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WO2008043373A1 - Isolant thermique composite et SES procédés de fabrication - Google Patents

Isolant thermique composite et SES procédés de fabrication Download PDF

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Publication number
WO2008043373A1
WO2008043373A1 PCT/EP2006/009729 EP2006009729W WO2008043373A1 WO 2008043373 A1 WO2008043373 A1 WO 2008043373A1 EP 2006009729 W EP2006009729 W EP 2006009729W WO 2008043373 A1 WO2008043373 A1 WO 2008043373A1
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WO
WIPO (PCT)
Prior art keywords
oxide
sulfide
group
heat insulating
insulating composite
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.)
Ceased
Application number
PCT/EP2006/009729
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English (en)
Inventor
Ralston Olivier Forsman-White
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.)
Advanced Glass Ceramics Establishment
Original Assignee
Advanced Glass Ceramics Establishment
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 Advanced Glass Ceramics Establishment filed Critical Advanced Glass Ceramics Establishment
Priority to PCT/EP2006/009729 priority Critical patent/WO2008043373A1/fr
Publication of WO2008043373A1 publication Critical patent/WO2008043373A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1051—Organo-metallic compounds; Organo-silicon compounds, e.g. bentone
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures

Definitions

  • the present invention relates to the field of heat insulating materials.
  • the present invention relates to heat insulating composites that can be mixed with plastic materials, more particularly those use for insulating high temperatures.
  • Plastic materials or composites are used in various articles including wire shielding, cable coating, spray valves, heat insulating panels, and fire doors are widely used in various domains, for example construction sites or hospitals.
  • the plastic should be lightweight, strong, fire resistant, and non-toxic. Ideally, these materials should be able to resist fire for several hours.
  • plastics are known to generate smoke and toxic gases in a fire. Although there are some plastics that can resist fire, for example, phenolic resins, these plastics are relatively expensive, generally environmental unfriendly, and hazardous to health.
  • this invention provides a heat insulating composite including: an inorganic silicate; a plurality of glass particles coated with polyorganosiloxane primer, said primer being formed from monomers having a general formula
  • each of Ru, R, 2 , and Ri 3 is independently selected from the group consisting of H, R, OR, OSiR 3 , wherein R is selected from the group consisting of H, alkyl group, aromatic group, acrylate group, ether group, and alkoxide group having 1 to 12 carbon atoms; and a binder composition for fusing the glass particles when the heat insulting composite is exposed to a temperature higher than 100 0 C.
  • the glass particles are formed by oxides selected from the group consisting of SiO 2 , B 2 O 3 , P 2 O 5 , GeO 2 , AS2O5, AS2O3, Sb 2 Oj, and their mixtures thereof, and more preferably SiO 2 .
  • the glass particles may be glass spheres.
  • the glass particles may further include modifiers selected from the group consisting of K 2 O, Na 2 O, CaO, BaO, PbO, ZnO, V 2 O 5 , ZrO 2 , Bi 2 O 3 , Al 2 O 3 , oxides of Ti, oxides of Th, and their mixtures thereof.
  • the glass particles have an average diameter of 0.05 micron to 1.5 micron, more preferably 0.75 micron.
  • the glass particles are in an amount of 50 to 95 weight percent with respect to the binder composition, more preferably 80 weight percent, and the binder composition is in an amount of 50 to 5 weight percent with respect to the glass particles, more preferably 20 weight percent.
  • the binder composition includes a major component selected from the group consisting of carbides, Gypsum powder, Blakite, nitrides, calcium carbonate, oxides, titanates, sulfides, zinc selenide, zinc telluride, inorganic siloxane compound and their mixtures thereof,
  • Carbides may be selected from the group consisting of aluminum carbide, calcium carbide, chromium carbide, hafnium carbide, molybdenum carbide, niobium carbide, silicon carbide, tantalum carbide, titanium carbide, tungsten carbide, vanadium carbide, zirconium carbide, and their mixtures thereof.
  • Nitrides may be selected from the group consisting of boron nitride, calcium nitride, chromium nitride, germanium nitride, magnesium nitride, aluminum nitride, zirconium nitride, and their mixtures thereof.
  • Oxides may be selected from the group consisting of aluminum oxide, germanium(IV) oxide, indium( ⁇ or III) oxide, magnesium oxide, silicon dioxide, silicon monoxide, thallium(IH) oxide, barium calcium oxide, tungsten oxide, barium oxide, barium strontium tungsten oxide, bismuth(III) oxide, bismuth strontium calcium copper oxide, cadmium oxide brown, cerium(IV) oxide, chromium( ⁇ i) oxide, chro ⁇ um(VI) oxide, cobalt(II) oxide, copper(l) oxide, copper( ⁇ ) oxide, dysprosium oxide, europium oxide, gadolinium oxide, gold(III) oxide hydrate, hafhium(IV) oxide, holmium(III) oxide, iridium(IV) oxide or iridium(IV) oxide hydrate, lanthanum oxide, lead(IV) oxide, lead(II) oxide yellow, lutetium (III) oxide, manganese(II, III or IV) oxides, mo
  • Titanates may be selected from the group consisting of barium titanate(IV), trontium titanate, and their mixtures thereof.
  • Sulfides may be selected from the group consisting of aluminum sulfide, antimony pentasulfide, antimony(III) sulfide, arsenic(II, UI, or V) sulfides, gallium(III) sulfide, germanium(II) sulfide, indium( ⁇ i) sulfide red, phosphorus pentasulfide, phosphorus trisulfide, selenium sulphide, barium sulfide, bismuth(III) sulfide, calcium sulfide, copper(I) sulfide, copper(_3) sulfide, gold(I or ID) sulfide, iron(II) sulfide, lead( ⁇ ) sulfide, lithium sulfide, manganese(II) s
  • the inorganic siloxane compound is AlSi ? kaolinate (Al 2 (S- 2 ⁇ 5 )(OH) 4 ).
  • the binder composition may further includes a minor component selected from the group consisting of carbides, metals, alloys, and their mixtures thereof.
  • Carbides may be selected from the group consisting of tungsten carbide, silicon carbide, and their mixtures thereof.
  • Oxides may be selected from the group consisting of aluminum oxide, beryllium oxide, magnesium oxide, zirconium oxide, mullite (AUSi 2 On), and their mixtures thereof.
  • Metals may be selected from the group consisting of tungsten, chromium, beryllium, nickel, iron, copper, titanium, aluminum, and their mixtures thereof. Alloys may be selected from the group consisting of low alloy steels, stainless steels, cast irons, brasses, bronzes, and their mixtures thereof.
  • the major component is in an amount of 70% to 80% by weight of the binder composition
  • the minor component is in an amount of 20% to 30% by weight of the binder composition.
  • the binder composition is hydrolyzed.
  • the inorganic silicate used in this invention can be sodium silicate.
  • the heat insulating composite may further include a plastic material selected from the group consisting of polybutylene terephthalte, polypropylene, polyacrylate and phenolic resins.
  • the polyorganosiloxane primer is formed from monomers selected from the group consisting of hexamethylcyclotrisiloxane, hexamethyldisiloxane, octamethylcyclotetrasiloxane, one linear all-methyl oligosiloxane of number average molecular weight of approximately 800, and decamethylcyclopentasiloxane, [3- (methacryloyloxy) propyl] trimethoxysilane, and their mixtures thereof. More preferably, the polyorganosiloxane primer is formed from [3-(methacryloyloxy) propyl] trimethoxysilane.
  • this invention provides a method of manufacturing a heat insulating composite including the steps of mixing glass particles and an inorganic silicate with a binder composition, wherein the glass particles are coated with polyorganosiloxane primer, said primer being formed from monomers having a general formula
  • each of Rn, R12, and R13 is independently selected from the group consisting of H, R, OR, OSiRa, wherein R is selected from the group consisting of H, alkyl group, aromatic group, acrylate group, ether group, and alkoxide group having 1 to 12 carbon atoms such that the glass particles are fused when the heat insulting composite is exposed to a temperature higher than 100 0 C,
  • the present invention provides a heat insulating composite material comprising: a heat insulating composite including: an inorganic silicate; a plurality of glass particles and a binder composition for fusing the glass particles when the heat insulting composite is exposed to a temperature higher than 100 0 C; and a polymeric material,
  • the polymeric material is provided in a particulate form. Further, the polymeric material may be provided in a pre-polymerised form.
  • the polymeric material may be a thermoplastic polymeric material or a thermoset polymeric material.
  • the polymeric material is selected from the group consisting of polybutylene terephthalte, polypropylene, polyacrylate and phenolic resins.
  • the plurality of glass particles is preferably coated with polyorganosiloxane primer, said primer being formed from monomers having a general formula
  • each of Rn, Ri 2, and Ri 3 is independently selected from the group consisting of H, R, OR, OSiR3, wherein R is selected from the group consisting of H, alkyl group, aromatic group, acrylate group, ether group, and alkoxide group having 1 to 12 carbon atoms.
  • the polyorganosiloxane primer is formed from monomers selected from the group consisting of hexamethylcyclotrisiloxane, hexamethyldisiloxane, octamethylcyclotetrasiloxane, one linear all-methyl oligosiloxane of number average molecular weight of approximately 800, and decamethylcyclopentasiloxa ⁇ e, [3-
  • the polyorganosiloxane primer is preferably formed from [3-(methacryloyloxy) propyl] trimethoxysilane.
  • the present invention provides heat insulating composite structure comprising: a heat insulating composite including: - an inorganic silicate; a plurality of glass particles and a binder composition for fusing the glass particles when the heat insulting composite is exposed to a temperature higher than 100 0 C; and a polymeric material.
  • the polymeric material is a thermoplastic polymeric material or a thermoset polymeric material.
  • the polymeric material selected from the group consisting of polybutylene terephthalte, polypropylene, polyacrylate and phenolic resins.
  • the plurality of glass particles is preferably coated with polyorganosiloxane primer, said primer being formed from monomers having a general formula
  • each of Rn, Ru, and Ri 3 is independently selected from the group consisting of H, R, OR, OSiRj, wherein R is selected from the group consisting of H, alkyl group, aromatic group, acrylate group, ether group, and alkoxide group having 1 to 12 carbon atoms.
  • the polyorganosiloxane primer may be formed from monomers selected from the group consisting of hexamethylcyclotrisiloxane, hexamethyldisiloxane, octamethylcyclotetrasiloxane, one linear all-methyl oligosiloxane of number average molecular weight of approximately 800, and decamethylcyolopentasiloxane, [3-
  • the polyorganosiloxane primer may be formed from [3-(methacryloyloxy) propyl] trimethoxysilane.
  • the structure is provided in a modular form.
  • the structure may be a fire resistant construct, a fire resistant wall, a fire resistant wall, a fire resistant closure, cable coating, cladding or the like,
  • the present invention provides a process for forming a heat insulating composite structure, the method including the steps of: providing the heat insulating composite material according to the fourth; and polymerizing the polymeric material of said heat insulating composite material so as to form a heat insulating composite structure.
  • the present invention provides heat insulating composite structure when made according to the method of the fifth aspect.
  • the structure may be provided in a modular form.
  • the structure may be a fire resistant construct, a fire resistant wall, a fire resistant wall, a fire resistant closure, cable coating, cladding or the like,
  • the heat insulating composite includes a plurality of glass particles, preferably glass spheres.
  • glass refers to all materials that can form glass, including oxides of Si (SiO 2 ), B (B 2 O 3 ), P (P 2 O 5 ), Ge (GeO 2 ), As (As 2 O 5 or As 2 O 3 ), Sb (Sb 2 O 3 ), which may also include modifiers, for example oxides of K (K 2 O), Na (Na 2 O), Ca (CaO), Ba (BaO), Pb (PbO), Zn (ZnO) 1 V (V 2 O 5 ), Zr (ZrO 2 ), and Bi (Bi 2 Os).
  • the species in brackets refers to the stable oxide forms of the corresponding elements. Oxides of Ti, Al, and Th may also be included in various concentrations. Among all, oxides of Si are particularly preferred due to low cost and high availability.
  • the glass spheres may have an average diameter of 0.05 mm to 1.5 mm. An average diameter of 0.75 micron is particularly preferred due to cost and availability considerations. It was found that, however, glass chunks having non-spherical shapes, for example cubic or even irregular shapes, also work for this invention. However, glass spheres are found to perform better for this invention and therefore is the preferred choice.
  • the above glass spheres are coated with polyorganosiloxane primer.
  • the primer is formed from monomers having a formula
  • Rn, R12, and R ⁇ can be independently selected from the group consisting of H, R, OR, OSiRj, wherein R is selected from the group consisting of H, alkyl group (e.g. methyl, ethyl, propyl, isopropyl, butyl, cyclopentyl, cyclohexyl), aromatic group (e.g. phenyl, tolyl, xenyl), acrylate group (e.g. methacryloxyalkyl), ether group, and alkoxide group (e.g. methoxy, ethoxy) having 1 to 12 carbon atoms.
  • the above organic groups may be partly or fully halogenated.
  • Suitable examples of the monomers may include hexamethylcyclotrisiloxane, hexamethyldisiloxane, octamethylcyclotetrasiloxane, one linear all-methyl oligosiloxane of number average molecular weight of approximately 800, and decamethylcyclopentasiloxane. These monomers are found to be able to promote advantageous changes in viscosity of the reaction mixture. It should be note that the primer may not be formed by only one monomer. In fact, it is preferred to use a mixture of monomers to have a better formation of siloxane network when the heat insulating composite of this invention is subjected to high temperatures.
  • the primer is preferred to be formed by the monomer [3-(MethacryIoyloxy) propyl] trimethoxysilane (CioItoOsSi), which has been shown in this invention to be able to provide significant cross-linking and surface bonding reactions with phenolic and other polymer matrix in the form of hydrosilylation with the methyl silane surface primer on the solid glass particles.
  • This particular monomer is also found to be able to flocculate (clump) and settle quickly,
  • the heat insulating composite of this invention also includes a binder composition for fusing the glass particles when the heat insulting composite is exposed to a temperature higher than 100 0 C.
  • the binder composition may include a major component, which can be selected from any one of the following compounds, or their mixtures: carbides including aluminum carbide (preferably in powder, -325 mesh); boron carbide (preferably in powder); calcium carbide; chromium carbide; hafnium carbide; molybdenum carbide; niobium carbide; silicon carbide (preferably in nanopowder); tantalum carbide; titanium carbide; tungsten carbide (preferably in powder); vanadium carbide (preferably in powder); zirconium carbide (preferably in powder); Gypsum powder; and Blakite; nitrides including boron nitride (preferably in powder); calcium nitride; chromium nitride; germanium nitride; magnesium nitride; aluminum nitride (preferably in
  • AlSi 2 kaolinate Al 2 (SIaOs)(OH)-O is particularly preferred. It is found that the heat-insulating composite formed with AlSi ⁇ kaolinate as the major component of the binder composition is less brittle and more homogenized, and is capable to withstand higher temperatures.
  • additional compounds including carbides including tungsten carbide (WC) and silicon carbide (SiC); oxides including aluminum oxide (Al 2 Oa), beryllium oxide (BeO), magnesium oxide (MgO), zirconium oxide (ZrO), mullite (Al ⁇ SiaO ⁇ ); metals including tungsten (W), chromium (Cr) 1 beryllium (Be), nickel (Ni), iron (Fe), copper (Cu), titanium (Ti) and aluminum (Al); and alloys including low alloy steels, stainless steels, cast irons, brasses and bronzes; and their mixtures thereof may also present in the binder composition as the minor component.
  • the presence of this minor component may further enhance the functionality of the minor components, for example, the working temperatures and pressures of the resulting heat insulating composite may be enhanced. However, it should be note that the presence of this minor component may be optionally.
  • the glass particles and the binder composition may be in any desired amounts.
  • the glass spheres may be in an amount of 50 to 95, more preferably 80, weight percent and the binder composition in an amount of 50 to 5, more preferably 20, weight percent.
  • the heat composite of this invention also includes a inorganic silicate, which may be generally known as "water glass".
  • Water glass is generally inexpensive and readily available, and it is found that mixing this water glass with the above glass particles and the binder composition, and then mix with a plastic material, fire resistant plastic materials are resulted. It is found that the primer allows the water glass to mix the glass particles and the water glass well with the plastic material, which can then enhance the fire resisting performance of existing plastic materials.
  • Suitable water glass includes sodium silicate solution.
  • Suitable polymer material that can be used in this invention includes polybutylene terephthalte (PBT), polypropylene (PP), and polyacrylate (PA), which can be in a weight or volume ratio of 20 to 40 percent of the finished composite.
  • Phenolic resin can also be used in this invention. Phenolic resin can be divided into two main types, namely novalac and resol types, depending on the reactant ratio and the catalyst applied during polymerization. Novalacs are made with acid catalyst and with phenol versus formaldehyde (P/F) ratio larger than one, and have linear structure and is cured with a cross-linking agent.
  • resols are made with alkaline catalyst and with P/F ratio less than one, and have multi- functionality structure that can be cured by itself without a curing agent, Usually novalacs are in solid whereas resols are in the form of solution.
  • Suitable polymer modifiers may include isocyanates, polyvinyl alcohol, resorcinol, tricresol, furfuryl alcohol, and various polyols, which may act as plasticizers, so that the plastics can be cured to form crosslinked polymers and are subsequently backed up with composite polymer matrices of polyester resin and glass fiber or epoxy resin with glass and/or carbon fibres.
  • a second polymer that is compatible with resols and capable of being cured along with the resol under the influence of the acid catalyst can also be added.
  • Typical resins that can be used in the co-polymerization are urea-aldehyde condensation products, epoxides, polyepoxyoraganosilicones, novalacs, polyvinyl acetates, polyvinyl butyral.
  • the binder composition and the glass particles "fused” to form an insulating ceramic-like structure.
  • This reaction is found to be endothe ⁇ nic, and more importantly, the resulting ceramic composition is found to be highly insulating and not brittle.
  • the composite of this invention may be formed as a layer on the outside of an object to be protected, and the heat will first attack the outer surface. It was found that as the heat progresses from the outer surface to the inner surface, plurality of laminated ceramic-like structures are formed, which may assist further in insulating the heat. Interestingly, these laminated ceramic-like structures are found to be rubber-like and therefore not brittle.
  • the results below show the temperature distribution of the heat-insulating composite having a thickness of 22mm, when the composite is subjected to a temperature of 900 0 C on the left hand side for 60 to 80 minutes.
  • the sample had thermal sensors inserted at intervals of 4mm and the temperature of the kiln was stabilized at 800 0 C before the sample was introduced. Detail results are shown as follows:
  • the composite of this invention is found to be even better in heat-insulating if it is exposed to elevated temperatures once,
  • the laminated ceramic-like structures formed during the first exposure to high temperatures are itself heat- insulating in the first place, which assists further in insulating the object to be protected from heat.
  • Table 1 below shows various examples of heat insulating polymer composite of this invention, and their properties, in which GT represents glass transition temperature.
  • HDT represents heat deflection temperature, which is the temperature at which a polymer deforms under a specific load.
  • GF refers to glass filled plastic resins.
  • Table 1 were done to investigate whether there are any notable advantages between a powdered version and the melted granulated version of the heat insulating material when it is mixed with the plastic material. It was proven that the powdered version gives better performance because better dispersion in the polymer may be achieved. Therefore it may be preferred to crush the granulates of the heat insulating material to particles having a size from
  • sol-gel method to for homogenizing the final composite plastic product, followed by sintering of the resulting sol-gel and then by crushing may be more cost and time efficient.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention se rapporte au domaine des matériaux d'isolation thermique. En particulier, la présente invention concerne des isolants thermiques composites qui peuvent être mélangés à des matériaux plastiques, plus particulièrement ceux utilisés pour une isolation à haute température.
PCT/EP2006/009729 2006-10-09 2006-10-09 Isolant thermique composite et SES procédés de fabrication Ceased WO2008043373A1 (fr)

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Application Number Priority Date Filing Date Title
PCT/EP2006/009729 WO2008043373A1 (fr) 2006-10-09 2006-10-09 Isolant thermique composite et SES procédés de fabrication

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Application Number Priority Date Filing Date Title
PCT/EP2006/009729 WO2008043373A1 (fr) 2006-10-09 2006-10-09 Isolant thermique composite et SES procédés de fabrication

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WO2008043373A1 true WO2008043373A1 (fr) 2008-04-17

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EP4281288A4 (fr) * 2021-01-19 2024-12-11 3M Innovative Properties Company Article doté d'un film collé et stratifié
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WO2006128672A1 (fr) * 2005-05-31 2006-12-07 Advanced Glass Ceramics Establishment Composite thermo-isolant et procedes de fabrication de celui-ci

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US4686253A (en) * 1986-02-20 1987-08-11 United States Gypsum Company Lightweight joint compound having improved paintability
EP0322135A1 (fr) * 1987-12-16 1989-06-28 Crompton Design Manufacturing Limited Matériaux pour des composants résistant au feu et à la chaleur et leur fabrication
WO2004069766A1 (fr) * 2003-02-08 2004-08-19 Technical Lightweight Composites Ltd Matieres composites
WO2006128672A1 (fr) * 2005-05-31 2006-12-07 Advanced Glass Ceramics Establishment Composite thermo-isolant et procedes de fabrication de celui-ci

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