WO2001070492A1 - High-temperature polymer/inorganic nanocomposites - Google Patents
High-temperature polymer/inorganic nanocomposites Download PDFInfo
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- WO2001070492A1 WO2001070492A1 PCT/US2000/007708 US0007708W WO0170492A1 WO 2001070492 A1 WO2001070492 A1 WO 2001070492A1 US 0007708 W US0007708 W US 0007708W WO 0170492 A1 WO0170492 A1 WO 0170492A1
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- nanocomposites
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- phosphonium
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/788—Of specified organic or carbon-based composition
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- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/832—Nanostructure having specified property, e.g. lattice-constant, thermal expansion coefficient
- Y10S977/833—Thermal property of nanomaterial, e.g. thermally conducting/insulating or exhibiting peltier or seebeck effect
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- 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
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- 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
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
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- 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
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- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
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- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31739—Nylon type
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- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Definitions
- a nanocomposite is defined as an interacting mixture of two phases, one of which is in the nanometer size range in at least one dimension. Due to the nanoscale dimensions of the reinforcement phase, nanocomposites display unique and improved properties compared to that of micro- or macro- composites. A wealth of unique properties and technological opportunities are offered by these materials. Hence, over the last few years, nanocomposite materials have become an integral part of the synthesis of new materials for a wide variety of applications including mechanical, optical, magnetic and dielectric applications.
- Polymer/inorganic nanocomposites have attracted much attention as the properties of polymers are further enhanced beyond what is achievable from more conventional particulate- filled or micro-composites.
- layered mica-type- silicates have been widely used as inorganic reinforcements for polymer matrices to create polymer nanocomposites with nanoscale dispersion of the inorganic phase within the polymer matrix.
- Layered silicate-polymer nanocomposites having (i) polymer chains intercalated between the silicate layers or (ii) individual silicate layers delaminated and dispersed in a continuous polymer matrix, have been fabricated.
- the invention provides new high-use temperature, lightweight polymer/inorganic nanocomposite materials with enhanced thermal stability and performance characteristics.
- the invention provides two techniques that enhance the thermal stability of the nanocomposite systems from their current limits of 100 - 150 °C to over 250 °C.
- the two unique approaches are based on innovative chemical design of the organic-inorganic interface using (i) more thermally stable surfactants/compatibility agents, and (ii) more thermally stable synthetic organically-modified layered- silicate reinforcements to create unique nanocomposites. These approaches offer processibility through both solution techniques, as well as solvent-free direct melt intercalation technique.
- nanocomposites are optimized in order to manufacture these materials in commercially applicable forms, e.g. films, fibers and molded components.
- the new technology provides hitherto unobtainable thermal stability and performance characteristics, and has numerous applications in automotive, aerospace, electronic and food and beverage industries.
- Figure 1 shows high temperature, high performance organic/inorganic nanocomposites.
- Figure 2 shows a chemical structure of the preferred tetraphenyl phosphonium surfactant.
- Figure 3 shows a schematic of polymer-layered silicate nanocomposite structures.
- Figure 4 provides a table of the properties of nylon-6 and layered silicate-nylon nanocomposites.
- Nanocomposites 1 have silicate layers 3 with alkyl ammonium surfactants 5 on the surface.
- the first part of the invention schematically shown in Figure IB, provides new organic/inorganic nanocomposite structures 11 by substituting high temperature organic phosphonium cations 15 for the standard compatibilizing agent, viz., alkyl ammonium cations.
- ion exchange occurs with the more thermally stable organic phosphonium cations, e.g. tetraphenyl phosphonium 15 ( Figure 2) . That modification enhances the thermal stability of the nanocomposites from the current level of about 100-150 'C to approximately 175-200 'C or more without affecting other physical or mechanical properties of the resulting nanocomposites.
- the inventors have synthesized a new class of phenyl phosphine-based arylene ether structural polymers that offer excellent mechanical and thermo-oxidative properties. Those polymers are somewhat similar in nature to phenyl phosphonium, are qualified for space missions by NASA and are being commercially produced.
- the invention also provides the innovative use of organically modified layered alu inosilicates 23 (ORMLAS) that combine the layered silicates and the organic co patibilizing agent 25 in a single chemical compound 21, rendering the material thermally stable, and highly organophilic.
- ORMLAS organically modified layered alu inosilicates 23
- This dual function compound is then miscible with a host of structural matrix resins such as polya ides (nylon T m 120 'C), polyether imide (Ultem ® T g 215 'C), polyi ides (T >275'C) and poly arylene ethers (T g >225-350'C).
- structural matrix resins such as polya ides (nylon T m 120 'C), polyether imide (Ultem ® T g 215 'C), polyi ides (T >275'C) and poly arylene ethers (T g >225-350'C).
- ORMLAS since the bonding of the organic group to the inorganic Si atom is through the Si- C bonds, the ORMLAS exhibits excellent thermal stability. Fabricating ORMLAS layered silicates with high temperature structural polymers offers an attractive combination of properties such as high heat distortion temperature, excellent impact resistance and excellent mechanical properties.
- the invention provides high use-temperature light-weight polymer/inorganic nanocomposites which have outstanding properties, compared to the state of the art layered silicate nanocomposites that use alkyl ammonium as the surfactant.
- a database of properties of control specimens is established for nanocomposites made from mixtures of a number of commodity polymers (e.g., Polystyrene, Nylon, modified Polyetherimide, Polyethylene oxide) with montmorillonite containing alkyl ammonium-surfactants (through cation- exchange) .
- Superior polymer/layered silicate nanocomposites are fabricated by using mixtures of polyetherimide (PEI) resins with montmorillonite containing organic phosphonium surfactants, e.g., tetraphenyl phosphonium (TPP) (through cation-exchange) , via direct polymer melt intercalation process.
- PEI polyetherimide
- montmorillonite containing organic phosphonium surfactants e.g., tetraphenyl phosphonium (TPP) (through cation-exchange)
- Superior nanocomposites are fabricated by direct polymer melt intercalating organically-modified layered aluminosilicates (ORMLAS) with polyetherimide and thermoplastic polyimide (PI) or polyarylene ether (PAE) resins.
- ORMLAS organically-modified layered aluminosilicates
- PI thermoplastic polyimide
- PAE polyarylene ether
- nanocomposites are designed by creating favorable interactions at the polymer-layered silicate interfaces. That is achieved by making the chemistry of the inorganic reinforcement phase more compatible with the organic polymer matrix, i. e. , by making the layered silicate surfaces organophilic.
- the normally hydrophilic silicate surfaces are rendered organophilic after ion-exchange reactions of the loosely-held cations in the interlayer spaces of the silicate structure with organic cations.
- Nanocomposites have been synthesized for a variety of commodity polymer systems. Nanocomposites with properties much superior to that of the corresponding unfilled and conventionally-filled polymers are hence obtained. This unique combination of improved properties, easy fabricability, and low-cost, offers tremendous potential for commercial applications of these materials.
- polymer/inorganic nanocomposites 31, schematically shown in Figure 3, exploits the ability of the layered inorganic silicates 23 to accommodate polymer 33 chains 35 between the layers 23 creating intercalated hybrids 37.
- Delaminated hybrids 39 are created by dispersing individual layers 23 in a continuous polymer matrix 41.
- Figure 3 shows a schematic representation 31 of the polymer/inorganic nanocomposite structures 37, 39 obtained using the layered silicates 23.
- Nanocomposites 37 have single polymer chains intercalated between the silicate layers 23.
- the host silicate layers 23 are delaminated and dispersed in a continuous polymer matrix 41.
- That synthetic design also exploits the ion-exchange capacity of these layered-silicates 23 which allows for a fine-tuning of their surface chemistry to create a favorable organic-inorganic interface.
- layered silicates in the synthesis of those nanocomposites arise from their unique crystal structure.
- Those layered silicate materials are fine-grained and have crystal structures with a "platy" habit.
- Their structure is common to the family of 2:1 layered- or phyllosilicates, well-known examples of which are mica and talc.
- the structure is composed of Si04 tetrahedra fused to edge-shared octahedra of aluminum or magnesium hydroxides.
- Layer stacking leads to regular Van der aals gaps between the layers, viz., interlayer or gallery.
- Isomorphic substitution of cations is common (for example, A13+ or Fe3+ substituting for Si4+ in the tetrahedral network) . That leads to a net negative charge on the structure, which is generally counter-balanced by cations residing in the interlayer spacing. Those cations are more or less readily exchanged and result in the cation-exchange capacity of the materials.
- Those interlayer cations are, for example, Na+ or K+ in pristine layered silicates.
- an organophilic surface chemistry is desired to create favorable interactions with the organic polymer matrix. Therefore, those inorganic cations are exchanged with various organic cations, e. g., alkyl ammonium cations.
- the hydrophilic silicate surface is thus rendered organophilic.
- Those surfactants typically are alkyl ammonium compounds e.g., dimethyl ditallow ammonium bromide.
- dimethyl ditallow ammonium bromide is the use of dimethyl ditallow ammonium bromide to cation-exchange with the Na+- montmorillonite - a layered silicate.
- Such ion-exchanged 'organo'silicate clays are commercially available.
- the properties of the nanocomposites can be optimized through interfacial surface chemical design.
- layered silicate nanocomposites has involved intercalation of a suitable monomer followed by in situ polymerization. Alternatively, polymer intercalation is carried out from solution. Those techniques limit use in the case of most technologically important polymers, since suitable monomers and compatible polymer-silicate solvent systems are not always available.
- the spectrum of nanocomposite systems that can be synthesized is considerably broadened by the advent of a more versatile and environmentally-friendly synthetic approach, called direct polymer melt intercalation. In that approach, the polymer and the silicate are mixed, and the mixture is heated above the softening point of the polymer. That technique allows the synthesis of a much wider range of polymer/inorganic nanocomposites.
- Polymers with varying degrees of polarity and crystallinity are directly intercalated into organically- modified layered silicates.
- Example of polymers use direct polymer melt intercalation include polystyrene, poly (dimethylsiloxane) , poly (vinylidene fluoride), poly (e- caprolactone) , and (polyethylene oxide) .
- Delamination of the silicate layers can also be achieved during nanocomposite synthesis through 'polymer melt intercalation' .
- An example is the delamination of the individual silicate layers achieved by suspending ditallow ammonium-exchanged montmorillonite in PDMS
- a key to obtaining superior properties at low inorganic loadings is the homogeneous nanoscale dispersion of the inorganic phase in the polymer, and the creation of favorable interactions at the organic-inorganic interface.
- Favorable interfacial chemistry leads to organic and inorganic phases being dispersed at a nanometer level .
- the superior properties of the new composites are obtained at low inorganic loadings.
- the use of low inorganic contents leads to significant advantages. High degrees of stiffness, strength and barrier properties are obtained with far less inorganic content than comparable glass- or mineral reinforced polymers. Considerable weight savings are, therefore, obtained.
- Nylon-layered nanocomposite automatic timing belt cover Some commercial applications of these materials are, for example, Nylon-layered nanocomposite automatic timing belt cover. Other applications include airplane interiors, fuel tanks, components in electrical and electronic parts, under- the-hood automotive structural parts, brakes and tires. Applications of nanocomposite barrier films may be used in food packaging and in other applications are also possibilities .
- the nanocomposites yield significant enhancements in properties at low inorganic loadings also provides ease-of-manufacturing and several cost-benefits. It allows for the use of simple manufacturing techniques (viz., extrusion, injection-molding and casting) which are normally used for pure polymers. Therefore, the nanocomposites can be manufactured at a much lower cost than the more conventional fiber- or mineral-reinforced composites which require more expensive fabrication procedures. That provides further reasons for their commercial appeal .
- Commodity polymers provide use-temperatures below 125 'C. Substructure applications for rockets and aircraft require higher long term use-temperatures of about 175 'C and 250 'C.
- the thermal stability of the current state-of-the-art nanocomposite systems is often limited by the thermal instability of the surfactants used to create favorable interactions at the interface.
- Those surfactants typically are alkyl ammonium compounds.
- One example is the use of dimethyl ditallow ammonium bromide to ion-exchange with the Na+-montmorillonite - a layered clay.
- the thermal stability of the nanocomposite system is, therefore, limited by the thermal stability of the alkyl ammonium compound. Degradation of those surfactant molecules, and hence that of the organic-inorganic interface, begins at temperatures around 100 - 110 'C.
- the invention provides more thermally stable surfactants, which optimize the dispersion of the inorganic phase, and also enhance the compatibility at the organic- inorganic interface through the creation of favorable interactions.
- the invention therefore provides enhanced use-temperatures of the nanocomposites.
- One part elevates the use-temperature of the nanocomposite system by using more thermally stable surfactants than the currently used alkyl ammonium compounds.
- the first part provides tetra-phenyl phosphonium compounds (with thermal stability in the range of 190' - 200 * C) to carry out a cation-exchange with the layered silicate reinforcement.
- Tetraphenyl phosphonium is a reactive salt with a net positive charge, as shown in Figure 2.
- the salt readily ion exchanges with the cations on the surface of the inorganic phase attaching itself from the oxide surface and thus rendering the surface organophilic. That surface modified system lends itself to direct melt intercalation.
- tetraphenyl phosphonium is a high temperature organic moiety with thermal stability in excess of 200 'C
- the first part of the invention provides nanocomposites which will satisfy the need for long-term use- temperatures of 175-200 'C.
- the second part of the invention extends the use- temperature of the nanocomposites to over 250 'C. It is based on the innovative use of organically-modified layered alumino-silicates (ORMLAS) that combine the layered silicate and the organic surfactant/compatibility agent in a single chemical compound.
- ORMLAS organically-modified layered alumino-silicates
- the organic surfactant groups are bonded to the structural Si atom through thermally stable Si-C bonds.
- the thermal stability of the overall system is therefore greatly enhanced. Therefore, those materials provide unique inorganic layered silicate reinforcements having markedly more thermally-stable surfactants "built-in" to the chemical structure.
- polyamides nylon Tm 120'C
- polyether imide Ultem T g 215'C
- polyimides T >275 * C
- PAE T m poly arylene ether
- ORMLAS materials are synthesized using the sol-gel process where the organic groups are incorporated into the molecular structure through the use of organically modified silicon alkoxides, i. e. , precursors containing Si-CxHx bonds. The organic functionality is therefore directly bonded to the structural Si atom by the Si-C bond.
- the organically modified aluminosilicate will be synthesized using mixtures of organically-modified silicon alkoxides and solutions of aluminum chloride.
- the standard approach combines an alcohol solution of aluminum chloride with an alcohol solution of organically functionalized alkoxysilane.
- the organically functionalized trialkoxysilane e. g.
- alkyltriethoxysilane provides alkyl organic groups connected directly through Si-C bonds.
- the mixture is then condensed (crosslinked) to form a gel at appropriate pH conditions by the addition of NaOH.
- the gel is aged, filtered, washed with distilled water, and then dried in vacuum. That procedure yields a stable layered organophilic compound.
- the resulting material is either precipitated as a powder, dried and ground to appropriate particle size, or cast into various shapes and forms. In that case, the ORMLAS is precipitated as a powder or ground and classified it into appropriate size particles for incorporation with the polymer matrix for direct melt intercalation.
- ORMLAS compounds are especially engineered to dela inate in the presence of a variety of polymer resins - thus promoting the dispersion of the inorganic layers in the polymer matrix. That versatile and innovative new feature yield nanocomposites which will satisfy needs for a range of use- temperatures extending to long-term use-temperatures over 250 * C.
- ORMLAS organically-modified layered silicates
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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US09/090,864 US6057035A (en) | 1997-06-06 | 1998-06-05 | High-temperature polymer/inorganic nanocomposites |
CA002401052A CA2401052A1 (en) | 2000-03-23 | 2000-03-23 | High-temperature polymer/inorganic nanocomposites |
JP2001568726A JP2004503607A (en) | 2000-03-23 | 2000-03-23 | High temperature polymer / inorganic nanocomposite |
AU2000240226A AU2000240226A1 (en) | 2000-03-23 | 2000-03-23 | High-temperature polymer/inorganic nanocomposites |
EP00919564A EP1268185A4 (en) | 2000-03-23 | 2000-03-23 | High-temperature polymer/inorganic nanocomposites |
PCT/US2000/007708 WO2001070492A1 (en) | 1997-06-06 | 2000-03-23 | High-temperature polymer/inorganic nanocomposites |
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US4892197P | 1997-06-06 | 1997-06-06 | |
US09/090,864 US6057035A (en) | 1997-06-06 | 1998-06-05 | High-temperature polymer/inorganic nanocomposites |
PCT/US2000/007708 WO2001070492A1 (en) | 1997-06-06 | 2000-03-23 | High-temperature polymer/inorganic nanocomposites |
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WO2001070492A1 true WO2001070492A1 (en) | 2001-09-27 |
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Cited By (2)
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WO2003034514A2 (en) * | 2001-10-12 | 2003-04-24 | Koninklijke Philips Electronics N.V. | A barrier and a method of manufacture thereof |
DE10353890A1 (en) * | 2003-11-17 | 2005-06-23 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Nanocomposites for use e.g. in adhesives, circuit boards, construction parts or fire retardants contain an organic binder and a layered silicate modified by phosphorus-containing cations |
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KR100450231B1 (en) * | 2002-01-23 | 2004-09-24 | 주식회사 엘지화학 | Organic clay compound for preparing polar polymer-clay nanocomposities, polar polymer-clay nanocomposities comprising same, and method of preparing polar polymer-clay nanocomposiites using same |
US6805904B2 (en) | 2002-02-20 | 2004-10-19 | International Business Machines Corporation | Process of forming a multilayer nanoparticle-containing thin film self-assembly |
US7141277B1 (en) | 2002-03-07 | 2006-11-28 | The United States Of America As Represented By The Secretary Of The Air Force | Self-generating inorganic passivation layers for polymer-layered silicate nanocomposites |
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