CN1546312A - Aerogel recombination flexible thermal insulation heat-proof thin film and process for preparing same - Google Patents

Aerogel recombination flexible thermal insulation heat-proof thin film and process for preparing same Download PDF

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Publication number
CN1546312A
CN1546312A CNA2003101092801A CN200310109280A CN1546312A CN 1546312 A CN1546312 A CN 1546312A CN A2003101092801 A CNA2003101092801 A CN A2003101092801A CN 200310109280 A CN200310109280 A CN 200310109280A CN 1546312 A CN1546312 A CN 1546312A
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sio
film
aerogel
kapton
heat
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CN100410069C (en
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倪星元
黄耀东
程银兵
沈军
周斌
吴广明
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Tongji University
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Tongji University
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Abstract

The invention is a kind of aerogel compound soft thermal retardation and insulation film and the manufacturing method. It uses orthosilicate ethyl ester and distilled water as material; the invention can produce transparent SiO2 multi-aperture aerogel with colloidal sols and jell. The aperture rate of the aerogel is bigger than 90%, the aperture radius size is about 20nm, the volume density is 0.03g/cm3, the specific surface is 1120m2/g, the aerogel is blended with organic silicon resin after being crushed, and they are distributed onto polymide film. The other surface of the polymide uses vacuum plating deposited metal aluminum film forms the compound soft thermal retardation film which uses SiO2 multi-aperture aerogel/polymide film/metal aluminum as structure, the heat conductivity of aerogel compound soft thermal insulation film is 0.035w/mk under temperature of 500oC; it is a kind of excellent thermal insulation materials.

Description

Aeroge composite and flexible insulation film and preparation method thereof
Technical field
The invention belongs to the insulation material technical field, be specifically related to a kind of aeroge composite and flexible insulation film and preparation method thereof.
Background technology
SiO 2Aeroge is the low-density porous material of a kind of high-specific surface area, because the existence of nanometer network structure, caused this material itself to have special nature, have a wide range of applications in various fields such as optics, electricity, acoustics, environmental protection, metallurgy, classified as the world's ten big hot topic science and technology by U.S.'s the 250th phase " science ".Also there are many people in China in the research of carrying out this respect.SiO 2The nanoporous aeroge is the solid-state material (Nicola Huling Ulrich Schubert Angew Chem Int Ed.1998,37:22~45) of present heat-insulating property the best as a kind of efficient and light weight insulation material.But few this of actual use mainly is because the mechanical strength of aeroge is not enough, and therefore difficult forming has hindered large tracts of land or widely-used on a large scale.Attempt with compound (Chinese patent 95197068.2 " a kind of composite, its preparation method and application that the contains aeroge " 96196879.6 " composites that contain aeroge and adhesive of aeroge and other material for addressing this problem the someone, its preparation method and application thereof ") but its goods are composite board, be not suitable for special-shaped object and coat, and be not to be exclusively used in heat preservation and insulation field.We have invented the flexible heat-insulating thermal insulation film that has fine heat-insulating property and mechanical performance concurrently on the basis of having carried out the compound research of nanoporous aerogel particle and organic siliconresin for this reason.
Summary of the invention
The objective of the invention is to propose a kind of flexible heat-insulating thermal insulation film that has good thermal insulation property and mechanical performance concurrently and preparation method thereof.
The flexible heat-insulating thermal insulation film that the present invention proposes is by SiO 2The composite membrane that porous aerogel layer, heat-resistant plastic film, metal fever reflecting layer are formed successively.
In the above-mentioned composite and flexible film, SiO 2The thickness of porous aerogel layer is 2-5mm, and heat-resistant plastic film's thickness is 0.8-2mm, and the thickness in metal fever reflecting layer is 0.001-0.004mm.
In the above-mentioned composite and flexible film, the heat-resistant plastic film can adopt Kapton, and aluminium (Al) can be adopted in the metal fever reflecting layer.
Among the present invention, porous aerogel is adiabatic material of main part, and it is presoma with the ethyl orthosilicate, adopts the method for colloidal sol-gel to be prepared acquisition.By optimizing operation, the porosity of aeroge and specific area are increased, aperture size and thermal conductivity descend.Aeroge hole rate reached as high as more than 90% before the present invention was compound, and aperture size is about 15-50nm, and specific area is 1000-1200m 2/ g, bulk density 0.025-0.035g/cm 3Be lower than 0.035w/mk as the thermal conductivity of heat preserving and insulating material goods 500 ℃ the time.The coefficient of heat conduction of silica material itself is very low, makes it the solid conduction and the gaseous exchange conduction of trap heat very effectively owing to having created very high hole ratio and low bulk density.Especially when the aperture during less than infrared wavelength insulation effect in essence sudden change and raising will be arranged.
The heat-resistant plastic film is through relatively selecting the very good Kapton of thermal property for use, even if the environment temperature about 350 ℃ can carbonization or rotten yet.Here polyimides has not only played the effect of the skeleton of whole film, itself also has good adiabatic function.Polyimides is flexible under the suitable thickness situation, collapsible and winding, therefore the insulation demand of very suitable various occasions and shape.Work as SiO 2After the nanoporous aeroge is compound with it, be that carrier is with SiO with the Kapton 2The nanoporous aeroge clads on needs insulations or the heat insulation object, thereby has improved the insulation characteristic greatly, has also greatly expanded range of application.
The 3rd thermal conduction mechanism is radiation heat conduction except solid and convection current, as the reflecting layer, has good heat reflection effect with metals such as metallic aluminiums.The method of aluminium with thermal evaporation is plated on the Kapton, intercepted the infra-red radiation of thermal source effectively, make heat insulating effect more improve a step.
The composite and flexible insulation film that the present invention proposes can prepare with following method: with ethyl orthosilicate, absolute ethyl alcohol and distilled water is raw material, prepares SiO with colloidal sol-gel method 2Porous aerogel; Aeroge mixes with high-temperature resistance adhesive through pulverizing, and evenly is applied on the Kapton; At another surface of Kapton Vacuum Coating method plated metal aluminium film, form with SiO 2Porous aerogel/Kapton/aluminium film is the composite and flexible insulation film of structure.
The detailed making step of the present invention is as follows:
Step 1 is a raw material with ethyl orthosilicate, absolute ethyl alcohol and distilled water, is that catalyst mixes back stirring 0.4-0.6hr by following volume ratio with HF, and the static 2-4hr that deposits obtains SiO 2Wet gel, ethyl orthosilicate: absolute ethyl alcohol: distilled water: HF are 1: (8-10): (0.4-0.6): (0.08-0.012);
Step 2 is with SiO 2Wet gel is put into trim,ethylchlorosilane solution, soaks 20-30hr and takes out, and treats to put into after the dry tack free baking oven and heats to 200-280 ℃ and heat-treat, and obtains transparent SiO 2Porous aerogel.The trim,ethylchlorosilane consumption of doing to modify on the surface is SiO 2Wet gel weight is 8-12%;
Step 3 is with the transparent SiO of modified processing 2Porous aerogel sieves and is crushed to the granule of the following diameter of 3mm, and by volume 1: (0.5-0.7) amount and organic siliconresin are mixed into pasty state, and to Kapton, coating layer thickness is 2-5mm, dries in the drying tunnel of coating machine with the coating machine coated;
Step 4 will be sent into the continuous vacuum coating machine through the Kapton of coating, not have plated metal aluminium film on the face of coated with conventional vacuum aluminizing method, and evaporation source is 98% aluminium wire.
Characteristics of the present invention are:
1. adopt the method for colloidal sol-gel to make nano-porous materials, the hole ratio height, the aperture is little, and the convection current of solid thermal conduction and hot-air is had good iris action.
2. adopt the constant pressure and dry method to prepare nano-porous materials, cost of manufacture greatly reduces, and goods can be used in a large number.
3. through finishing nano-porous materials can evenly be mixed with adhesive, be applied on the Kapton.
4. be that carrier is with SiO with the flexible polyimide film 2The nanoporous aeroge clads on needs insulations or the heat insulation object, and heat preserving and insulating material can be folded or twine, and has greatly expanded the scope of application.
Description of drawings
Fig. 1 is a flexible heat-insulating thermal insulation film structural representation.
Number in the figure: 1 is SiO 2The porous aerogel layer, 2 is the heat-resistant plastic film, 3 is metallic reflector.
The specific embodiment
Embodiment 1:
100ml ethyl orthosilicate, 1000ml absolute ethyl alcohol, 50ml distilled water and 10mlHF are evenly mixed the back stir 0.5hr, the static 3hr that deposits obtains SiO 2Wet gel.Then with SiO 2Wet gel is put into the solution that is uniformly mixed into by 1000ml n-hexane and 100ml trim,ethylchlorosilane and is done the surface modification.Treat to take out behind the 24hr, treat to put into baking oven after the dry tack free, heat to 200 ℃ and heat-treat, obtain transparent SiO 2Porous aerogel.
Embodiment 2:
Transparent SiO with modified processing 2Porous aerogel sieves and is crushed to the 3mm granule of diameter once, and 1: 0.6 by volume amount and organic siliconresin are mixed into pasty state, pours in the hopper of coating machine, uses the coating machine coated to Kapton, coating layer thickness 3mm.The speed of service 5m/min of film on coating machine, 110 ℃ of drying tunnel temperatures,, in the drying tunnel of coating machine, dry.
Embodiment 3: will send into the continuous vacuum coating machine through the laminated film of coating, and not have plated metal aluminium (Al) film on the face of coated composite at film with the vacuum aluminizing method of routine.The working vacuum degree is 4 * 10 -2Pa, evaporation source are 98% aluminium wire, the speed of service 50m/min of film on coating machine.Promptly obtain required well behaved flexible heat-insulating thermal insulation film.

Claims (5)

1. aeroge composite and flexible insulation film is characterized in that for by SiO 2The composite membrane that porous aerogel layer, heat-resistant plastic film, metal fever reflecting layer are formed successively; Wherein, SiO 2The thickness of porous aerogel layer is 2-5mm, and heat-resistant plastic film's thickness is 0.8-2mm, and the thickness in metal fever reflecting layer is 0.001-0.004mm.
2. insulation film according to claim 1 is characterized in that SiO 2The hole ratio of porous aerogel is more than 90%, and aperture size is 15-50nm, and specific area is 1000-1200m 2/ g, bulk density 0.025-0.035g/cm 3
3. insulation film according to claim 1 is characterized in that the heat-resistant plastic film is a Kapton, and the metal fever reflecting layer is an aluminium.
4. the preparation method as the described aeroge composite thermal insulation of one of claim 1-3 film is characterized in that with ethyl orthosilicate, absolute ethyl alcohol and distilled water be raw material, prepares SiO with colloidal sol-gel method 2Porous aerogel; Aeroge mixes with high-temperature resistance adhesive through pulverizing, and evenly is applied on the Kapton; At another surface of Kapton Vacuum Coating method plated metal aluminium film, form with SiO 2Porous aerogel/Kapton/aluminium film is the composite and flexible insulation film of structure.
5. preparation method according to claim 4 is characterized in that:
Step 1 is a raw material with ethyl orthosilicate, absolute ethyl alcohol and distilled water, is that catalyst mixes back stirring 0.4-0.6hr by following volume ratio with HF, and the static 2-4hr that deposits obtains SiO 2Wet gel, ethyl orthosilicate: absolute ethyl alcohol: distilled water: HF are 1: (8-10): (0.4-0.6): (0.08-0.012);
Step 2 is with SiO 2Wet gel is put into trim,ethylchlorosilane solution, soaks 20-30hr and takes out, and treats to put into after the dry tack free baking oven and heats to 200-280 ℃ and heat-treat, and obtains transparent SiO 2Porous aerogel, the trim,ethylchlorosilane consumption of doing to modify on the surface is SiO 2Wet gel weight is 8-12%;
Step 3 is with the transparent SiO of modified processing 2Porous aerogel sieves and is crushed to the granule of the following diameter of 3mm, and by volume 1: (0.5-0.7) amount and organic siliconresin are mixed into pasty state, and to Kapton, coating layer thickness is 2-5mm, dries in the drying tunnel of coating machine with the coating machine coated;
Step 4 will be sent into the continuous vacuum coating machine through the Kapton of coating, not have plated metal aluminium film on the face of coated with conventional vacuum aluminizing method, and evaporation source is 98% aluminium wire.
CNB2003101092801A 2003-12-11 2003-12-11 Aerogel recombination flexible thermal insulation heat-proof thin film and process for preparing same Expired - Fee Related CN100410069C (en)

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Cited By (13)

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CN103009711A (en) * 2013-01-22 2013-04-03 昆山汉品电子有限公司 Diffusion and heat insulating film
CN103450685A (en) * 2013-08-09 2013-12-18 苏州纳埃净化科技有限公司 Manufacturing method of nano porous material
CN103527901A (en) * 2013-10-31 2014-01-22 上海交通大学 Non-vacuum multilayer flexible heat insulation quilt and manufacturing method thereof
CN103753886A (en) * 2014-01-27 2014-04-30 苏州乾雄金属材料有限公司 Heat-insulation metal material
CN103922351A (en) * 2013-01-14 2014-07-16 成都首能新能源开发有限公司 Preparation method of silica aerogel thermal insulation coating layer
CN104031386A (en) * 2014-05-26 2014-09-10 中国科学院宁波材料技术与工程研究所 Composite aerogel and preparation method thereof
CN104276851A (en) * 2014-09-10 2015-01-14 吴建坤 Manufacturing technique of silicon dioxide aerogel heat-insulation film
CN104608439A (en) * 2015-01-14 2015-05-13 太仓市其盛化纤厂 Thermal insulation glass
CN106042550A (en) * 2016-06-01 2016-10-26 苏州市君悦新材料科技股份有限公司 Flexible heat preservation and heat insulation film and preparation method thereof
CN106513283A (en) * 2016-09-08 2017-03-22 南京航空航天大学 Nano SiO2 aerogel flexible heat preservation film
CN107630205A (en) * 2017-08-03 2018-01-26 深圳市科益实业有限公司 A kind of insulation construction and preparation method thereof
WO2020134973A1 (en) * 2018-12-27 2020-07-02 青岛海尔电冰箱有限公司 Thermal insulating material and refrigerator
CN114934394A (en) * 2022-05-31 2022-08-23 广东宜纳新材料科技有限公司 Preparation method of fiber composite gel flexible membrane

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AU4175296A (en) * 1994-11-23 1996-06-17 Hoechst Aktiengesellschaft Composite material containing aerogel, process for manufacturing said material and the use thereof
ATE235438T1 (en) * 1995-09-11 2003-04-15 Cabot Corp AIRGEL AND ADHESIVE COMPOSITE MATERIAL, METHOD FOR THE PRODUCTION THEREOF AND ITS USE
DE19635971C2 (en) * 1996-09-05 2003-08-21 Porextherm Daemmstoffe Gmbh Thermal insulation molded body and method for its production
DE19702240A1 (en) * 1997-01-24 1998-07-30 Hoechst Ag Multilayer composite materials which have at least one airgel-containing layer and at least one further layer, processes for their production and their use
TR200300968T1 (en) * 2000-12-22 2004-05-21 Arcelik As An insulated unit

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CN103922351A (en) * 2013-01-14 2014-07-16 成都首能新能源开发有限公司 Preparation method of silica aerogel thermal insulation coating layer
CN103009711A (en) * 2013-01-22 2013-04-03 昆山汉品电子有限公司 Diffusion and heat insulating film
CN103450685A (en) * 2013-08-09 2013-12-18 苏州纳埃净化科技有限公司 Manufacturing method of nano porous material
CN103527901B (en) * 2013-10-31 2016-10-12 上海交通大学 A kind of Non-vacuum multilayer flexible heat insulation quilt and preparation method thereof
CN103527901A (en) * 2013-10-31 2014-01-22 上海交通大学 Non-vacuum multilayer flexible heat insulation quilt and manufacturing method thereof
CN103753886A (en) * 2014-01-27 2014-04-30 苏州乾雄金属材料有限公司 Heat-insulation metal material
CN104031386A (en) * 2014-05-26 2014-09-10 中国科学院宁波材料技术与工程研究所 Composite aerogel and preparation method thereof
CN104276851A (en) * 2014-09-10 2015-01-14 吴建坤 Manufacturing technique of silicon dioxide aerogel heat-insulation film
CN104608439A (en) * 2015-01-14 2015-05-13 太仓市其盛化纤厂 Thermal insulation glass
CN106042550A (en) * 2016-06-01 2016-10-26 苏州市君悦新材料科技股份有限公司 Flexible heat preservation and heat insulation film and preparation method thereof
CN106513283A (en) * 2016-09-08 2017-03-22 南京航空航天大学 Nano SiO2 aerogel flexible heat preservation film
CN106513283B (en) * 2016-09-08 2019-11-12 南京航空航天大学 A kind of Nano-meter SiO_22Aeroge flexible heat-insulating film
CN107630205A (en) * 2017-08-03 2018-01-26 深圳市科益实业有限公司 A kind of insulation construction and preparation method thereof
WO2020134973A1 (en) * 2018-12-27 2020-07-02 青岛海尔电冰箱有限公司 Thermal insulating material and refrigerator
CN114934394A (en) * 2022-05-31 2022-08-23 广东宜纳新材料科技有限公司 Preparation method of fiber composite gel flexible membrane

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