Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/22—Expanded, porous or hollow particles
  • C08K7/24—Expanded, porous or hollow particles inorganic
  • C08K7/28—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/20—Homopolymers or copolymers of hexafluoropropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • 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
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249971—Preformed hollow element-containing
  • Y10T428/249974—Metal- or silicon-containing element

Definitions

• thermoplastic or thermosetting polymer phase with a reinforcing powder or fiber produces a range of filled materials and, under the correct conditions, can form a true polymer composite.
• a filler material typically is comprised of inorganic materials that act as either pigments or extenders for the polymer systems. Fillers are often replacements for a more expensive component in the composition.
• a vast variety of fiber-reinforced composites have been made typically to obtain fiber reinforcement properties to improve the mechanical properties of the polymer in a specific composite.
• the invention relates to a composite of a ceramic particle and a polymer having improved and novel properties.
• the material of the invention is provided through a selection of non metallic, ceramic particle specie, particle size (P s ) distribution, polymer type, molecular weight, surfcae modification and viscoelastic character and processing conditions.
• the material attains adjustable chemical/physical properties through ceramic particle selection and polymer selection.
• the resulting composite materials exceed the contemporary composites in terms of density, surface character, reduced toxicity, improved malleability, improved ductility, improved viscoelastic properties (such as tensile modulus, storage modulus, elastic-plastic deformation and others) electrical/magnetic properties, resistance to condition of electricity, vibration or sound, and machine molding properties.
• Figure 1 shows the polymer properties of the composites of the invention.
• the invention relates to novel composites made by combining a ceramic particle particulate with a polymer to achieve novel physical surface and viscoelastic properties.
• a ceramic material that is or can be formed into a particulate having a particle size ranging from about 10 microns to about 1,000 microns can be used in the invention.
• the maximum size is such that the particle size (P 8 ) of the particle is less than 20% of either the least dimension or the thinnest part under stress in an end use article.
• Such particles can be substantially spherical, substantially amorphous or can achieve virtually any three- dimensional shape formable by small particle size materials.
• thermoplastic and thermosetting resins can be used in the invention. Such resins are discussed in more detail below.
• the composites are specifically formed by blending the particulate and interfacial modifier with thermoplastic and then forming the material into a finished composite.
• Thermosetting composites are made by combining the particulate and interfacial modifier with an uncured material and then curing the material into a finished composite.
• the particulate material is typically coated with an interfacial modifier, a surface chemical treatment that supports or enhancing the final properties of the composite.
• a composite is more than a simple admixture.
• a composite is defined as a combination of two or more substances intermingled with various percentages of composition, in which each component results in a combination of separate materials, resulting in properties that are in addition to or superior to those of its constituents.
• the mixed material In a simple admixture the mixed material have little interaction and little property enhancement.
• One of the materials is chosen to increase stiffness, strength or density.
• Atoms and molecules can form bonds with other atoms or molecules using a number of mechanisms. Such bonding can occur between the electron cloud of an atom or molecular surfaces including molecular-molecular interactions, atom-molecular interactions and atom-atom interactions. Each bonding mechanism involves characteristic forces and dimensions between the atomic centers even in molecular interactions.
• van der Waals' forces are different than covalent and ionic bonding. These van der Waals' forces tend to be forces between molecules, not between atomic centers.
• the van der Waals' forces are typically divided into three types of ferees including dipole-dipole forces, dispersion forces and hydrogen bonding. Dipole-dipole forces are a van der Waals' force arising from temporary or permanent variations in the amount or distribution of charge on a molecule.
• VDW London forces increase with increasing size and there is no limit to the size of molecules, these forces can become rather large. In general, however, they are very weak. Dipole structures arise by the separation of charges on a molecule creating a generally or partially positive and a generally or partially negative opposite end. The forces arise from electrostatic interaction between the molecule negative and positive regions. Hydrogen bonding is a dipole-dipole interaction between a hydrogen atom and an electronegative region in a molecule, typically comprising an oxygen, fluorine, nitrogen or other relatively electronegative (compared to H) site. These atoms attain a dipole negative charge attracting a dipole-dipole interaction with a hydrogen atom having a positive charge.
• Dispersion force is the van der Waals' force existing between substantially non-polar uncharged molecules. While this force occurs in non-polar molecules, the force arises from the movement of electrons within the molecule. Because of the rapidity of motion within the electron cloud, the non-polar molecule attains a small but meaningful instantaneous charge as electron movement causes a temporary change in the polarization of the molecule. These minor fluctuations in charge result in the dispersion portion of the van der Waals' force.
• Such VDW forces because of the nature of the dipole or the fluctuating polarization of the molecule, tend to be low in bond strength, typically 50 kJ mol "1 or less.
• the range at which the force becomes attractive is also substantially greater than ionic or covalent bonding and tends to be about 3-10 A.
• van der Waals composite materials of this invention we have found that the unique combination of particulate, the varying but controlled particle size of the particle component, the modification of the interaction between the particulate and the polymer, result in the creation of a unique van der Waals' bonding.
• the van der Waals' forces arise between particulate atoms/crystals in the particulate and are created by the combination of particle size, polymer and interfacial modifiers in the composite.
• materials that are not fully accurately characterized as "composite” have merely comprised a polymer filled with particulate with little or no van der Waals' interaction between the particulate filler material.
• the interaction between the selection of particle size distribution and interfacially modified polymer enables the particulate to achieve an intermolecular distance that creates a substantial van der Waals' bond strength.
• the prior art materials having little viscoelastic properties do not achieve a true composite structure. This leads us to conclude that this intermolecular distance is not attained in the prior art.
• molecule can be used to relate to a particle, a particle comprising non-metal crystal or an amorphous aggregate, other molecular or atomic units or sub-units of non metal or inorganic mixtures, coin the composites of the invention, the van der Waals' forces occur between collections of metal atoms that act as "molecules" in the form of mineral, inorganic, or non-metal atom aggregates.
• the composite of the invention is characterized by a composite having intermolecular forces between particles about 30 kJ-mol "1 and a bond dimension of 3-10 A.
• the particulate in the composite of the invention has a range of particle sizes such that about at least 5 wt.-% of particulate in the range of about 10 to 500 microns and about at least 5 wt.-% of particulate in the range of about 10 to 250 microns, and a polymer, the composite having a van der Waals' dispersion bond strength between molecules in adjacent particles of less than about 4 kJ-mol "1 and a bond dimension of 1.4 to 1.9 A or less than about 2 kJ-mol "1 and the van der Waals' bond dimension is about 1.5 to 1.8 A.
• an interfacial modifier is an organic material that provides an exterior coating on the particulate promoting the close association (but with substantially no covalent bonding to particle or polymer) of polymer and particulate.
• Minimal amounts of the modifier can be used including about 0.005 to 3 wt.-%, or about 0.02 to 2 wt.%.
• Such a coating can have a thickness of about 0.01 to 1 micron.
• the term "particulate" typically refers to a material made into a product having a particle size greater than 10 microns and having a particle size distribution containing at least some particulate in the size range of 10 to 4000 microns. The particles have a range of sizes and circularity parameters.
• this particulate In a packed state, this particulate has an excluded volume of about 13 to 61 vol.-% or about 30 to 75 vol.-%. Alternatively, the particulate can have greater than about 30 vol.%, greater than about 40 vol.% or about 40 to 70 vol.-% particle loading.
• the particulate can comprise two three or more particulates sources, in a blend of materials of differing chemical and physical nature.
• non-metallic relates to a material substantially free of a metal in an oxidation state, approximately 0.
• a ceramic particle is typically defined as an inorganic crystalline oxide material.
• Ceramics are typically solid and inert. Ceramic materials tend to be brittle, hard, strong in compression and weak in shear or tension. Ceramics generally have a very high melting point that is typically greater than 1,000 0 C, but often ranges from 1,800 to 3,000 0 C and in some cases even higher.
• ceramic materials include materials derived from clay, such as kao unite. More recent ceramic materials include various silicates, aluminum oxide, silicon carbide and tungsten carbide. Other ceramics include oxides of aluminum and zirconium.
• Non-oxide ceramics include metal carbides, metal borides, metal nitrides and metal suicides. Other materials can be used in the composites of the invention including minerals, hollow and solid glass spheres and other particulates.
• inorganic relates to a material substantially free of carbon in the form or organic carbon or covalently bonded carbon compounds. Accordingly, compounds such as calcium carbonate or sodium bicarbonate are considered inorganic materials while most organic compounds including small molecules such as methane, ethane, ethylene, propylene, related polymer species, etc., are commonly considered organic materials.
• a “mineral” is defined as an element or chemical compound that is normally crystalline and that has been formed as a result of geological processes (Ernest H. Nickel, 1995, The definition of a mineral, The Canadian Mineralogist, vol. 33, pp. 689 - 690).
• non-metal, inorganic or mineral (mineral) is defined, as above, as an element or chemical compound that is normally crystalline and that has been formed as a result of geological processes.
• a “glass sphere or bubble” is defined as a glass body having a generally spherical shape having a hollow interior.
• the glass sphere typically has a particle size (P s ) that ranges from about 1 to 150 microns, typically about 10 to 120 microns, preferably about 10 to 100 microns.
• P s particle size
• the internal space within the glass bubble typically ranges from about 6 to 120 microns, often about 8 to 100 microns.
• Solid glass spheres can also have similar particle sizes.
• a "inorganic mineral” as understood in the context of this application includes natural inorganic materials that are not ceramics as defined above. Inorganic compounds are considered to be of a mineral, not biological origin. Inorganic minerals as understood in this application do not include organo, metallic chemistry compounds including metal ions surround by organic ligands. Inorganic compound as minerals typically include inorganic minerals that are found in nature or their synthetic equivalents. Commonly available inorganic minerals include mineral carbonates, mineral aluminates, mineral alumo-silicates, mineral oxides, mineral hydroxides, mineral bicarbonates, mineral sulfates, mineral fluorides, mineral phosphates, mineral alumo-phosphates, mineral alumo-silicates.
• Garnet is a useful mineral having the formula X 3 Y 2 (SiO 4 )S wherein X is divalent Ca, Fe or Mg and Y is trivalent Al, Fe or Cr.
• inorganic minerals include bauxite (aluminum ore), calcium carbonate, calcium hydroxide, calcium sulfate, cuprous and cupric sulfide, lead oxide, magnesium carbonate, magnesium oxide, magnesium sulfate, magnesium alum compounds, such as potassium alumo-silicate, potassium borate, potassium carbonate, potassium sulfate and other compounds, including sodium silicate, sodium sulfate, etc.
• the interfacial modification technology depends on the ability to isolate the particles from that of the continuous polymer phase.
• the isolation of the particulates requires placement of a continuous molecular layer(s) of interfacial modifier to be distributed over the surface of the particles. Once this layer is applied, the behavior at the interface of the interfacial modifier to polymer dominates the physical properties of the composite (e.g. tensile and elongation behavior) while the bulk nature of the particle dominates the bulk material characteristics of the composite (e.g. density, thermal conductivity, compressive strength).
• the correlation of particulate bulk properties to that of the final composite is especially strong due to the high volume percentage loadings of particulate phase associated with the technology.
• Circularity (perimeter) 2 /area.
• Such materials such as the ceramic microspheres and hollow glass bubbles have a circularity of 4 ⁇ (for smooth spherical particles) to 50 (smooth particles with an aspect ratio of 10).
• Many inorganic and mineral particulate have an oblong, multi lobe, rough non-regular shape or aspect.
• Such materials have a circularity of 13 to 35 or 13 to 30 and obtain the improved viscoelastic properties of the invention.
• the multiplier for the derivation of the particle morphology index must be adjusted for the aspect ratio of the particle.
• the particle morphology index is defined as:
• PMI (P s ) (P sh ) (P r ) (P p )
• the particle morphology index 1 to 200.
• Certain particles with a range of sizes or particle size (P s ) and aspect ratios, some roughness and porosity can range from 200 to 10 4 .
• Other particles with a broadened range of sizes or particle size (P s ) and aspect ratios, substantial roughness and increased porosity can range from 2x10 4 to 10 6 .
• the amount of interfacial modifier increases with the particle morphology index.
• Interfacial modifying chemistries are capable of altering the surface of the particulate by coordination bonding, Van der Waals forces, covalent bonding, or a combination of all three.
• the surface of the interfacially modified particle behaves as a particle of the interfacial modifier.
• useful technical ceramic materials are selected from barium titanate, boron nitride, lead zerconate or lead tantalite, silicate aluminum oxynitrides, silicane carbide, silicane nitride, magnesium silicate, titanium carbide, zinc oxide, zinc dioxide(zerconia)
• particularly useful ceramics of use in this invention comprise the crystalline ceramics and most preferred in compositions of the invention are the silica aluminum ceramics that can be made into useful particulate.
• Such ceramics are substantially water insoluble and have a particle size that ranges from about 10 to 500 microns, has a density that ranges from about 1.5 to 3 gram/cc and are commonly commercially available.
• polyethylene naphthalate and polybutylene naphthalate materials can be made by copolymerizing as above using as an acid source, a naphthalene dicarboxylic acid.
• the naphthalate thermoplastics have a higher Tg and higher stability at high temperature compared to the terephthalate materials.
• all these polyester materials are useful in the composite materials of the invention. Such materials have a preferred molecular weight characterized by melt flow properties.
• Useful polyester materials have a viscosity at 265°C of about 500-2000 cP, preferably about 800-1300 cP.
• thermoplastic examples include styrenic copolymers.
• the term styrenic copolymer indicates that styrene is copolymerized with a second vinyl monomer resulting in a vinyl polymer.
• Such materials contain at least a 5 mol-% styrene and the balance being 1 or more other vinyl monomers.
• An important class of these materials are styrene acrylonitrile (SAN) polymers.
• SAN polymers are random amorphous linear copolymers produced by copolymerizing styrene acrylonitrile and optionally other monomers. Emulsion, suspension and continuous mass polymerization techniques have been used.
• SAN copolymers possess transparency, excellent thermal properties, good chemical resistance and hardness.
• ASA polymers are random amorphous terpolymers produced either by mass copolymerization or by graft copolymerization. In mass copolymerization, an acrylic monomer styrene and acrylonitrile are combined to form a heteric terpolymer. In an alternative preparation technique, styrene acrylonitrile oligomers and monomers can be grafted to an acrylic elastomer backbone. Such materials are characterized as outdoor weatherable and UV resistant products that provide excellent accommodation of color stability property retention and property stability with exterior exposure. These materials can also be blended or alloyed with a variety of other polymers including polyvinyl chloride, polycarbonate, polymethyl methacrylate and others.
• Polymer blends or polymer alloys can be useful in manufacturing the pellet or linear extrudate of the invention.
• Such alloys typically comprise two miscible polymers blended to form a uniform composition.
• Scientific and commercial progress in the area of polymer blends has lead to the realization that important physical property improvements can be made not by developing new polymer material but by forming miscible polymer blends or alloys.
• a polymer alloy at equilibrium comprises a mixture of two amorphous polymers existing as a single phase of intimately mixed segments of the two macro molecular components. Miscible amorphous polymers form glasses upon sufficient cooling and a homogeneous or miscible polymer blend exhibits a single, composition dependent glass transition temperature (Tg).
• Tg composition dependent glass transition temperature
• Phenolic polymers can also be used in the manufacture of the structural members of the invention.
• Phenolic polymers typically comprise a phenol-formaldehyde polymer. Such polymers are inherently fire resistant, heat resistant and are low in cost.
• Phenolic polymers are typically formulated by blending phenol and less than a stoichiometric amount of formaldehyde. These materials are condensed with an acid catalyst resulting in a thermoplastic intermediate polymer called NOVOLAK. These polymers are oligomeric species terminated by phenolic groups. In the presence of a curing agent and optional heat, the oligomeric species cure to form a very high molecular weight thermoset polymer.
• the fluorocarbon polymers useful in this invention are perflourinated and partially fluorinated polymers made with monomers containing one or more atoms of fluorine, or copolymers of two or more of such monomers.
• fluorinated monomers useful in these polymers or copolymers include tetrafluoroethylene (TFE), hexafluoropropylene(HFP), vinylidene fluoride (VDF), perfluoroalkylvinyl ethers such as perfluoro-(n-propyl-vinyl) ether (PPVE) or perfluoromethylvinylether (PMVE).
• TFE tetrafluoroethylene
• HFP hexafluoropropylene
• VDF vinylidene fluoride
• PPVE perfluoroalkylvinyl ethers
• PPVE perfluoro-(n-propyl-vinyl) ether
• PMVE perfluoromethylvinyl
• Particularly useful materials for the fluorocarbon polymers are TFE-HFP-VDF terpolymers (melting temperature of about 100 to 260 0 C; melt flow index at 265°C. under a 5 kg load is about 1-30 g-10 min "1 .), hexafluoropropylene-tetrafluoroethylene- ethylene (HTE) terpolymers (melting temperature about 150 to 280 0 C; melt flow index at 297°C under a 5 kg load of about 1-30 g-10 min "1 .), ethylene-tetrafluoroethylene (ETFE) copolymers (melting temperature about 250 to 275°C; melt flow index at 297°C under a 5 kg load of about 1-30 g-10 min "1 .), hexafluoropropylene-tetrafluoroethylene (FEP) copolymers (melting temperature about 250 to 275°C; melt flow index at 372°C under a 5 kg load of about 1-30 g-10
• Preferred copolymers are those composed of from at least about 70 and up to 99 mole percent vinylidene fluoride, and correspondingly from about 1 to 30 percent tetrafluoroethylene, such as disclosed in British Patent No. 827,308; and about 70 to 99 percent vinylidene fluoride and 1 to 30 percent hexafluoropropene (see for example U.S. Patent No. 3,178,399); and about 70 to 99 mole percent vinylidene fluoride and 1 to 30 percent trifluoroethylene Terpolymers of vinylidene fluoride, trifluoroethylene and tetrafluoroethylene such as described in U.S. Patent No.
• 2,968,649 and terpolymers of vinylidene fluoride, trifluoroethylene and tetrafluoroethylene are also representative of the class of vinylidene fluoride copolymers which are useful in this invention.
• Such materials are commercially available under the KYNAR trademark from Arkema Group located in King of Prussia, PA or under the DYNEON trademark from Dyneon LLC of Oakdale, MN. Fluorocarbon elastomer materials can also be used in the composite materials of the invention.
• Fluorocarbon elastomers contain VF 2 and HFP monomers and optionally TFE and have a density greater than 1.8 gm-cm "3' ; these polymers exhibit good resistance to most oils, chemicals, solvents, and halogenated hydrocarbons, and excellent resistance to ozone, oxygen, and weathering. Their useful application temperature range is -4O 0 C to 300 0 C. Fluorocarbon elastomer examples include those described in detail in Lentz, U.S. Pat. No. 4,257,699, as well as those described in Eddy et al, U.S. Pat. No. 5,017,432 and Ferguson et al., U.S. Pat. No. 5,061,965. The disclosures of each of these patents are totally incorporated herein by reference.
• Latex fluorocarbon polymers are available in the form of the polymers comprising the PFA, FEP, ETFE, HTE, THV and PVDF monomers.
• Fluorinated poly(meth)acrylates can generally be prepared by free radical polymerization either neat or in solvent, using radical initiators well known to those skilled in the art.
• Other monomers which can be copolymerized with these fluorinated (meth)acrylate monomers include alkyl (meth)acrylates, substituted alkyl (meth)acrylates, (meth)acrylic acid, (meth)acrylamides, styrenes, vinyl halides, and vinyl esters.
• the fluorocarbon polymers can comprise polar constituents.
• Such polar groups or polar group containing monomers may be anionic, nonionic, cationic, or amphoteric.
• the more commonly employed polar groups or polar group-containing organic radicals include organic acids, particularly carboxylic acid, sulfonic acid and phosphonic acid; carboxylate salts, sulfonates, phosphonates, phosphate esters, ammonium salts, amines, amides, alkyl amides, alkyl aryl amides, imides, sulfonamides, hydroxymethyl, thiols, esters, silanes, and polyoxyalkylenes, as well as other organic radicals such as alkylene or arylene substituted with one or more of such polar groups.
• the liquid forms can be further diluted in order to deliver the desired concentration.
• aqueous emulsions, solutions, and dispersions are preferred, up to about 50% of a cosolvent such as methanol, isopropanol, or methyl perfluorobutyl ether may be added.
• a cosolvent such as methanol, isopropanol, or methyl perfluorobutyl ether
• the aqueous emulsions, solutions, and dispersions comprise less than about 30% cosolvent, more preferably less than about 10% cosolvent, and most preferably the aqueous emulsions, solutions, and dispersions are substantially free of cosolvent.
• Interfacial modifiers provide the close association of the particle with the polymer.
• Interfacial modifiers used in the non-reactive or non-crosslinking application fall into broad categories including, for example, stearic acid derivatives, titanate compounds, zirconate compounds, phosphonate compounds, aluminate compounds.
• Aluminates, phosphonates, titanates and zirconates useful contain from about 1 to about 3 ligands comprising hydrocarbyl phosphate esters and/or hydrocarbyl sulfonate esters and about 1 to 3 hydrocarbyl ligands which may further contain unsaturation and heteroatoms such as oxygen, nitrogen and sulfur.
• interfacial modifiers are dictated by particulate, polymer, and application.
• the particle surface is substantially continuously coated even if having substantial morphology.
• the coating isolates the particulate from the polymer.
• the maximum density of a composite is a function of the densities of the materials and the volume fractions of each. Higher density composites are achieved by maximizing the per unit volume of the materials with the highest densities. These materials are extremely hard and difficult to deform, usually resulting in brittle fracture. When compounded with deformable polymeric binders, these brittle materials may be formed into usable shapes using traditional thermoplastic equipment. However, the maximum densities achievable will be less then optimum.
• Preferred titanates and zirconates include isopropyl tri(dioctyl)pyrophosphato titanate (available from Kenrich Chemicals under the designation KR38S), organo titanates KR-238J and KR9S, neopentyl(diallyl)oxy, tri(dodecyl)benzene-sulfonyl titanate (available from Kenrich Chemicals under the trademark and designation LICA 09), neopentyl(diallyl)oxy, trioctylphosphato titanate (available from Kenrich Chemicals under the trademark and designation LICA 12), neopentyl(diallyl)oxy, tri(dodecyl)benzene-sulfonyl zirconate (available from Kenrich Chemicals under the designation NZ 09), neopentyl(diallyl)oxy, tri(dioctyl)phosphato zirconate (available from Kenrich Chemicals under the designation NZ 12), and neopentyl
• Thermosetting polymers can be used in an uncured form to make the composites with the interfacial modifiers. Once the composite is formed the reactive materials can chemically bond the polymer phase if a thermoset polymer is selected.
• the reactive groups in the thermoset can include methacrylyl, styryl, or other unsaturated or organic materials.
• interfacial modifier can also be added to particles in bulk blending operations using high intensity Littleford or Henschel blenders. Alternatively, twin cone mixers can be followed by drying or direct addition to a screw compounding device. Interfacial modifiers may also be reacted with the particulate in aprotic solvent such as toluene, tetrahydrofuran, mineral spirits or other such known solvents.
• R and R' are independanly a hydrocarbyl, Cl -C 12 alkyl group or a C7-20 alkyl or alkaryl group wherein the alkyl or alkaryl groups may optionally contain one or more oxygen atoms or unsaturation;
• X is sulfate or phosphate;
• Y is H or any common substituent for alkyl or aryl groups;
• m and n are 1 to 3.
• Titanates provide antioxidant properties and can modify or control cure chemistry.
• Zirconate provides excellent bond strength but maximizes curing, reduces formation of off color in formulated thermoplastic materials.
• a useful zirconate material is neopentyl(diallyl) oxy-tri (dioctyl) phosphato- zirconate.
• Blending systems such as ribbon blenders obtained from Drais Systems, high density drive blenders available from Littleford Brothers and Henschel are possible. Further melt blending using Banberry, veferralle single screw or twin screw compounders is also useful.
• liquid ingredients are generally charged to a processing unit first, followed by polymer polymer, particulate and rapid agitation. Once all materials are added a vacuum can be applied to remove residual air and solvent, and mixing is continued until the product is uniform and high in density.
• Dry blending is generally preferred due to advantages in cost. However certain embodiments can be compositionally unstable due to differences in particle size.
• the composite can be made by first introducing the polymer, combining the polymer stabilizers, if necessary, at a temperature from about ambient to about 60 0 C with the polymer, blending a particulate (modified if necessary) with the stabilized polymer, blending other process aids, interfacial modifier, colorants, indicators or lubricants followed by mixing in hot mix, transfer to storage, packaging or end use manufacture.
• twin screw compounding When compounding with twin screw compounders or extruders, a preferred process can be used involving twin screw compounding as follows.
• formulations containing small volumes of continuous phase 1. Add polymer binder. 2. Add interfacial modifier to twin screw when polymer binder is at temperature.
• Certain selections of polymers and particulates may permit the omission of the interfacial modifier and their related processing steps.
• THV220A (Dyneon Polymers, Oakdale MN) is a polymer of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride. The material is intended for extrusion applications, has a melting point of 120 0 C and a specific gravity of 1.9 g/cc.
• NZ 12 is neopentyl(diallyl)oxy-tri(dioctyl)phosphato-zirconate. It is available from KenRich Petrochemicals (Bayonne, NJ). NZ12 has a specific gravity of 1.06 g/cc and is readily soluble in isopropyl alcohol (IPA). Methods and Procedures
• Powder characterization is completed to determine packing behavior of the powdered materials.
• Packing fraction is determined by dividing the packing density of the powder by the true density as determined via helium pycnometry. Packing fraction is defined as:
• P f packing fraction
• P d packing density
• d pync pyncnometer density.
• Packing density is determined by measuring the bulk powder weight within a volume. The packing density is commonly determined by placing the powder within a metallurgical press. The press setup is available from Buehler International (Lake Bluff, IL). For frangible materials, pressure is reduced to the appropriate level to reduce breakage of the powder particles thereby preventing artificially high packing density values. For very frangible materials, a tap density is used.
• the pycnometer density is determined by helium gas pycnometry (AccuPync 1330 manufactured by Micromeretics Corporation - Norcross, GA).
• the interfacial modifier is first solubilized with isopropyl alcohol (IPA).
• IPA isopropyl alcohol
• the IPA/modifier mixture is applied to the powdered material previously placed within a rotating stainless steel rotating cooking stock pot.
• the 3 gallon stainless steel cooking pot was coupled to a DC drive and motor for controlled rotation with the pot orientated at 30 degrees from horizontal.
• IPA/modifier mixture is added along with additional IPA in enough volume to fully wet and flood the particles.
• the outer part of the pot is then heated externally with an industrial heat gun to volatize the IPA. After a sufficient time, the modified particles become free flowing - an indication that they are ready for compounding within our laboratory twin screw compounding equipment.
• the polymer and modified particles are fed in appropriate ratios using K-tron K20 gravimetric weight loss feeders.
• the raw ingredients are fused together within a 19mm B&P twin screw compounder. Barrel zone temperatures (5), screw speed, volumetric throughput, and die characteristics (number of openings and opening diameter) are varied depending on the nature of the particles and polymers being compounded. Commonly, torque, pressure, and melt temperature are monitored responses.
• a useful way to ensure the proper ratio of polymer and particulate(s) is to place compounded pellets into the heated metallurgical press; we call this the "puck density".
• Temperatures and volumetric throughput vary depending on the rheological behavior of the materials being extruded.
• motor amp load and extrusion pressures are monitored responses and used to gauge ease of extudability .
• the materials are extruded through a 19mm x 3 mm rectangular die plate onto a moving belt to minimize extrudate draw-down.
• ASTM Type IV dogbones were die cut from the extruded strips. The dog-bones were then tensile tested using a Lloyd Instruments universal testing machine produced by
• Example 1 Aluminum Oxide
• Aluminum oxide (AI2O3) was obtained from Sterling Supply, Inc (Minneapolis, MN), part number AO 120. The particles were -120 mesh size ( ⁇ 125 micron). Composites of THV 220A and AI 2 O 3 materials were made with both the unmodified powder and powder modified with two parts per hundred by weight (pph) NZ 12.
• the pycnometer density of the AI2O3 was measured using the lab Accupyc helium displacement pycnometer and determined to be 3.974 g/cc.
• the press density of the AI 2 O 3 was measured using the lab Buhler metallurgical press and 1 inch diameter cylindrical press die. The press density was found to be 2.556 g/cc which was followed by calculation of the packing fraction of AI2O3, found to be 64.3%.
• the NZ 12 was first dissolved in isopropanol (IPA) and then added to the AI2O3. Additional IPA was added to make the mixture a slurry.
• IPA isopropanol
• the IPA, NZ 12, AI 2 O 3 mix was blended using a rotating stock pot (discussed above) and heated to -95 0 C via a heat gun to boil off the excess IPA. Once cooled, the modified particle pycnometer density was determined to be 3.834 g/cc.
• both coated and uncoated AI 2 O 3 powder was compounded into Dyneon THV220A using lab 19mm twin screw compounder.
• the proper ratio of polymer and particulate was controlled by using two KTron K20 gravimetric weight loss feeders. Feed rates were calculated based on the feeder maximum feed rates and the desired material composition with a target throughput rate of 39 cc/min. All samples were run with the same screw configuration and the same temperature profile of all zones at 185 0 C and were run with a 19 hole die. All samples were cut into pellets at the die face for extrusion and were air cooled. Based on the packing fraction of the AI2O3 powder, a target particulate loading of 60 vol% was chosen.
• the unmodified AI2O3 ran through the extruder at a motor load of 12.0 amps. This material was stiff.
• the modified AI 2 O 3 ran through the extruder at a high observed motor load of 11.0 amps. Again the motor load climbed to the highest observed value but unlike the unmodified materials which climbed steadily, the interfacially modified material motor load fluctuated up and down but overall climbed up to the maximum. This material was more flexible than the unmodified materials.
• a ceramic composite and polymer composite comprises about 30 to 87 vol% of a ceramic particulate having a particle size greater than about 5 microns having a coating of about 0.005 to 5 wt-% of an interfacial modifier (IM), the percentage based on the composite; and a polymer phase.
• the IM can be used at about about 0.01 to 3 wt-%, about 0.05 to 2 wt-% or about 0.02 to 1.8 wt-% of an interfacial modifier; and a polymer phase.
• the composite can have a tensile strength of about 0.1 to 30 times about 2 to 30 times about 0.1 to 25 or 30 times, or 0.2 to 15 times that of the base polymer.
• the composite can have a tensile elongation of about 5% to 100%, about 8% to 100% or about 10% to 100% of the base polymer.
• the composite has combination of a tensile strength of about 10 to 20 time that of the base polymer and a tensile elongation of about 15% and 90% of base polymer and can have a shear of at least 5 or 10 sec "1 and can have a tensile strength of at least 0.2, 0.8 or 1 Mpa.
• the composite can comprise greater than the 30 volume percent or 50 volume percent of the ceramic particulate.
• the composite can comprise a mixed particulate wherein the ceramic composite has a particle size Ps of about 10 to 200 microns and the composite additionally comprises a particulate with a second particle size Ps 1 that differs from Ps by at least 5 microns, alternatively the composite has a mixed particle size according to the formula Ps ⁇ 2 Ps 1 or Ps ⁇ 0.05 Ps 1 .
• the next particulate can comprise, in addition to the ceramic particle, a variety of particulate including metallic, nonmetallic, hollow glass series, solid glass spheres, inorganic minerals, etc. and mixtures thereof.
• a particulate polymer composite comprising a ceramic particle in a polymer phase, the composite comprises about 90 to 40 volume-% of a ceramic particle, having a density greater than 0.10 gm-cm "3 and less than 5 gm-cm "3 , a particle size greater than 5 microns, a circularity greater than 12.5, 14 or 20 and an aspect ratio less than 9 or 3; and about 10 to 70 volume-% of a polymer phase; wherein the particle has an IM coating that is 0.2 to 1 microns thick comprising about 0.005 to 3 wt.-% of an interfacial modifier, based on the composite; and the composite density is less than 10 gm-cm " , about 0.4 to 5 gm-cm "3 , or about 0.9 to 10 gm-cm "3 , about 1 to 5 or 8 gm-cm "3 or about 1.5 to 4 or 6 gm- cm "3
• a shaped article comprises the composite having about 87 to 48 volume-% of a particulate having a particle size greater than 10 microns, and having a particle size distribution having at least 10 wt.-% of a particulate within about 10 to 100 microns, at least 10 wt.-% of the polymer particulate within about 10 to 500 microns, a circularity greater than 13 and an aspect ratio less than 1 :3; about 13 to 51 volume-% of a polymer phase.
• a dental article comprises about 87 to 48 volume-% of a particulate having a particle size greater than 10 microns, and having a particle size distribution having at least 10 wt.-% of a particulate within about 10 to 100 microns, at least 10 wt.-% of the polymer particulate within about 100 to 500 microns, a circularity greater than 12.5 and an aspect ratio less than 1 :9; about 13 to 51 volume-% of a polymer phase.
• a shaped article comprises about 87 to 48 volume-% of a particulate having a particle size greater than 10 microns, and having a particle size distribution having at least 10 wt.-% of a particulate within about 10 to 100 microns, at least 10 wt.-% of the polymer particulate within about 100 to 500 microns, a circularity greater than 12.5 and an aspect ratio less than 1 :9; about 13 to 51 volume-% of a polymer phase.
• the shaped article is a dental article, a transportation bumper, a commercial or residential weather strip, an abrasive layer, a vapor resistant hose, a transportation interior panel, a sealant for a fenestration unit or installation, a structural member for a sound box, a transportation brake pad, an LED heat dissipation fixture, a refrigeration unit thermal seal, and a fenestration composition that act as a thermal or barrier to mass transfer.
• the shaped article of the transportation panel is a sound deadening panel for an automotive and boat application.
• the shaped article of the fenestration unit is insulated glass unit.

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