[go: up one dir, main page]

WO2008043373A1 - Heat insulating composite and methods of manufacturing thereof - Google Patents

Heat insulating composite and methods of manufacturing thereof Download PDF

Info

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
Authority
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
Other languages
French (fr)
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/en
Publication of WO2008043373A1 publication Critical patent/WO2008043373A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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.

Landscapes

  • 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

The present invention relates to the field of heat insulating materials. Particularly, the present invention relates to heat insulating composites that can be mixed with plastic materials, more particularly those use for insulating high temperatures.

Description

Heat Insulating Composite and Methods of Manufacturing Thereof
Field of the Invention
The present invention relates to the field of heat insulating materials. Particularly, the present invention relates to heat insulating composites that can be mixed with plastic materials, more particularly those use for insulating high temperatures.
Background of the Invention
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. Ideally, the plastic should be lightweight, strong, fire resistant, and non-toxic. Ideally, these materials should be able to resist fire for several hours. However, 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.
Objects of the Invention
Therefore, it is an object of this invention to provide a heat-insulating material which substantially ameliorates at some of the deficiencies as set forth in the prior art. As a minimum, it is an object of this invention to provide the public with a useful choice.
Summary of the Invention
Accordingly, in a first aspect 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
Figure imgf000003_0001
wherein each of Ru, R,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; and a binder composition for fusing the glass particles when the heat insulting composite is exposed to a temperature higher than 1000C.
Preferably, the glass particles are formed by oxides selected from the group consisting of SiO2, B2O3, P2O5, GeO2, AS2O5, AS2O3, Sb2Oj, and their mixtures thereof, and more preferably SiO2. Alternatively, the glass particles may be glass spheres.
Additionally, the glass particles may further include modifiers selected from the group consisting of K2O, Na2O, CaO, BaO, PbO, ZnO, V2O5, ZrO2, Bi2O3, Al2O3, oxides of Ti, oxides of Th, and their mixtures thereof.
Preferably, the glass particles have an average diameter of 0.05 micron to 1.5 micron, more preferably 0.75 micron.
Optionally 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(π 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(πi) oxide, chroπύum(VI) oxide, cobalt(II) oxide, copper(l) oxide, copper(π) 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, molybdenum(IV) oxide, nickel oxide, πiobium(II) oxide, niobium(IV) oxide, niobium(V) oxide, osmium tetroxide, palladium(II) oxide or its hydrate, ρalladium(II) oxide hydrate, prasedymium(πi) oxide, rhenium(IV) oxide or its hydrate, rhodium(III) oxide or its hydrate, samarium oxide, silver(I or II) oxides, strontium oxide, tantalum(V) oxide, terbium oxide, terbium(III) oxide, thulium(III) oxide, tin(II or IV) oxides, tungsten(VI) oxide, vanadium(D3, IV, or V) oxides, ytterbium oxide, zinc oxide, zirconium(IV) oxide, antimony tin oxide, iτon(IH) oxide, yttrium(III) oxide, calcium oxide, and their mixtures thereof. 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(πi) 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(ϋ) sulfide, lithium sulfide, manganese(II) sulfide, mercury(II) sulfide red, palladium(II) sulfide, platinum(TV) sulfide, rhenium(VII) sulfide, silver sulfide, sodium sulfide, strontium sulfide, thallium(I) sulfide, Un(JI) sulfide, titanium(IV) sulfide, tungsten(IV) sulfide, zinc sulfide, molybdenum(IV) sulfide, and their mixtures thereof.
Preferably, the inorganic siloxane compound is AlSi? kaolinate (Al2(S-2θ5)(OH)4). Optionally, 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 (AUSi2On), 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.
Preferably, the major component is in an amount of 70% to 80% by weight of the binder composition, and the minor component is in an amount of 20% to 30% by weight of the binder composition.
Advantageously, 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.
Preferably, 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.
In a second aspect 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
Figure imgf000006_0001
wherein 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 1000C,
In a third aspect 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 1000C; 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.
Preferably 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
Figure imgf000007_0001
wherein 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.
Preferably 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 decamethylcyclopentasiloxaπe, [3-
(methacryloyloxy) propyl] trimethoxysilanβ, and their mixtures thereof.
The polyorganosiloxane primer is preferably formed from [3-(methacryloyloxy) propyl] trimethoxysilane.
In a fourth aspect, 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 1000C; and a polymeric material.
The polymeric material is a thermoplastic polymeric material or a thermoset polymeric material. Preferably 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
Figure imgf000008_0001
wherein 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-
(methacryloyloxy) propyl] trimethoxysilane, and their mixtures thereof.
The polyorganosiloxane primer may be formed from [3-(methacryloyloxy) propyl] trimethoxysilane.
Preferably 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,
In a fifth aspect, 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.
In a sixth aspect, 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,
Detailed Description of the Preferred Embodiment
This invention is now described by way of example with reference to the figure in the following paragraphs.
Objects, features, and aspects of the present invention are disclosed in or are apparent from the following description. It is to be understood by one of ordinary skilled in the art that the pTesent discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention, which broader aspects are embodied in the exemplary constructions.
The heat insulating composite includes a plurality of glass particles, preferably glass spheres. The term "glass" refers to all materials that can form glass, including oxides of Si (SiO2), B (B2O3), P (P2O5), Ge (GeO2), As (As2O5 or As2O3), Sb (Sb2O3), which may also include modifiers, for example oxides of K (K2O), Na (Na2O), Ca (CaO), Ba (BaO), Pb (PbO), Zn (ZnO)1 V (V2O5), Zr (ZrO2), and Bi (Bi2Os). 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
Figure imgf000010_0001
Each of 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 1000C. 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 nanopowder); zirconium nitride; calcium carbonate in various forms, including low in alkalies form, powder, random crystals; oxides including aluminum oxide in various forms, including calcined, powder, Corundum, fused, granular, mesoporous and pellets; geπnanium(IV) oxide; indium(II or IH) oxide; magnesium oxide in various forms including nanopowder, fused, fused in pieces form, fused in chips form; silicon dioxide in various forms including fused in pieces form and fused in granules forms; silicon monoxide; thalliumQII) oxide; barium calcium oxide; tungsten oxide; barium oxide; barium strontium tungsten oxide; bismuth(H[) oxide (preferably in powder); bismuth strontium calcium copper oxide (preferably in powder); cadmium oxide brown (preferably in powder); cerium(IV) oxide in various forms including powder, fused in pieces form; chromium(III) oxide in various forms including powder, fused in pieces form; chτomiurn(VI) oxide preferably in crystals; cobalt(II) oxide; copper(I) oxide (preferably in powder); copper(II) oxide (preferably in powder); dysprosium oxide; europium oxide (preferably in 99.9% 28,922-1); gadolinium oxide; gold(HI) oxide hydrate; hafhium(lV) oxide (preferably in powder); holπύum(III) oxide (preferably in 99.9% 20,844-2); iridium(IV) oxide or iridium(IV) oxide hydrate; lanthanum oxide; lead(IV) oxide; lead(II) oxide yellow (preferably in powder); lutetium (III) oxide; manganese(π, HI or W) oxides; molybdenum(IV) oxide; nickel oxide; niobium(H) oxide; niobium(IV) oxide; niobium(V) oxide in various forms including lumps and pore 22 A, 99.5%; osmium tetroxide; palladium(II) oxide or its hydrate; palladium(π) oxide hydrate; prasedymiuin(III) oxide; rheπium(IV) oxide or its hydrate; rhodium(IH) oxide or its hydrate; samarium oxide in various forms including powder and fused; silver(I or II) oxides; strontium oxide; taπtalum(V) oxide (preferably in lumps); terbium oxide; terbium(III) oxide; thulium(III) oxide; tin(II or IV) oxides (preferably in nanopowder); tungsten(VI) oxide (preferably in powder, more preferably in nanopowder); vanadium(iπ, IV, or V) oxides; ytterbium oxide; zinc oxide in various forms including powder, more preferably nanopowder, or hydrate; zirconium(IV) oxide in various forms including powder, more preferably nanopowder, and sulphated forms; antimony tin oxide (preferably in nanopowder); iron(III) oxide (preferably in nanopowder); yttrium(III) oxide (preferably in nanopowder); calcium oxide (preferably in anhydrous powder); titanates including barium titanate(IV) or tronthim titanate (preferably in nanopowder); sulfides including aluminum sulfide (preferably in granular form); antimony pentasulfide; antimony(IH) sulfide (preferably in powder); arsenic(II, HI, or V) sulfides; gallium(iπ) sulfide; germanium(II) sulfide; indium(III) sulfide red; phosphorus pentasulfide; phosphorus trisulfide; selenium sulphide; barium sulfide; bismuth(III) sulfide; calcium sulfide; copper(I) sulfide (preferably in powder, more preferably anhydrous); copper(H) sulfide (preferably in powder); gold(I or DOT) sulfide; iron(II) sulfide; lead(ll) sulfide; lithium sulfide; τnaπganese(II) sulfide; mercury(π) sulfide red; palladium(II) sulfide; platinum(IV) sulfide; rhenium(VII) sulfide; silver sulfide; sodium sulfide; strontium sulfide; thallium(I) sulfide; tin(II) sulfide; titanium(IV) sulfide (preferably in powder or anhydrous form); tungsten(TV) sulfide (preferably in powder); zinc sulfide (preferably in pieces); molybdenum(IV) sulfide (preferably in powder); zinc selenide (preferably having coating quality and/or in powder); zinc telluride (preferably having coating quality); and inorganic siloxane compound including AlSi2 kaolinate (Al2(Si2θs)(OH)4),
Among all of the above compounds, AlSi2 kaolinate (Al2(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.
Other than the above major component of the binder composition, additional compounds including carbides including tungsten carbide (WC) and silicon carbide (SiC); oxides including aluminum oxide (Al2Oa), beryllium oxide (BeO), magnesium oxide (MgO), zirconium oxide (ZrO), mullite (AlβSiaOπ); 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. Typically, 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. By contrast, 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.
It was found that, surprisingly, when the heat-insulating composite of this invention is heated above a certain temperature, typically over 1000C, the binder composition and the glass particles "fused" to form an insulating ceramic-like structure. This reaction is found to be endotheπnic, and more importantly, the resulting ceramic composition is found to be highly insulating and not brittle. Typically, 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 9000C 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 8000C before the sample was introduced. Detail results are shown as follows:
Alter 30minutes:
Surface temperature - 815 degrees centigrade 2mm = 500 degrees centigrade 6 mm — 250 degrees centigrade 10 mm = 122 degrees centigrade 14 mm 66 degrees centigrade 18mm 30 degrees centigrade 22mm - 22 degrees centigrade
After 60 minutes: Surface temperature = 825 degrees centigrade 2mm = 500 degrees centigrade 6 mm = 250 degrees centigrade 10 mm = 130 degrees centigrade 14 mm 75 degrees centigrade 18mm 35 degrees centigrade 22mm = 25 degrees centigrade
It can be seen that a large portion of the composite of this invention is still kept at a temperature below 1000C. This demonstrates the effectiveness of the heat-insulating property of the composite of this invention.
What is even more advantageous is that 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. One will note that the tests in
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
5 microns to nano-sized particles if the granulated version is to be used.
It was also found that the use of the 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.
Figure imgf000016_0001
Table 1
While the preferred embodiment of the present invention has been described in detail by the examples, it is apparent that modifications and adaptations of the present invention will occur to those skilled in the art. Furthermore, the embodiments of the present invention shall not be interpreted to be restricted by the examples or figures only. It is to be expressly understood, however, that such modifications and adaptations are within the scope of the present invention, as set forth in the following claims. For instance, features illustrated or described as part of one embodiment can be used on another embodiment to yield a still further embodiment. Thus, it is intended that the present invention cover such modifications and variations as come within the scope of the claims and their equivalents.

Claims

CLAIMS:
1. A heat insulating composite including: an inorganic silicate; a plurality of glass particles coated with polyorganosiloxane primer, said primer heing formed from monomers having a general formula
Figure imgf000018_0001
wherein each of Rn, Ri ■%, and Rn 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; and a binder composition for fusing the glass particles when the heat insulting composite is exposed to a temperature higher than 100°C
2. The heat insulating composite of claim 1 , wherein the glass particles axe foπned by oxides selected from the group consisting of SiO2, B2O3, P2O5, GeC>2, AS2O5, AS2O3, Sb2O3, and their mixtures thereof.
3, The heat insulating composite of claim 2, wherein the glass particles are formed by SiO2.
4. The heat insulating composite of claim 2, wherein the glass particles are glass spheres.
5. The heat insulating composite of any one of claims 2 to 4, wherein the glass particles further include modifiers selected from the group consisting of K2O, Na2θ, CaO, BaO, PbO, ZnO, V2Os, ZrO2, Bi2O3, Al2O3, oxides of Ti, oxides of Th, and their mixtures thereof.
6. The heat insulating composite of claim 1, wherein the glass particles have an average diameter of 0.05 micron to 1.5 micron.
7. The heat insulating composite of claim 6, wherein the glass particles have an average diameter of 0.75 micron.
8. The heat insulating composite of claim 1, wherein the glass particles are in an amount of 50 to 95 weight percent with respect to the binder composition, and the binder composition is in an amount of 5 to 50 weight percent with respect to the glass particles.
9. The heat insulating composite of claim 8, wherein the particles are in an amount of 80 weight percent, and the binder composition is in an amount of 20 weight percent.
10. The heat insulating composite of claim 1, wherein 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.
11. The heat insulating composite of claim 10, wherein the carbides are 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.
12. The heat insulating composite of claim 10, wherein the nitrides are selected from the group consisting of boron nitride, calcium nitride, chromium nitride, germanium nitride, magnesium nitride, aluminum nitride, zirconium nitride, and their mixtures thereof.
13. The heat insulating composition of claim 10, wherein the oxides are selected from the group consisting of aluminum oxide, geπnanium(IV) oxide, indium(II or III) oxide, magnesium oxide, silicon dioxide, silicon monoxide, thallium(πi) oxide, barium calcium oxide, tungsten oxide, barium oxide, barium strontium tungsten oxide, bisffiuth(III) oxide, bismuth strontium calcium copper oxide, cadmium oxide brown, cerium(IV) oxide, chromium(III) oxide, chromium(VI) oxide, cobalt(II) oxide, copper(I) oxide, copper(II) oxide, dysprosium oxide, europium oxide, gadolinium oxide, gold(III) oxide hydrate, hafnium(IV) oxide, holmium(πi) oxide, iridium(IV) oxide or iridium(IV) oxide hydrate, lanthanum oxide, lead(IV) oxide, lead(II) oxide yellow, lutetium (ID) oxide, manganese(π, III or IV) oxides, molybdenum(IV) oxide, nickel oxide, niobium(II) oxide, niobium(IV) oxide, niobium(V) oxide, osmium tetroxide, palladium(IΪ) oxide or its hydrate, palladium(II) oxide hydrate, prasedymium(iπ) oxide, rhenium(IV) oxide or its hydrate, rhodium(IΪI) oxide or its hydrate, samarium oxide, silver(l or II) oxides, strontium oxide, tantalum(V) oxide, terbium oxide, terbium(III) oxide, thulium(III) oxide, tin(ϋ or IV) oxides, tungsten(VI) oxide, vanadium(IU, IV, or V) oxides, ytterbium oxide, zinc oxide, zirconium(IV) oxide, antimony tin oxide, iron(IH) oxide, yttrium(III) oxide, calcium oxide, and their mixtures thereof.
14. The heat insulating composite of claim 10, wherein the titanates are selected from the group consisting of barium titanate(IV), trontium titanate, and their mixtures thereof.
15. The heat insulating composite of claim 10, wherein the sulfides are selected from the group consisting of aluminum sulfide, antimony pentasulfide, antimony(m) sulfide, arsenic(ll, ID, or V) sulfides, gallium(III) sulfide, germanium(II) sulfide, indium(III) sulfide red, phosphorus pentasulfide, phosphorus trisulfide, selenium sulphide, barium sulfide, bismuth(iπ) sulfide, calcium sulfide, copper(I) sulfide, copper(II) sulfide, gold(I or III) sulfide, iron(H) sulfide, lead(IT) sulfide, lithium sulfide, manganese(II) sulfide, mercury(IT) sulfide red, palladhim(II) sulfide, platinum(IV) sulfide, rhenium(VII) sulfide, silver sulfide, sodium sulfide, strontium sulfide, thallium(I) sulfide, tin(II) sulfide, titanium(IV) sulfide, tungsten(IV) sulfide, zinc sulfide, molybdenum(IV) sulfide, and their mixtures thereof.
16. The heat insulating composite of claim 10, wherein the inorganic siloxane compound is AlSi2 kaolinate (Al2(Si2O5)(OH)4).
17. The heat insulating composite of Claim 10, wherein the binder composition further includes a minor component selected from the group consisting of carbides, metals, alloys, and their mixtures thereof.
18. The heat insulating composite of claim 17, wherein the carbides are selecting from the group consisting of tungsten carbide, silicon carbide, and their mixtures thereof.
19. The heat insulating composite of claim 17, wherein the oxides are selected from the group consisting of aluminum oxide, beryllium oxide, magnesium oxide, zirconium oxide, mullite (Al6Si2Oi3), and their mixtures thereof.
20. The heat insulating composite of claim 17, wherein the metals are selected from the group consisting of tungsten, chromium, beryllium, nickel, iron, copper, titanium, aluminum, and their mixtures thereof.
21. The heat insulating composite of claim 17, wherein the alloys are selected from the group consisting of low alloy steels, stainless steels, cast irons, brasses, bronzes, and their mixtures thereof.
22. The heat insulating composite of claim 17, wherein the major component is in an amount of 70% to 80% by weight of the binder composition, and the minor component is in an amount of 20% to 30% by weight of the binder composition.
23. The heat insulating composite of claim 1, wherein the binder composition is hydrolyzed.
24. The heat insulating composite of claim 1, wherein the inorganic silicate is sodium silicate.
25. The heat insulating composite of claim 1, wherein the amount of the inorganic silicate is 30 to 40 weight percent with respect to the glass particles and the binder composition.
26. The heat insulating composite of claim 1 further including a plastic material selected from the group consisting of polybutylene terephthalte, polypropylene, polyacrylate and phenolic resins.
27. The heat insulating composite of claim 1, wherein 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.
28. The heat insulating composite of claim 27, wherein the polyorganosiloxane primer is formed from [3-(methacryloyloxy) propyl] trimethoxysilane.
29. 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
Figure imgf000022_0001
wherein each of Ru, Ru, and Ru 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 such that the glass particles are fused when the heat insulting composite is exposed to a temperature higher than 1000C.
30. The method of claim 29, wherein the glass particles are formed by oxides selected from the group consisting OfSiO2, B2O3, P2Os, GeO2, As2Os, AS2O3, Sb2Os, and their mixtures thereof.
31. The method of claim 30, wherein the glass particles are formed by SiO2.
32. The method of claim 30, wherein the glass particles are glass spheres.
33. The method of any one of claims 30 or 32, wherein the glass particles further include modifiers selected from the group consisting Of K2O, Na2O, CaO, BaO, PbO, ZnO,
V2O5, ZrO2, Bi2O3, Al2O3, oxides of Ti, oxides of Th, and their mixtures thereof.
34. The method of claim 31, wherein the glass particles have an average diameter of 0.05 micron to 1.5 micron.
35. The method of claim 34, wherein the glass particles have an average diameter of 0.75 micron.
36. The method of claim 29, wherein the glass particles are in an amount of 50 to 95 weight percent with respect to the binder composition, and the binder composition is in an amount of 5 to 50 weight percent with respect to the glass particles.
37. The method of claim 36, wherein the particles are in an amount of 80 weight percent, and the binder composition is in an amount of 20 weight percent.
38. The method of claim 29, wherein 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.
39. The method of claim 38, wherein the carbides are 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.
40. The method of claim 38, wherein the nitrides are selected from the group consisting of boron nitride, calcium nitride, chromium nitride, germanium nitride, magnesium nitride, aluminum nitride, zirconium nitride, and their mixtures thereof.
41. The method of claim 38, wherein the oxides are selected from the group consisting of aluminum oxide, geπnaniumQTV) oxide, indium(II or UI) oxide, magnesium oxide, silicon dioxide, silicon monoxide, thallium(III) oxide, barium calcium oxide, tungsten oxide, barium oxide, barium strontium tungsten oxide, bismuth(UI) oxide, bismuth strontium calcium copper oxide, cadmium oxide brown, cerium(IV) oxide, chromium(m) oxide, chromium(VI) oxide, cobalt(II) oxide, copρer(I) oxide, copper(H) oxide, dysprosium oxide, europium oxide, gadolinium oxide, gold(III) oxide hydrate, hafhium(IV) oxide, holmium(πi) oxide, iridium(IV) oxide or iridium(TV) oxide hydrate, lanthanum oxide, lead(IV) oxide, leadQI) oxide yellow, lutetium (LQ) oxide, manganese(π, III or IV) oxides, iriolybdenum(rV) oxide, nickel oxide, niobium(IT) oxide, niobium(IV) oxide, niobium(V) oxide, osmium tetroxide, palladium(π) oxide or its hydrate, palladium(II) oxide hydrate, ρrasedymium(III) oxide, rhenium(TV) oxide or its hydrate, rhodium(]TJ) oxide or its hydrate, samarium oxide, silver(I or U) oxides, strontium oxide, tantalum(V) oxide, terbium oxide, terbiurn(TH) oxide, thulium(HI) oxide, tin(π or IV) oxides, tungsten(VI) oxide, vanadium(III, TV, or V) oxides, ytterbium oxide, zinc oxide, zirconiurn(IV) oxide, antimony tin oxide, iron(III) oxide, yttrium(III) oxide, calcium oxide, and their mixtures thereof.
42. The method of claim 38, wherein the titanates are selected from the group consisting of barium titanate(IV), trontium titanate, and their mixtures thereof.
43. The method of claim 38, wherein the sulfides are selected from the group consisting of aluminum sulfide, antimony pentasulfide, antimony(III) sulfide* arsenicCII, III, or V) sulfides, gallium(iπ) sulfide, germaniurn(II) sulfide, indium(III) sulfide red, phosphorus pentasulfide, phosphorus trisulfide, selenium sulphide, barium sulfide, bismuth(III) sulfide, calcium sulfide, copper(I) sulfide, copper(II) sulfide, gold(I or III) sulfide, iron(II) sulfide, lead(II) sulfide, lithium sulfide, manganese(II) sulfide, mercury(π) sulfide red, palladium(II) sulfide, platinum(IV) sulfide, rhenium(Vπ) sulfide, silver sulfide, sodium sulfide, strontium sulfide, thalliumφ sulfide, tin(II) sulfide, titanium(IV) sulfide, tungsten(TV) sulfide, zinc sulfide, molybdenum(IV) sulfide, and their mixtures thereof.
44. The method of claim 38, wherein the inorganic siloxane compound is AlSi2 kaolinate (Al2(Si2O5)(OH)*).
45. The method of claim 38, wherein the binder composition further includes a minor component selected from the group consisting of carbides, metals, alloys, and their mixtures thereof
46. The method of claim 45, wherein the carbides are selecting from the group consisting of tungsten carbide, silicon carbide, and their mixtures thereof.
47. The method of claim 45, wherein the oxides are selected from the group consisting of aluminum oxide, beryllium oxide, magnesium oxide, zirconium oxide, mullite (Al6Si2O]3), and their mixtures thereof.
48. The method of claim 45, wherein the metals are selected from the group consisting of tungsten, chromium, beryllium, nickel, iron, copper, titanium, aluminum, and their mixtures thereof.
49. The method of claim 45, wherein the alloys are selected from the group consisting of low alloy steels, stainless steels, cast irons, brasses, bronzes, and their mixtures thereof.
50. The method of claim 45, wherein the major component is in an amount of 70% to 80% by weight of the binder composition, and the minor component is in an amount of 20% to 30% by weight of the binder composition.
51. The method of claim 29 further including the step of hydrolyzing the binder composition.
52. The method of claim 29, wherein the inorganic silicate is sodium silicate.
53. The method of claim 29, wherein the amount of the inorganic silicate is 30 to 40 weight percent with respect to the glass particles and the binder composition.
54. The method of claim 29 further including the step of mixing with a plastic material wherein the plastic material is selected from the group consisting of polybutylene terephthalte, polypropylene, polyacrylate and phenolic resins.
55. The method of claim 29, wherein 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.
56. The method of claim 55, wherein the polyorganosiloxane primer is formed from [3- (methacryloyloxy) propyl] trimethoxysilane,
57. 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 1000C; and a polymeric material.
58. The heat insulating composite material of claim 57, wherein the polymeric material is provided in a particulate pre-polymerised form form.
59. The heat insulating composite material of any one of claims 55 to 58, wherein the polymeric material is a thermoplastic polymeric material.
60. The heat insulating composite material of any one of claims 55 to 58, wherein the polymeric material is a thermoset polymeric material.
61. The heat insulating composite material of any one of claims 57 to 59, wherein the polymeric material selected from the group consisting of polybutylene terephthalte, polypropylene, polyacrylate and phenolic resins.
62. The heat insulating composite material of any one of claims 55 to 61, wherein the plurality of glass particles is coated with polyorganosiloxane primer, said primer being formed from monomers having a general formula
Figure imgf000027_0001
wherein each of Rn, R12, and R^ is independently selected from the group consisting of H, R, OR, OS-R3, 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.
63. The heat insulating composite material of claim 62, wherein 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.
64. The heat insulating composite material of claim 63, wherein the polyorganosiloxane primer is formed from [3-(methacryloyloxy) propyl] trimethoxysilane.
65. A 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 1000C; and a polymeric material.
66. The heat insulating composite structure of claim 65 wherein the polymeric material is a thermoplastic polymeric material.
67, The heat insulating composite structure of claim 65 wherein the polymeric material is a thermoset polymeric material.
68, The heat insulating composite structure of claim 65, wherein the polymeric material selected from the group consisting of polybutylene terephthalte, polypropylene, polyacrylate and phenolic resins.
69. The heat insulating composite structure of any one of claims 65 to 68, wherein the plurality of glass particles is coated with polyorganosiloxane primer, said primer being formed from monomers having a general formula
Figure imgf000028_0001
wherein each of Rn, Ri2, and RB is independently selected from the group consisting of H, R, OR, OSiRs, 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.
70. The heat insulating composite structure of claim 69, wherein 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.
71 The heat insulating composite material of claim 70, wherein the polyorganosiloxane primer is formed from [3-(methacryloyloxy) propyl] trimethoxysilane.
72. A heat insulating composite structure of any one of claims 65 to 71, wherein said structure is provided in a modular form.
73. A heat insulating composite structure of any one of claims 65 to 71, wherein said structure is a fire resistant construct, a fire resistant wall, a fire resistant wall, a fire resistant closure, cable coating, cladding or the like.
74. A process for forming a heat insulating composite structure, the method including the steps of: providing the heat insulating composite material according to any one of claim
57 to 64; and polymerizing the polymeric material of said heat insulating composite material so as to form a heat insulating composite structure.
75. A heat insulating composite structure when made according to the method of claim 72.
76. A heat insulating composite structure of claim 75, wherein said structure is provided in a modular form.
77. A heat insulating composite structure of claim 75, wherein said structure is a fire resistant construct, a fire resistant wall, a fire resistant wall, a fire resistant closure, cable coating, cladding or the like.
PCT/EP2006/009729 2006-10-09 2006-10-09 Heat insulating composite and methods of manufacturing thereof Ceased WO2008043373A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2006/009729 WO2008043373A1 (en) 2006-10-09 2006-10-09 Heat insulating composite and methods of manufacturing thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2006/009729 WO2008043373A1 (en) 2006-10-09 2006-10-09 Heat insulating composite and methods of manufacturing thereof

Publications (1)

Publication Number Publication Date
WO2008043373A1 true WO2008043373A1 (en) 2008-04-17

Family

ID=38137486

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/009729 Ceased WO2008043373A1 (en) 2006-10-09 2006-10-09 Heat insulating composite and methods of manufacturing thereof

Country Status (1)

Country Link
WO (1) WO2008043373A1 (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103122155A (en) * 2011-11-18 2013-05-29 上海沪正纳米科技有限公司 Preparation method of high-performance window film insulation medium
CN108707280A (en) * 2018-05-28 2018-10-26 赵锋 A method of improving polypropylene plastics thermal change type temperature
US10174569B2 (en) 2013-06-20 2019-01-08 Aspect International (2015) Private Limited NMR/MRI-based integrated system for analyzing and treating of a drilling mud for drilling mud recycling process and methods thereof
US10444170B2 (en) 2015-07-02 2019-10-15 Aspect Ai Ltd. System and method for analysis of fluids flowing in a conduit
US10598581B2 (en) 2013-11-06 2020-03-24 Aspect Imaging Ltd. Inline rheology/viscosity, density, and flow rate measurement
US10655996B2 (en) 2016-04-12 2020-05-19 Aspect Imaging Ltd. System and method for measuring velocity profiles
US10670574B2 (en) 2015-01-19 2020-06-02 Aspect International (2015) Private Limited NMR-based systems for crude oil enhancement and methods thereof
US10809338B2 (en) 2015-04-12 2020-10-20 Aspect Ai Ltd. System and method for NMR imaging of fluids in non-circular cross-sectional conduits
CN114394596A (en) * 2021-12-30 2022-04-26 铜陵日飞创客科技有限公司 Special long-life bearing for high-power plowing plough
CN114507073A (en) * 2020-11-16 2022-05-17 三菱综合材料电子化成株式会社 Zirconium nitride powder and preparation method thereof
CN115896517A (en) * 2022-11-30 2023-04-04 西安宝德九土新材料有限公司 Preparation method of rhenium and hafnium carbide composite tungsten copper infiltration ablation-resistant material
CN117602908A (en) * 2024-01-19 2024-02-27 佛山市南海联兴得利装饰材料有限公司 A sound insulation and fireproof board and its preparation method and application
EP4281288A4 (en) * 2021-01-19 2024-12-11 3M Innovative Properties Company ARTICLE WITH A GLUED AND LAMINATED FILM
CN119591386A (en) * 2024-12-09 2025-03-11 中冶武汉冶金建筑研究院有限公司 Low-carbon aluminum silicon carbide brick for ladle and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4686253A (en) * 1986-02-20 1987-08-11 United States Gypsum Company Lightweight joint compound having improved paintability
EP0322135A1 (en) * 1987-12-16 1989-06-28 Crompton Design Manufacturing Limited Materials for and manufacture of fire and heat resistant components
WO2004069766A1 (en) * 2003-02-08 2004-08-19 Technical Lightweight Composites Ltd Composite materials
WO2006128672A1 (en) * 2005-05-31 2006-12-07 Advanced Glass Ceramics Establishment Heat insulating composite and methods of manufacturing thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4686253A (en) * 1986-02-20 1987-08-11 United States Gypsum Company Lightweight joint compound having improved paintability
EP0322135A1 (en) * 1987-12-16 1989-06-28 Crompton Design Manufacturing Limited Materials for and manufacture of fire and heat resistant components
WO2004069766A1 (en) * 2003-02-08 2004-08-19 Technical Lightweight Composites Ltd Composite materials
WO2006128672A1 (en) * 2005-05-31 2006-12-07 Advanced Glass Ceramics Establishment Heat insulating composite and methods of manufacturing thereof

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103122155A (en) * 2011-11-18 2013-05-29 上海沪正纳米科技有限公司 Preparation method of high-performance window film insulation medium
US10174569B2 (en) 2013-06-20 2019-01-08 Aspect International (2015) Private Limited NMR/MRI-based integrated system for analyzing and treating of a drilling mud for drilling mud recycling process and methods thereof
US10598581B2 (en) 2013-11-06 2020-03-24 Aspect Imaging Ltd. Inline rheology/viscosity, density, and flow rate measurement
US10670574B2 (en) 2015-01-19 2020-06-02 Aspect International (2015) Private Limited NMR-based systems for crude oil enhancement and methods thereof
US10809338B2 (en) 2015-04-12 2020-10-20 Aspect Ai Ltd. System and method for NMR imaging of fluids in non-circular cross-sectional conduits
US10444170B2 (en) 2015-07-02 2019-10-15 Aspect Ai Ltd. System and method for analysis of fluids flowing in a conduit
US10655996B2 (en) 2016-04-12 2020-05-19 Aspect Imaging Ltd. System and method for measuring velocity profiles
CN108707280A (en) * 2018-05-28 2018-10-26 赵锋 A method of improving polypropylene plastics thermal change type temperature
CN114507073A (en) * 2020-11-16 2022-05-17 三菱综合材料电子化成株式会社 Zirconium nitride powder and preparation method thereof
EP4281288A4 (en) * 2021-01-19 2024-12-11 3M Innovative Properties Company ARTICLE WITH A GLUED AND LAMINATED FILM
CN114394596A (en) * 2021-12-30 2022-04-26 铜陵日飞创客科技有限公司 Special long-life bearing for high-power plowing plough
CN114394596B (en) * 2021-12-30 2023-08-22 铜陵日飞创客科技有限公司 Special long-life bearing of high-power plough
CN115896517B (en) * 2022-11-30 2024-05-24 西安宝德九土新材料有限公司 Preparation method of rhenium and hafnium carbide composite tungsten copper-infiltrated ablation-resistant material
CN115896517A (en) * 2022-11-30 2023-04-04 西安宝德九土新材料有限公司 Preparation method of rhenium and hafnium carbide composite tungsten copper infiltration ablation-resistant material
CN117602908A (en) * 2024-01-19 2024-02-27 佛山市南海联兴得利装饰材料有限公司 A sound insulation and fireproof board and its preparation method and application
CN117602908B (en) * 2024-01-19 2024-04-30 佛山市南海联兴得利装饰材料有限公司 Sound-insulation heat-preservation fireproof plate and preparation method and application thereof
CN119591386A (en) * 2024-12-09 2025-03-11 中冶武汉冶金建筑研究院有限公司 Low-carbon aluminum silicon carbide brick for ladle and preparation method thereof

Similar Documents

Publication Publication Date Title
WO2008043373A1 (en) Heat insulating composite and methods of manufacturing thereof
CN1254451C (en) Inorganic matrix composition and composite material incorporating said matrix composition
Li et al. Simultaneously improved flame retardance and ceramifiable properties of polymer-based composites via the formed crystalline phase at high temperature
KR101596378B1 (en) Composite composition of inorganic oxide particles and silicone resin, and transparent composite material
JPH0772250B2 (en) Solvent-free room temperature curable organosiloxane composition, method for producing the same, and use thereof
EP0856494B2 (en) Binding agent for mineral wool and mineral wool product bonded therewith
WO2006128672A1 (en) Heat insulating composite and methods of manufacturing thereof
TW201024377A (en) A silicone composition and a method for preparing the same
TWI313283B (en) Curable epoxy resin composition
CN109880176B (en) Low temperature cerammed polymer-based composites
JP2016514662A (en) Thermosetting ceramic composition and preparation method thereof
JPH073163A (en) Solventless liquid organosiloxane composition and use thereof
US2610957A (en) Interbonded fibrous glass
TW200914529A (en) Curable epoxy resin composition and cured product thereof
CN1367719A (en) Phenolic coated refractory aggregates
WO2010139011A1 (en) Fire performance polymer comprising glass composition
CN104448701A (en) Epoxy resin composition, purpose of same, and fillings for epoxy resin composition
JP2015199625A (en) Core-shell structure, method for producing the same, and heat conductive resin composition
JP2738904B2 (en) Water-containing organosiloxane liquid composition and its use
CA1080380A (en) Molding compound
US20160251515A1 (en) Curable resin composition, article, and method for fabricating the same
JP6946088B2 (en) A composition for a cured resin, a cured product of the composition, a method for producing the composition and the cured product, and a semiconductor device.
KR101667445B1 (en) Silane based compound, method for preparing the same and polycarbonate resin composition comprising the same
AU2013282679A1 (en) Heat-resistant inorganic fiber
EP3371124A1 (en) A process for providing inorganic polymer ceramic-like materials

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 06792407

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06792407

Country of ref document: EP

Kind code of ref document: A1