface organique et procédé de production correspondant
CN104893400B (zh) * 2015-05-27 2018-07-10 中国印刷科学技术研究院 一种触变微胶囊干燥剂及其制备方法
US10925811B2 (en) * 2017-03-18 2021-02-23 Kerr Corporation Porous composite filler compositions
WO2019002912A1 (fr) * 2017-06-27 2019-01-03 ETH Zürich Matériaux nanocomposites comprenant des nanoparticules cationiques et des polymères anioniques utiles dans des procédés destinés à leur impression en 3d
CN108079914B (zh) * 2017-12-13 2021-02-09 温州生物材料与工程研究所 一步法制备多聚胺类化合物微胶囊的方法
CN108641479B (zh) * 2018-04-13 2021-09-07 山东国瓷康立泰新材料科技有限公司 一种喷墨打印用超白陶瓷墨水及其制备方法
US11492547B2 (en) 2020-06-04 2022-11-08 UbiQD, Inc. Low-PH nanoparticles and ligands

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3007878A (en) * 1956-11-01 1961-11-07 Du Pont Aquasols of positively-charged coated silica particles and their production
US3620978A (en) * 1968-07-18 1971-11-16 Du Pont Process for preparing stable positively charged alumina-coated silica sols
US4280918A (en) * 1980-03-10 1981-07-28 International Business Machines Corporation Magnetic particle dispersions
US4791091A (en) * 1987-09-30 1988-12-13 Allied-Signal Inc. Catalyst for treatment of exhaust gases from internal combustion engines and method of manufacturing the catalyst
US5217804A (en) * 1990-11-06 1993-06-08 Eastman Kodak Company Magnetic particles
US5650002A (en) * 1995-11-13 1997-07-22 E. I. Du Pont De Nemours And Company TiO2 light scattering efficiency when incorporated in coatings
US6417264B1 (en) * 1998-12-24 2002-07-09 Tokuyama Corporation Cationic polymer-modified silica dispersion and production process for the same
US6420039B1 (en) * 1998-10-02 2002-07-16 Cabot Corporation Recording medium
US20030196692A1 (en) * 2002-04-17 2003-10-23 Catalysts & Chemicals Industries Co., Ltd. Photovoltaic cell

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3796634A (en) * 1970-03-19 1974-03-12 Us Health Education & Welfare Insolubilized biologically active enzymes
US4904411A (en) * 1986-04-25 1990-02-27 Ceramics Process Systems Corp. Highly loaded, pourable suspensions of particulate materials
US5403750A (en) * 1991-03-06 1995-04-04 W. R. Grace & Co.-Conn. Biocompatible, low protein adsorption affinity matrix
FR2719502B1 (fr) * 1994-05-09 1996-06-07 Rhone Poulenc Chimie Dispersion colloïdale à base d'oxyde de cérium et d'oxyde de titane son procédé de préparation, son application au revêtement de substrats et substrats ainsi revêtus.
AU687093B2 (en) 1994-09-27 1998-02-19 Nycomed Imaging As Contrast agent
WO2002041987A2 (fr) * 2000-10-25 2002-05-30 Tufts University Microspheres polymeriques
DE10120802A1 (de) 2001-04-27 2002-10-31 Basf Ag Verfahren zur Herstellung von gecoateten Nanopartikeln
EP1277766B1 (fr) * 2001-07-20 2009-06-24 Rohm And Haas Company Composé polymère contenant des groupes d'ester de silicium et compositions les contenant
US20030124194A1 (en) 2002-01-02 2003-07-03 Gaw Debra A. Amine functionalized superparamagnetic nanoparticles for the synthesis of bioconjugates and uses therefor
DE60313398T2 (de) * 2002-06-26 2008-01-10 Eastman Kodak Company Tintenstrahlaufzeichnungselement und Druckverfahren
US20050014851A1 (en) * 2003-07-18 2005-01-20 Eastman Kodak Company Colloidal core-shell assemblies and methods of preparation
US8137548B2 (en) * 2003-10-17 2012-03-20 Zirchrom Separations, Inc. Chelator-modified inorganic oxide particles

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3007878A (en) * 1956-11-01 1961-11-07 Du Pont Aquasols of positively-charged coated silica particles and their production
US3620978A (en) * 1968-07-18 1971-11-16 Du Pont Process for preparing stable positively charged alumina-coated silica sols
US4280918A (en) * 1980-03-10 1981-07-28 International Business Machines Corporation Magnetic particle dispersions
US4791091A (en) * 1987-09-30 1988-12-13 Allied-Signal Inc. Catalyst for treatment of exhaust gases from internal combustion engines and method of manufacturing the catalyst
US5217804A (en) * 1990-11-06 1993-06-08 Eastman Kodak Company Magnetic particles
US5650002A (en) * 1995-11-13 1997-07-22 E. I. Du Pont De Nemours And Company TiO2 light scattering efficiency when incorporated in coatings
US6420039B1 (en) * 1998-10-02 2002-07-16 Cabot Corporation Recording medium
US6417264B1 (en) * 1998-12-24 2002-07-09 Tokuyama Corporation Cationic polymer-modified silica dispersion and production process for the same
US20030196692A1 (en) * 2002-04-17 2003-10-23 Catalysts & Chemicals Industries Co., Ltd. Photovoltaic cell

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080011441A1 (en) * 2004-07-28 2008-01-17 Degussa Gmbh Highly-Filled, Aqueous Metal Oxide Dispersion
US7704315B2 (en) * 2004-07-28 2010-04-27 Degussa Ag Highly-filled, aqueous metal oxide dispersion
US20070219291A1 (en) * 2006-03-20 2007-09-20 Fuji Xerox Co., Ltd. Inkjet ink, and inkjet ink set, inkjet ink tank, inkjet-recording method and inkjet-recording apparatus using the same
WO2010093909A1 (fr) * 2009-02-12 2010-08-19 The Regents Of The University Of California Sphères creuses d'oxyde métallique et nanoparticules y étant encapsulées
US10322194B2 (en) 2012-08-31 2019-06-18 Sloan-Kettering Institute For Cancer Research Particles, methods and uses thereof
WO2014100380A3 (fr) * 2012-12-19 2014-08-14 Sloan-Kettering Institute For Cancer Research Particules multimodales, procédés et utilisations associées
US10105456B2 (en) 2012-12-19 2018-10-23 Sloan-Kettering Institute For Cancer Research Multimodal particles, methods and uses thereof
WO2014100380A2 (fr) * 2012-12-19 2014-06-26 Sloan-Kettering Institute For Cancer Research Particules multimodales, procédés et utilisations associées
EP2944609A4 (fr) * 2013-01-08 2016-08-17 Kmtr Co Ltd Procédé de préparation d'une composition produisant des superoxydes et composition produisant des superoxydes préparée par le procédé
US10888227B2 (en) 2013-02-20 2021-01-12 Memorial Sloan Kettering Cancer Center Raman-triggered ablation/resection systems and methods
US10912947B2 (en) 2014-03-04 2021-02-09 Memorial Sloan Kettering Cancer Center Systems and methods for treatment of disease via application of mechanical force by controlled rotation of nanoparticles inside cells
US10688202B2 (en) 2014-07-28 2020-06-23 Memorial Sloan-Kettering Cancer Center Metal(loid) chalcogen nanoparticles as universal binders for medical isotopes
US10919089B2 (en) 2015-07-01 2021-02-16 Memorial Sloan Kettering Cancer Center Anisotropic particles, methods and uses thereof
CN105645418A (zh) * 2016-01-15 2016-06-08 东南大学 一种黑色素掺杂单分散二氧化硅胶体粒子的量产制备方法
US11560487B2 (en) 2020-09-22 2023-01-24 Swimc Llc Coating compositions containing low molecular weight chitosan composition

Also Published As

Publication number Publication date
US20050186337A1 (en) 2005-08-25
US20050192381A1 (en) 2005-09-01
WO2005009603A1 (fr) 2005-02-03
US8287952B2 (en) 2012-10-16
US7541017B2 (en) 2009-06-02

Similar Documents

Publication Publication Date Title
US20050014851A1 (en) Colloidal core-shell assemblies and methods of preparation
Masoudi et al. The effect of poly (ethylene glycol) coating on colloidal stability of superparamagnetic iron oxide nanoparticles as potential MRI contrast agent
Luna-Xavier et al. Synthesis and characterization of silica/poly (methyl methacrylate) nanocomposite latex particles through emulsion polymerization using a cationic azo initiator
Guerrero‐Martínez et al. Recent progress on silica coating of nanoparticles and related nanomaterials
Anand et al. Role of surfactants on the stability of nano-zinc oxide dispersions
Rouxel et al. Effect of ultrasonication and dispersion stability on the cluster size of alumina nanoscale particles in aqueous solutions
Williams et al. Surface modification of magnetic nanoparticles using gum arabic
US20060105170A1 (en) Magnetic particle and process for preparation
WO2004000916A2 (fr) Dispersions stables de nanoparticules dans un milieu aqueux
CN106459612B (zh) 二氧化钛
EP3954744B1 (fr) Dispersion aqueuse de particules et procédé de formation d'une dispersion aqueuse de particules
EP1769843A2 (fr) Utilisation de Sels d'Acide 2,3-Dihydroxynaphtalene 6-Sulfonique en tant que Dispersants.
WO2014057976A1 (fr) Nanoparticules de silice de type cœur-enveloppe et procédé pour les produire, procédé de production de nanoparticules de silice creuses l'employant et nanoparticules de silice creuses obtenues par ledit procédé de production
Nguyen et al. SPION‐Decorated Nanofibers by RAFT‐Mediated Free Radical Emulsion Polymerization‐Induced Self Assembly
JP2011001205A (ja) 多孔質シリカカプセルの製造方法
van Wijk et al. Formation of hybrid poly (styrene-co-maleic anhydride)–silica microcapsules
GB2526659A (en) Process for preparation of superparamagnetic hollow spherical nanostructures
Yi et al. Fluorescence-functionalized magnetic nanocomposites as tracking and targeting systems: Their preparation and characterizations
CN105457556B (zh) 一种分散剂、其制备方法及其在纳米氧化铝分散中的应用
Puentes-Vara et al. Effects of surfactant and polymerization method on the synthesis of magnetic colloidal polymeric nanoparticles
Zhao et al. Redispersity/solubility of nanopowder in solvents
Nikolić et al. Synthesis and characterization of silica core/nano-ferrite shell particles
JP2008239897A (ja) ポリマー微粒子
Takeda et al. Importance of dispersibility of TiO2 in preparation of TiO2-dispersed microspheres by Shirasu porous glass (SPG) membrane emulsification
Suwabe et al. Low-temperature synthesis of water-dispersible magnetic composite particles with high monodispersity

Legal Events

Date Code Title Description
AS Assignment

Owner name: EASTMAN KODAK COMPANY, NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BRINGLEY, JOSEPH F.;REEL/FRAME:014320/0286

Effective date: 20030711

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

AS Assignment

Owner name: CREDIT SUISSE, CAYMAN ISLANDS BRANCH, AS ADMINISTR

Free format text: FIRST LIEN OF INTELLECTUAL PROPERTY SECURITY AGREEMENT;ASSIGNOR:CARESTREAM HEALTH, INC.;REEL/FRAME:019649/0454

Effective date: 20070430

Owner name: CREDIT SUISSE, CAYMAN ISLANDS BRANCH, AS ADMINISTR

Free format text: SECOND LIEN INTELLECTUAL PROPERTY SECURITY AGREEME;ASSIGNOR:CARESTREAM HEALTH, INC.;REEL/FRAME:019773/0319

Effective date: 20070430

AS Assignment

Owner name: CARESTREAM HEALTH, INC., NEW YORK

Free format text: RELEASE OF SECURITY INTEREST IN INTELLECTUAL PROPERTY (FIRST LIEN);ASSIGNOR:CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH;REEL/FRAME:026069/0012

Effective date: 20110225