WO1997013803A1 - Aerogelbeschichtete folie - Google Patents
Aerogelbeschichtete folie Download PDFInfo
- Publication number
- WO1997013803A1 WO1997013803A1 PCT/EP1996/004434 EP9604434W WO9713803A1 WO 1997013803 A1 WO1997013803 A1 WO 1997013803A1 EP 9604434 W EP9604434 W EP 9604434W WO 9713803 A1 WO9713803 A1 WO 9713803A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- airgel
- gel
- film according
- fibers
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
- Y10T428/249969—Of silicon-containing material [e.g., glass, etc.]
Definitions
- the invention relates to thermal insulation materials based on aerogels, a process for their production and their use
- Aerogels are highly porous, low-density materials that are made by forming a gel and then removing the liquid while largely maintaining the gel structure.
- aerogels are materials in which the liquid is removed from the gel under supercritical conditions, while in gel drying under subcritical conditions of Xerogels and in the case of removal of the liquid from the frozen state by sublimation speaks of cryogels.
- Aerogels in the sense of the invention comprise all these materials and can also contain any other gases in addition to air.
- the gases can also be removed from the airgel under vacuum.
- aerogels with porosities of over 60% and densities below 0.6 g / cm 3 have a very low thermal conductivity and are therefore suitable as thermal insulation materials. Due to their low density, such materials are not mechanically stable.
- airgel-containing compositions are described, for example, in EP-A 0 340 707 and DE-A 44 37 424, which additionally contain a binder. To be mechanically demanding
- the airgel can be reinforced by incorporating fibers (see, for example, DE-A 44 30 642).
- fibers see, for example, DE-A 44 30 642.
- aerogels can also be applied as a thin layer on flexible foils, with which airgel materials with good mechanical stability can be produced.
- DE-A 38 44 003 describes films coated with silica gel, which also contain photochromic compounds.
- a washing liquid which contains up to 5% polyvinyl alcohol in addition to the photochromic substances, is placed in a liquor container for its production.
- a transparent film for example a polyacrylate film, is passed through the liquor and sprayed onto the liquid film formed in this way, water glass and sulfuric acid solution, with silica gel separating out.
- the film coated in this way is subjected to drying at approximately 80 ° C. and a pressure of 0.1 to 0.5 bar.
- this manufacturing process does not produce a product with a gel structure, so it is not an airgel-coated film.
- the invention therefore relates to a coated film comprising an airgel layer.
- the airgel preferably in the form of powder or granules, is enclosed in the film.
- the airgel can be evacuated, but does not have to.
- the film coated according to the invention has good mechanical stability.
- films are all common film materials such as polyester, for example polyethylene terephthalate (PET), cellulose and its derivatives, for example cellophane ®, polyolefins, such as polyethylene, polypropylene, polystyrene, polymethyl (meth) acrylates, polyvinyl chloride, polyamides, and polycarbonates are suitable, with molecular weights and Orientations are generally not critical.
- the films can also contain fibers (eg glass fibers).
- Metal foils for example made of aluminum, are likewise suitable, in which case opaque applications are pursued.
- Preferred film materials are polypropylene and polyethylene terephthalate, with biaxially oriented films being particularly preferred. Films which are characterized by the lowest possible flammability are also advantageous.
- the film can also be printed or colored.
- the films are preferably pretreated by conventional methods known to those skilled in the art.
- a chemical pretreatment for example with aminosiloxanes or imines, or a pretreatment by coronary discharge processes is preferred.
- the foils prepared in this way generally have a thickness of 5 to 1000 ⁇ m.
- the films can be textured or structured in order to achieve special optical effects.
- the film is structured such that the transmission of directed light varies depending on the angle of incidence.
- This effect can e.g. can be achieved by using a film that has been shaped into a suitable profile (e.g. sawtooth-like profile), with this profile producing lamellas.
- the slats are preferably arranged so that their edges are as perpendicular as possible to the direction of incidence of the light.
- more or less strong reflection and thus less or more transmission occurs on the inclined surfaces. This can e.g.
- the structuring of the film can e.g. To avoid contamination from dust deposits on the side facing away from the airgel, be covered by another flat film.
- the coated film according to the invention preferably contains aerogels with porosities above 60%, particularly preferably above 70%, and in particular above 80%.
- the density of the airgel is generally below 0.6 g / cm 3 , preferably below 0.4 g / cm 3 .
- the porosity is defined as a percentage of the pore volume in the total volume of the airgel.
- the thermal conductivity of the airgel should preferably be less than 40 mW / mK and particularly preferably less than 25 mW / mK.
- the aerogels used according to the invention are generally obtained in a) a sol is produced, b) fibers are optionally added to the sol, c) the sol obtained in b) is converted into a gel, d) the liquid contained in the gel is exchanged, and e) the one obtained in d) Gel is dried so that an airgel is formed.
- Metal oxide compounds suitable for the sol-gel technique in particular Si and Al compounds (CJ. Brinker, GW Scherer, Sol-Gel-Science, 1 990, Chapters 2 and 3) such as Si or Al alkoxides, water glass, organic polycondensates based on
- the sol can consist of particulate or colloidal Si or Al oxide. Si compounds, in particular water glass, are preferably used.
- the sol particles carry functional groups on the surface that are capable of condensation. These groups are called surface groups in the following. Sol particles composed of Si or Al compounds typically carry hydrophilic hydroxyl groups (OH). Due to the production process, residues of alkoxy groups (OR) may also be present if alkoxides are used as starting materials (CJ. Brinker, G.W. Scherer, Sol-Gel-Science, 1 990, Chapter 1 0).
- an IR opacifier e.g. Soot, titanium dioxide, iron oxides or zirconium dioxide, the radiation contribution to thermal conductivity can be reduced.
- Dyes and / or color pigments can optionally be added to achieve coloring.
- a fiber material is optionally added.
- Inorganic fibers such as glass fibers or mineral fibers, organic fibers such as polyester fibers, aramid fibers, nylon fibers or fibers of plant origin, and mixtures thereof can be used as the fiber material.
- the fibers can also be coated, e.g. Polyester fibers bonded with a metal such as Aluminum are metallized.
- Glass fibers and fibers made of the material that serves as the raw material for the uncoated film are preferred.
- the coating can also serve a better connection of the airgel to the fibers, in analogy to so-called “coupling agents” on glass fibers in glass fiber reinforced plastics.
- the volume fraction of the fibers should be 0.1 to 30%, preferably 0.1 to 10% and b) the thermal conductivity of the fiber material should be as low as possible, preferably ⁇ 1 W / mK.
- densities of up to 0.9 g / cm 3 can also occur.
- the fiber diameter in a) non-metallized fibers should preferably be 0.1 to 30 ⁇ m and / or in b) metallized fibers preferably 0.1 to 20 ⁇ m.
- the radiation contribution to thermal conductivity can be further reduced by adding IR-opaque fibers, e.g. soot-blackened PET fibers can be used.
- IR-opaque fibers e.g. soot-blackened PET fibers can be used.
- the mechanical strength of the airgel layer is further influenced by the length and distribution of the fibers in the airgel.
- the fibers can e.g. can be introduced as disordered or aligned fibers. In this case, in order to ensure sufficient strength of the composite, they should preferably be at least 1 cm long.
- the fibers can be coated with a suitable size.
- the coating can also serve to better bind the gel to the fibers.
- the sol can be converted into a gel (step c), for example, by hydrolysis and condensation of Si or Al alkoxides, gelling of particulate or colloidal Si or Al oxide or a combination of these methods.
- a gel for example, by hydrolysis and condensation of Si or Al alkoxides, gelling of particulate or colloidal Si or Al oxide or a combination of these methods.
- the production of gels containing Si is described, for example, in WO 93/06044.
- the preparation of the organic gels is e.g. in US-A-5,086,085 and US-A-4,873,21 8.
- the gel should be washed with water free of electrolytes. Fibers can also be added during gel formation, especially in the case of single fibers, when the sol has already reached a high viscosity but is not yet solid.
- the aging of the gel generally takes place at a temperature from 20 ° C. to the boiling point of the liquid contained in the gel. If the gel liquid is, for example, water and the gel matrix is SiO 2 , the aging process generally takes place at 20 to 90 ° C., preferably 20 to 70 ° C., at a pH of 6 to 11, preferably 6 to 9, within 1 minute to 48 hours, especially 5 minutes to 24 hours.
- the liquid contained in the gel is replaced in at least one washing process (step d) by the same or a different liquid which is suitable for the subsequent drying in step e).
- Steps a) to d) are generally carried out at a temperature between the freezing point of the liquid contained in the gel and 70 ° C., but at most the boiling temperature of the liquid contained in the gel.
- the gel obtained in step d) can advantageously be dried subcritically to form an airgel composite.
- the drying process is characterized in that
- step d) the gel obtained in step d) is reacted with one or more surface-modifying substances such that such a large proportion of the surface groups of the gel are replaced by groups of the surface-modifying substance that further condensation between the surface groups on different pore surfaces is largely suppressed and / or by change of the contact angle between the pore surface and the liquid from which drying takes place, the capillary forces are reduced, e2) if necessary the liquid contained in the gel is exchanged and e3) the resulting gel at a temperature below the critical temperature of the liquid contained in the gel and a pressure of 0.001 bar up to the vapor pressure of this liquid is dried at this temperature.
- step d) a liquid suitable for the following process steps must be used for washing. If the gel contains water, for example, it is advisable to wash the gel with a protic or aprotic organic solvent until the water content of the gel is 5 5% by weight, preferably ⁇ 2% by weight.
- ethers, esters or ketones and aliphatic or aromatic hydrocarbons are used as organic solvents.
- Preferred solvents are methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dioxane, n-hexane, n-heptane and toluene. Mixtures of the solvents mentioned can also be used.
- the solvent must be largely inert with regard to the surface-modifying substance used in the following step.
- the surface-modifying substances used in step e1) convert a large proportion of the hydrophilic or reactive surface groups on the pore surfaces to hydrophobic or surface groups unsuitable for further condensation.
- R ' n MX m By reaction with surface-modifying substances of the general formula R ' n MX m , the original surface groups are partially or completely replaced by inert groups of the MR' n type.
- n and m are integers greater than zero, the sum of which corresponds to the valency of M.
- R ' is hydrogen or a non-reactive organic linear, branched, cyclic, aromatic or heteroaromatic radical such as C 1 -C 8 alkyl, preferably C 6 -C 6 alkyl, particularly preferably methyl or ethyl, cyclohexyl or phenyl; the R 'are independently the same or different or can be bridged.
- the silylated gel can preferably be washed with a protic or aprotic solvent until the unreacted surface-modifying substance has essentially been removed (residual content ⁇ 1% by weight).
- Suitable solvents are those mentioned for step d). Analogously, the solvents mentioned there as preferred are also preferred here.
- step e3) the optionally reinforced, surface-modified gel at temperatures from -30 to 200 ° C., preferably 0 to 100 ° C., and a pressure of 0.001 to 20 bar, preferably 0.01 to 5 bar, is particularly preferred preferably 0.1 to 2 bar, dried. Temperatures higher than 200 ° C and / or pressures higher than 20 bar are easily possible, but they are associated with unnecessary effort and bring no advantages.
- Drying is generally continued until the gel has a residual solvent content of less than 0.1% by weight.
- Contact and convection drying are suitable drying methods.
- drying of the gel can be accomplished using dielectric drying techniques, e.g. can be significantly accelerated by microwave drying.
- the solvent in step e2) is exchanged, if necessary, for a solvent that absorbs microwaves well, e.g. Water, ethanol or preferably acetone.
- the gels can then be quickly dried in a microwave dryer. It is also possible to dry with visible light.
- Gels with are particularly advantageous for solvent exchange and drying a thickness between 0.5 and 5 mm, since the duration for the exchange of solvents or the drying time is essentially determined by diffusion of the solvent or the solvent vapor.
- step a an acidic ion exchange resin is preferably used.
- the composite material obtained in this way is hydrophobic if the surface groups applied by the surface modification are hydrophobic, for example when using trimethylchlorosilane.
- the hydrophobicity can subsequently be reduced, for example by expulsion or partial pyrolysis become.
- step e) the gel obtained in step d) can be dried to an airgel composite, for example by converting the liquid contained in the gel into a supercritical state and then removing the liquid from the solid by flash evaporation at supercritical temperature.
- a liquid suitable for drying such as liquid CO 2 or methanol, must be used for the exchange in step d).
- Typical processes for supercritical drying from CO 2 are, for example, in US-A-4, 610,863 or in Bommel MJ, de Haan, AB, Journal of Materials Science, 29, (1 994), pp. 943-948, and from methanol in EP-B-0396076 or WO 93/06044.
- the gel can be reacted between step d) and e), optionally after the solvent exchange, with a surface-modifying substance which leads to a hydrophobization of the surface.
- the solvent may have to be exchanged again for the liquid suitable for drying. Suitable for this are e.g. the above-mentioned substances and processes for surface modification.
- the reaction can advantageously also take place after drying by a reaction in the gas phase.
- the aerogels used according to the invention preferably contain no binders as additives in order to keep the thermal conductivity as low as possible.
- the films according to the invention are produced in such a way that a suitable sol, if appropriate after step b), is applied to an optionally pretreated film and converted to a gel by polycondensation.
- a suitable sol if appropriate after step b
- the condensing agent for example a base
- the application can be carried out using different thick and thin layer techniques known to the person skilled in the art, such as spraying, dipping, dip coating, filling and spreading.
- the gel which may be diluted, can be subjected to an ultrasound treatment before coating.
- Another production variant for the film according to the invention is the production of a, preferably glass fiber-reinforced, airgel with subsequent gluing of the airgel layer onto the optionally pretreated film.
- a further production of the film according to the invention is carried out by applying airgel powder or airgel granulate, whereby a granulate can also be a made-up powder, to which adhesion promoters, for example in the form of hot melt adhesives, may be added to an optionally pretreated film.
- a second film of the same or different type is then placed on the airgel layer and, if necessary, with the aid of vacuum technology and, if appropriate, heated to the first film pressed and partially melted and / or glued to it so that areas of the airgel are enclosed.
- the foils can already contain depressions which are conducive to airgel inclusion.
- the invention also relates to a film obtainable by this process.
- This procedure can be repeated any number of times to build up thicker layers or laminates.
- the films according to the invention are used, for example, as thermal insulation materials.
- a Hostaphan ® PET film (Hoechst Diafoil Company, Grees, South Carolina) is treated with an oxygen plasma for 3 hours at 2.0 torr and then placed on a horizontal surface with a 1 cm increase on the sides for further coating with a silica solution .
- the film is then covered with a layer of 1 mm of a 9% water glass solution, the cations of which have been separated off beforehand by an ion exchange column.
- the pH of the solution was previously adjusted to 4.7 by the slight addition of 0.1N sodium hydroxide solution.
- the pad is tightly closed and heated to 80 ° C on a hot plate. Within a few (10) minutes the solution gels to a solid gel, which is aged for 3 hours at 80 ° C.
- the base with the film and the gel adhering to it is then cooled at a rate of 2 ° C. per minute and covered with 9 ml of acetone and left to stand for 20 minutes.
- the acetone below contains water from the gel layer. It is poured off and made up with new acetone. The process is repeated until the water content of the poured aqueous acetone solution is below 1% (Karl Fischer titration).
- the film is then covered with a solution of 5% trimethylchlorosilane in acetone.
- the pad is closed again and left for 1 hour.
- the supernatant solution is then poured off, washed three times with fresh acetone for 20 minutes each, and the film with the surface-modified gel adhering to it is placed in an unsealed state for drying in a drying cabinet at 50.degree.
- the dried film is removed and cooled.
- the airgel layer shows slight cracks, but also adheres to the film when dry.
- 5 layers of the film produced in this way are heated using the heating wire method (see, for example, O. Nielson, G. Haischenpöhler, J. prom, J. Fricke, High Temperatures-High Pressures, Vol. 21, 267-274 (1,989 The measured conductivity is 21 mW / mK.
- the film coated with the gel is removed from the oven after drying and carefully covered with a cover film made of the same material to protect it from mechanical destruction and used for measuring the thermal conductivity.
- PET polyester (polyethylene terephthalate)
- PVDC polyvinylidene chloride
- a "high density” polyethylene HDPE film is used and placed in the holder.
- a 1 mm thick layer of a glass fiber fleece GH 50.502 from the company "Glasfaser Rege ⁇ sburg” is placed on the sol, which has previously been annealed at 600 ° C. for 30 minutes.
- the sol is produced analogously to Example 1 and poured over the glass fiber fleece.
- a 1 mm high sol layer forms on the HDPE film, in which the fleece is evenly distributed. Further processing is carried out according to example 1. After drying, the film coated with airgel is covered with a second HDPE film. Since all layers are translucent, the fiber structure of the enclosed glass fiber fleece can be clearly recognized.
- the thermal conductivity of the sample is 18 mW / mK.
- Example 23 Analogously to Example 23, a PET film is used as the base. A 2 mm thick fiber-reinforced airgel layer is produced on it and then covered with an HDPE film. The thermal conductivity of the sample is 1 6 mW / mK.
- 60 ml of an aqueous dispersion of styrene / acrylate copolymer, solids content: 19% by weight (34 ml of Mowilith DM 760, 26 ml of water) are placed in a 200 ml beaker and 125 ml of hydrophobic airgel granules with a particle size in the range of 50 to 250 microns (bulk density 0.08 g / cm 3 ) mixed with a propeller at 1200 rpm until a flowable suspension arises.
- This is applied as a heat-insulating adhesive in a layer thickness of 0.1 mm using a doctor blade on a polyester film.
- PET polyethylene terephthalate
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Silicon Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Formation Of Insulating Films (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT96934647T ATE220083T1 (de) | 1995-10-11 | 1996-10-11 | Aerogelbeschichtete folie |
KR1019980702630A KR19990064149A (ko) | 1995-10-11 | 1996-10-11 | 에어로겔 피복된 시이트 |
DE59609414T DE59609414D1 (de) | 1995-10-11 | 1996-10-11 | Aerogelbeschichtete folie |
CA 2232628 CA2232628A1 (en) | 1995-10-11 | 1996-10-11 | Aerogel-coated film |
US09/051,258 US6316092B1 (en) | 1995-10-11 | 1996-10-11 | Aerogel-coated sheet |
EP96934647A EP0854892B1 (de) | 1995-10-11 | 1996-10-11 | Aerogelbeschichtete folie |
JP51472097A JP3703032B2 (ja) | 1995-10-11 | 1996-10-11 | エーロゲル被覆フィルム |
NO19981452A NO315241B1 (no) | 1995-10-11 | 1998-03-31 | Aerogelbelagt folie, fremgangsmåter for fremstilling derav samt anvendelseav folien |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19537821A DE19537821A1 (de) | 1995-10-11 | 1995-10-11 | Aerogelbeschichtete Folie |
DE19537821.0 | 1995-10-11 | ||
DE19606114.8 | 1996-02-20 | ||
DE19606114A DE19606114A1 (de) | 1996-02-20 | 1996-02-20 | Aerogelbeschichtete Folie |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997013803A1 true WO1997013803A1 (de) | 1997-04-17 |
Family
ID=26019409
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/004434 WO1997013803A1 (de) | 1995-10-11 | 1996-10-11 | Aerogelbeschichtete folie |
Country Status (12)
Country | Link |
---|---|
US (1) | US6316092B1 (de) |
EP (1) | EP0854892B1 (de) |
JP (1) | JP3703032B2 (de) |
KR (1) | KR19990064149A (de) |
CN (1) | CN1105737C (de) |
AT (1) | ATE220083T1 (de) |
CA (1) | CA2232628A1 (de) |
DE (1) | DE59609414D1 (de) |
ES (1) | ES2177810T3 (de) |
MX (1) | MX9802834A (de) |
NO (1) | NO315241B1 (de) |
WO (1) | WO1997013803A1 (de) |
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US7534821B2 (en) * | 2005-08-11 | 2009-05-19 | Xerox Corporation | Polymeric aerogel nanocomposites |
KR100763430B1 (ko) * | 2006-11-23 | 2007-10-04 | (주)에스케이아이 | 보온단열재 |
KR20080047150A (ko) * | 2006-11-24 | 2008-05-28 | 한국생산기술연구원 | 에어로겔 단열시트가 내장된 휴대용 정보기기 |
US8734931B2 (en) | 2007-07-23 | 2014-05-27 | 3M Innovative Properties Company | Aerogel composites |
WO2010080238A2 (en) * | 2008-12-18 | 2010-07-15 | 3M Innovative Properties Company | Telechelic hybrid aerogels |
KR101560738B1 (ko) * | 2009-02-11 | 2015-10-16 | 삼성전자 주식회사 | 유기 에어로젤, 이의 형성용 조성물 및 이의 제조방법 |
KR20110049572A (ko) * | 2009-11-05 | 2011-05-12 | 삼성전자주식회사 | 유기 에어로젤, 유기 에어로젤용 조성물 및 상기 유기 에어로젤의 제조 방법 |
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- 1996-10-11 ES ES96934647T patent/ES2177810T3/es not_active Expired - Lifetime
- 1996-10-11 JP JP51472097A patent/JP3703032B2/ja not_active Expired - Fee Related
- 1996-10-11 KR KR1019980702630A patent/KR19990064149A/ko not_active Application Discontinuation
- 1996-10-11 CA CA 2232628 patent/CA2232628A1/en not_active Abandoned
- 1996-10-11 DE DE59609414T patent/DE59609414D1/de not_active Expired - Lifetime
- 1996-10-11 WO PCT/EP1996/004434 patent/WO1997013803A1/de not_active Application Discontinuation
- 1996-10-11 CN CN96197560A patent/CN1105737C/zh not_active Expired - Fee Related
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EP2813338B1 (de) | 2003-06-24 | 2016-08-17 | Aspen Aerogels Inc. | Verfahren zur Herstellung von Gelfolien |
CN108841142A (zh) * | 2017-06-28 | 2018-11-20 | 郑善 | 一种具有空气净化功能的pet聚酯切片的应用 |
CN108841141A (zh) * | 2017-06-28 | 2018-11-20 | 郑善 | 一种具有空气净化功能的pet聚酯切片的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN1105737C (zh) | 2003-04-16 |
NO315241B1 (no) | 2003-08-04 |
CN1199411A (zh) | 1998-11-18 |
JPH11513431A (ja) | 1999-11-16 |
ES2177810T3 (es) | 2002-12-16 |
CA2232628A1 (en) | 1997-04-17 |
NO981452D0 (no) | 1998-03-31 |
KR19990064149A (ko) | 1999-07-26 |
ATE220083T1 (de) | 2002-07-15 |
EP0854892A1 (de) | 1998-07-29 |
US6316092B1 (en) | 2001-11-13 |
DE59609414D1 (de) | 2002-08-08 |
EP0854892B1 (de) | 2002-07-03 |
MX9802834A (es) | 1998-11-30 |
NO981452L (no) | 1998-03-31 |
JP3703032B2 (ja) | 2005-10-05 |
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