CN109707956B - Vacuum heat insulation plate and preparation method thereof - Google Patents
Vacuum heat insulation plate and preparation method thereof Download PDFInfo
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- CN109707956B CN109707956B CN201811624910.1A CN201811624910A CN109707956B CN 109707956 B CN109707956 B CN 109707956B CN 201811624910 A CN201811624910 A CN 201811624910A CN 109707956 B CN109707956 B CN 109707956B
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- vacuum insulation
- graphene oxide
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- 238000009413 insulation Methods 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims description 9
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- 239000002131 composite material Substances 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 43
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007822 coupling agent Substances 0.000 claims abstract description 33
- 239000012528 membrane Substances 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000012686 silicon precursor Substances 0.000 claims abstract description 17
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
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- 238000000034 method Methods 0.000 claims description 29
- 238000013329 compounding Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000003365 glass fiber Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- YSZKOFNTXPLTCU-UHFFFAOYSA-N barium lithium Chemical group [Li].[Ba] YSZKOFNTXPLTCU-UHFFFAOYSA-N 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- 229920006284 nylon film Polymers 0.000 claims description 9
- 239000011491 glass wool Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 229920006267 polyester film Polymers 0.000 claims description 5
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000005049 silicon tetrachloride Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000010422 painting Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
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- 230000000694 effects Effects 0.000 abstract description 6
- 229920001296 polysiloxane Polymers 0.000 abstract 1
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- 229920001778 nylon Polymers 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
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- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
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- 239000003607 modifier Substances 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 235000011089 carbon dioxide Nutrition 0.000 description 2
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- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- QHQNYHZHLAAHRW-UHFFFAOYSA-N 2-trimethoxysilylethanamine Chemical compound CO[Si](OC)(OC)CCN QHQNYHZHLAAHRW-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- OYYIUTLHIPZHDP-UHFFFAOYSA-N 4-[2-aminoethyl(diethoxy)silyl]butan-1-amine Chemical compound CCO[Si](CCN)(OCC)CCCCN OYYIUTLHIPZHDP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 description 1
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
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- 238000002210 supercritical carbon dioxide drying Methods 0.000 description 1
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- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Thermal Insulation (AREA)
Abstract
The invention provides a vacuum insulation panel, which comprises an aerogel composite membrane; the aerogel composite membrane is of a closed structure and is closed to form a vacuum cavity; a core material is filled in the vacuum cavity, and a getter is filled in the core material; the aerogel composite membrane sequentially comprises an aerogel felt and a film-coated material from outside to inside; the aerogel felt is attached to the surface of the film coating material; the aerogel blanket comprises a silicone aerogel; the organic silicon aerogel is prepared by preparing an organic silicon precursor from graphene oxide modified by an aminosilane coupling agent and performing hydrolysis, sol-gel and drying. According to the invention, the oxidized graphene is pretreated by using the aminosilane coupling agent, the characteristics of large surface area, more reactive groups and high strength of the oxidized graphene are utilized to enhance and improve the characteristics of brittleness and frangibility of aerogel, and the thermal bridge effect of the vacuum insulation panel can be reduced by utilizing the smaller gaps of the aerogel.
Description
Technical Field
The invention relates to the technical field of heat insulation materials, and relates to an aerogel vacuum heat insulation plate and a preparation method thereof.
Background
The vacuum heat insulation plate is one of vacuum heat insulation materials, is formed by compounding a filling core material and a vacuum protection surface layer, effectively avoids heat transfer caused by air convection, can greatly reduce the heat conductivity coefficient, has the characteristics of environmental protection, high efficiency and energy saving, is the most advanced high efficiency heat insulation material in the world at present, has the advantages of thin heat insulation layer thickness, small volume and light weight by the extremely low heat conductivity coefficient when the heat insulation technical requirements are the same, is suitable for products with higher energy-saving requirements, and has greater technical and economic significance. The refrigerator door and the upper door of the freezing box are required to be light and thin, and the vacuum heat insulation plate is adopted for heat insulation, so that the refrigerator has the advantages of light weight and small volume.
At present, vacuum insulation panels in the market are all faced with the conditions of poor mechanical damage resistance and thermal insulation failure at high and low temperatures in the use process. The method is characterized in that a door body is not well foamed in a repairing process, a door shell attached to a vacuum insulation panel is cleaned by dry ice (-80 ℃), the heat insulation performance of the vacuum insulation panel is damaged in the process of cleaning the door shell by the dry ice, even the vacuum insulation panel is directly failed, the vacuum insulation panel is taken down again to be attached to a new VIP plate, the production efficiency is reduced, and meanwhile, the cost is also reduced. Therefore, the aerogel vacuum insulation panel and the manufacturing process thereof are provided, and the problem that the conventional vacuum insulation panel is easy to lose efficacy under special severe conditions is solved. However, since the inside thereof is under negative pressure for a long time, gas easily permeates, resulting in an increase in the inside pressure, thereby causing the vacuum insulation panel to fail.
Generally, a vacuum insulation panel is composed of a core material, a coating material, and a getter. On one hand, the coating material maintains an internal vacuum state in order to wrap the core material, and on the other hand, can prevent permeation of external gas and prolong the service life of the vacuum insulation panel during the use of the vacuum insulation panel, so that the coating material is required to have barrier property and can block permeation of common gas.
The barrier property of the film coating material is generally realized by a metal film or a metal coating film, a common metal material is aluminum, and the aluminum has good ductility, low cost and good barrier property, and is widely used in the film coating material of the vacuum insulation panel, however, the thermal conductivity coefficient of the aluminum is higher (225w/mk), which often causes the thermal bridge effect of the prepared vacuum insulation panel to be larger and the thermal conductivity coefficient to be higher.
Disclosure of Invention
The invention aims to provide an aerogel vacuum insulation panel;
another object of the present invention is to provide a method for preparing the aerogel vacuum insulation panel.
In order to achieve the above object, an embodiment of the present invention provides a vacuum insulation panel, including an aerogel composite membrane; the aerogel composite film is of a closed structure and is closed to form a vacuum cavity; a core material is filled in the vacuum cavity, and a getter is filled in the core material;
the aerogel composite membrane sequentially comprises an aerogel felt and a film-coated material from outside to inside; the aerogel felt is attached to the surface of the film coating material;
the aerogel felt comprises organic silicon aerogel, wherein the organic silicon aerogel is prepared by preparing an organic silicon precursor from graphene oxide modified by an aminosilane coupling agent and performing hydrolysis, sol-gel and drying.
In a further improvement of the embodiment of the present invention, the coating material is selected from any one of a metal film, a metal plating film, and a non-metal film material.
As a further improvement of the embodiment of the present invention, the film-coating material includes a nylon film, an ethylene ethyl alcohol film, a polyester film, and a nylon film disposed from outside to inside with respect to the vacuum chamber.
In a further improvement of the embodiment of the present invention, the core material is at least one selected from the group consisting of silica powder, chopped glass fiber, long-chopped glass fiber, and glass wool.
As a further improvement of an embodiment of the present invention, the particle size of the silica powder is in the range of 15 to 100 nm;
the filament diameter of the short-cut glass fiber is 6-11 mu m, and the length of the short-cut glass fiber is 9-11 mm;
the diameter of the glass wool is 0.5-4 mu m, and the length of the glass wool is more than 11 mm.
As a further improvement of the embodiment of the invention, the getter is composed of a barium-lithium getter and a calcium oxide composite getter, the barium-lithium getter and calcium oxide are compounded at any ratio, the barium-lithium getter and calcium oxide are sealed and dried during compounding, the compounding temperature is 70 ℃, and the drying time is more than 1 h.
As a further improvement of the embodiment of the invention, the thickness of the vacuum heat insulation plate is 8-30mm, and the thickness of the aerogel felt is 0.5-5 mm.
On the other hand, the embodiment of the invention provides a preparation method of a vacuum insulation panel, which comprises the following steps: the outer surface of the vacuum heat-insulating plate is coated with an aerogel composite membrane, and the aerogel composite membrane sequentially comprises an aerogel felt and a film-coated material from outside to inside relative to the vacuum heat-insulating plate;
attaching the aerogel composite membrane to a vacuum insulation panel or attaching an aerogel felt to the surface of the vacuum insulation panel, and drying to prepare the aerogel vacuum insulation panel;
the aerogel felt comprises organosilicon aerogel prepared from graphene oxide modified by aminosilane coupling agent.
As a further improvement of the embodiment of the present invention, the attaching of the aerogel composite film on the vacuum insulation panel specifically comprises the following steps:
s1, preparing aminosilane coupling agent modified graphene oxide;
s2, dispersing the modified graphene oxide in a solvent, adding an organic silicon precursor, and performing a sol-gel-drying process to prepare the modified graphene oxide modified aerogel felt;
s3, compounding the aerogel felt and the film-coating material by a wet sticking method or a hot melting method to prepare an aerogel composite film;
s4, attaching the aerogel composite membrane to a vacuum insulation panel;
and S5, drying to obtain the aerogel vacuum insulation panel.
As a further improvement of the embodiment of the present invention, the specific way of attaching the aerogel blanket to the surface of the vacuum insulation panel is painting or spraying.
The embodiment of the invention has the following beneficial effects:
1. according to the embodiment of the invention, the aerogel felt is compositely designed on the surface of the conventional vacuum insulation panel membrane material, so that the air molecules can be 'bound' by fully utilizing the small air gaps of the aerogel, and the surface of the vacuum insulation panel is coated with the aerogel, so that the heat bridge effect of the vacuum insulation panel can be reduced;
2. the aerogel vacuum insulation panel related to the embodiment of the invention effectively prevents external mechanical damage, and simultaneously ensures the service life of the vacuum insulation panel at low ring temperature or high ring temperature by utilizing the heat preservation function of the aerogel felt on the outer layer of the membrane material, and resists the failure of the vacuum insulation panel caused by external temperature change;
3. the vacuum heat-insulating plate related to the embodiment of the invention is convenient to recycle, improves the production efficiency, reduces the product rejection rate and has stronger practicability;
4. according to the aerogel material adopted by the embodiment of the invention, the characteristics of brittleness and frangibility of the aerogel are enhanced and improved by utilizing the characteristics of the nanometer size effect, large surface area, more reactive groups and high strength of the graphene oxide material;
5. according to the embodiment of the invention, the graphene oxide is pretreated by using the aminosilane coupling agent, and the aminosilane coupling agent reacts with an epoxy group on the graphene oxide to introduce a reactive silane group to the graphene oxide, so that reaction sites are increased, and the reaction efficiency is improved;
6. according to the aerogel felt adopted in the embodiment of the invention, short glass fibers which are irritant to human bodies are not used, and the aerogel is connected with graphene oxide by a chemical method to prepare the graphene oxide modified aerogel.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the detailed description of the present application. It should be apparent that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive work based on the embodiments in the present application are within the scope of protection of the present application.
The embodiment of the invention provides a vacuum insulation panel, which comprises an aerogel composite membrane; the aerogel composite membrane is of a closed structure and is closed to form a vacuum cavity; a core material is filled in the vacuum cavity, and a getter is filled in the core material;
the aerogel composite membrane sequentially comprises an aerogel felt and a film-coated material from outside to inside; the aerogel felt is adhered to the surface of the film coating material;
the aerogel felt comprises organic silicon aerogel, the organic silicon aerogel is prepared by preparing an organic silicon precursor from graphene oxide modified by an aminosilane coupling agent, and the organic silicon precursor is prepared by hydrolysis, sol-gel and drying. Modifying graphene oxide by using an aminosilane coupling agent, and then preparing the modified graphene oxide and the aerogel into a composite material; in this embodiment, the graphene oxide is prepared by oxidizing and hydrolyzing flake graphite with strong acid; the graphene oxide can also be prepared by an improved hummers method.
The surface of the graphene oxide contains abundant hydroxyl, epoxy groups and carboxyl; and the graphene oxide is treated by the amino silane coupling agent, the silane coupling agent reacts with an epoxy group on the graphene oxide, and a reactive silane group is introduced onto the graphene oxide, so that reaction sites are increased, and the reaction efficiency and activity are improved.
In the embodiment of the invention, the film coating material is selected from any one of a metal film, a metal plated film or a non-metal film material; the non-metal film material comprises a nylon film, an ethylene ethyl alcohol film, a polyester film and a nylon film which are arranged from outside to inside relative to the vacuum cavity.
The vacuum cavity is filled with a core material, and the core material is at least one selected from silicon dioxide powder or chopped glass fiber, long-cut glass fiber and glass wool.
Preferably, the particle size of the silicon dioxide powder is in the range of 15-100 nm;
the short-cut glass fiber has the fiber diameter of 6-11 mu m and the length of 9-11 mm;
the glass wool has a diameter of 0.5-4 μm and a length of more than 11 mm.
In the embodiment of the invention, the getter is specifically a barium-lithium getter and calcium oxide composite getter, the barium-lithium getter and calcium oxide are compounded at any ratio, the barium-lithium getter and calcium oxide are sealed and dried during compounding, the compounding temperature is 70 ℃, and the drying time is more than 1 h.
Preferably, the thickness of the vacuum insulation panel is 8 to 30mm, and the thickness of the aerogel blanket is 0.5 to 5 mm.
The embodiment of the invention provides a preparation method of a vacuum insulation panel, which comprises the following steps: the outer surface of the vacuum heat-insulating plate is coated with an aerogel composite membrane, and the aerogel composite membrane sequentially comprises an aerogel felt and a film-coated material from outside to inside relative to the vacuum heat-insulating plate;
attaching the aerogel composite membrane to a vacuum insulation panel or attaching an aerogel felt to the surface of the vacuum insulation panel, and drying to prepare the aerogel vacuum insulation panel;
the aerogel felt comprises organosilicon aerogel prepared from graphene oxide modified by aminosilane coupling agent.
Specifically, the method for coating the aerogel composite film on the vacuum insulation panel specifically comprises the following steps:
s1, preparing aminosilane coupling agent modified graphene oxide;
s2, dispersing the modified graphene oxide in a solvent, adding an organic silicon precursor, and performing a sol-gel-drying process to prepare the modified graphene oxide modified aerogel felt;
s3, compounding the aerogel felt and the film-coating material by a wet sticking method or a hot melting method to prepare an aerogel composite film;
s4, attaching the aerogel composite membrane to a vacuum insulation panel;
and S5, drying to obtain the aerogel vacuum insulation panel.
Specifically, the aerogel felt is attached to the surface of the vacuum insulation panel by painting or spraying.
When the film-coated material is selected from non-metallic film materials, including nylon films, ethylene ethyl alcohol films, polyester films and nylon films which are arranged from outside to inside relative to the vacuum cavity, the preparation process of the aerogel composite film specifically comprises the following steps:
s1, compounding the aerogel felt and a nylon membrane through a wet adhesion method to obtain an aerogel felt-nylon composite membrane material;
s2, compounding the aerogel felt-nylon composite membrane material with an ethylene ethyl alcohol membrane through a hot melting method to prepare the aerogel felt-nylon-ethylene ethyl alcohol composite membrane material;
s3, compounding the composite film material obtained in the step S2 and a polyester film through a hot melting method;
s4, compounding the composite film material obtained in the step S3 and a nylon film through a hot melting method to obtain an aerogel composite film;
s5, making the aerogel composite film into a bag for later use through a bag making process;
s6, filling the core material and the getter into the bag prepared in the step S5, and sealing the aerogel composite film bag;
s7, vacuumizing the aerogel composite film bag to prepare the aerogel vacuum insulation board.
In the embodiment of the invention, the compounding steps of the aerogel felt and the nylon membrane by a wet adhesion method are as follows:
s1, applying the adhesive to the surface of the aerogel felt;
s2, naturally drying the aerogel felt, and controlling the humidity after drying within 5%;
and S3, contacting the nylon membrane with the aerogel felt, and compounding by means of a viscous adhesive.
In the embodiment of the invention, the compounding steps by a hot melting method are as follows:
s01: heating through a casting machine to melt the film material, wherein the heating temperature is 180-200 ℃, and the heating time is 1-3 s;
s02: and compounding different films in a molten state.
In the embodiment of the invention, the specific method for preparing the aminosilane coupling agent to treat the graphene oxide comprises the following steps:
s1, treating the graphene oxide by using an aminosilane coupling agent, and introducing a reactive silane group to the graphene oxide;
specifically, the specific method for treating graphene oxide by using an aminosilane coupling agent comprises the following steps:
s101, dispersing graphene oxide into a polar solvent to prepare a graphene oxide solution, wherein ultrasonic dispersion is selected as a dispersion mode; in this example, the polar solvent is N, N-dimethyl sulfoxide.
S102, adding an aminosilane coupling agent into the graphene oxide solution, heating to a reaction temperature of about 60-70 ℃ and carrying out overnight reaction;
wherein the reaction amount of the aminosilane coupling agent is 10-100 times of the mass of the graphene oxide;
in this embodiment, the aminosilane coupling agent may be selected from at least one of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-B (aminoethyl) -C-aminopropylmethyldimethoxysilane, N-B (aminoethyl) -C-aminopropylmethyldiethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, and aminoethyltrimethoxysilane.
And S103, filtering through a filter, washing away unreacted aminosilane coupling agent by using a polar solvent, and drying in an oven to obtain the modified graphene oxide treated by the aminosilane coupling agent.
S2, preparing an organic silicon precursor; in the embodiment, the organosilicon precursor is selected from at least one of tetraethoxysilane and silicon tetrachloride;
s3, dispersing the modified graphene oxide in a solvent, and adding an organic silicon precursor to perform a sol-gel process;
specifically, the sol-gel process specifically comprises the following steps:
adding an organic silicon precursor into anhydrous alcohol, then adding graphene oxide for ultrasonic dispersion, adding acid, adjusting the pH value to 1-3, and promoting hydrolysis of the organic silicon precursor;
adding ammonia water, adjusting pH value to alkalinity to 10-12, carrying out sol condensation process, and standing overnight to form gel.
After the gelling process is finished, aging the prepared gel, and adding a hydrophobic modifier for end capping; the selected hydrophobic modifier comprises at least one of trimethylchlorosilane, hexamethyldisiloxane, methyltriethoxysilane and methyltrimethoxysilane.
In the embodiment, the gel is aged, the aging temperature is controlled to be 40-60 ℃, and the aging time is 48 hours; after the hydrophobic modifier is added, the modification time is 24 hours; washing with non-polar solvent to replace the polar solvent every 12 hours, and repeating for 5-8 times; the nonpolar solvent is preferably n-hexane in this example.
And S4, drying, and preparing the modified graphene oxide modified aerogel.
In this embodiment, the drying method may be selected from supercritical carbon dioxide drying, freeze drying or Soxhlet extraction.
The following examples were prepared according to the methods in the above examples and tested for thermal insulation properties to give the following experimental results:
by comparing the above embodiments with comparative examples in which unmodified and modified aerogels are made into aerogel blankets, the embodiments of the present invention have the following advantageous effects:
1. according to the embodiment of the invention, the aerogel felt is compositely designed on the surface of the conventional vacuum insulation panel membrane material, so that the air molecules can be 'bound' by fully utilizing the small air gaps of the aerogel, and the surface of the vacuum insulation panel is coated with the aerogel, so that the heat bridge effect of the vacuum insulation panel can be reduced;
2. the aerogel vacuum insulation panel related to the embodiment of the invention effectively prevents external mechanical damage, and simultaneously ensures the service life of the vacuum insulation panel at low ring temperature or high ring temperature by utilizing the heat preservation function of the aerogel felt on the outer layer of the membrane material, and resists the failure of the vacuum insulation panel caused by external temperature change;
3. the vacuum heat-insulating plate related to the embodiment of the invention is convenient to recycle, improves the production efficiency, reduces the product rejection rate and has stronger practicability;
4. according to the aerogel material adopted by the embodiment of the invention, the characteristics of brittleness and frangibility of the aerogel are enhanced and improved by utilizing the characteristics of the nanometer size effect, large surface area, more reactive groups and high strength of the graphene oxide material;
5. according to the embodiment of the invention, the graphene oxide is pretreated by using the aminosilane coupling agent, and the aminosilane coupling agent reacts with an epoxy group on the graphene oxide to introduce a reactive silane group to the graphene oxide, so that reaction sites are increased, and the reaction efficiency is improved;
6. according to the aerogel felt adopted in the embodiment of the invention, short glass fibers which are irritant to human bodies are not used, and the aerogel is connected with graphene oxide by a chemical method to prepare the graphene oxide modified aerogel.
It should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should make the description as a whole, and the technical solutions in the embodiments can also be combined appropriately to form other embodiments understood by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention and is not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention are included in the scope of the present invention.
Claims (11)
1. The vacuum insulation panel is characterized by comprising an aerogel composite membrane;
the aerogel composite film is of a closed structure and is closed to form a vacuum cavity;
a core material is filled in the vacuum cavity, and a getter is filled in the core material;
the aerogel composite membrane sequentially comprises an aerogel felt and a film-coated material from outside to inside; the aerogel felt is attached to the surface of the film coating material;
the aerogel felt comprises an organic silicon aerogel, wherein the organic silicon aerogel is prepared by mixing an amino silane coupling agent modified graphene oxide with an organic silicon precursor and performing hydrolysis, sol-gel and drying;
the preparation method comprises the following steps of preparing aminosilane coupling agent modified graphene oxide by using an aminosilane coupling agent and graphene oxide, wherein the reaction amount of the aminosilane coupling agent is 10-100 times of the mass of the graphene oxide; the organic silicon precursor is selected from at least one of ethyl orthosilicate and silicon tetrachloride.
2. A vacuum insulation panel according to claim 1 wherein said coating material is selected from any one of metal film, metal coated film and non-metal film material.
3. The vacuum insulation panel according to claim 1, wherein the film-coated material comprises a nylon film, an ethylene ethyl alcohol film, a polyester film, and a nylon film arranged from outside to inside with respect to the vacuum cavity.
4. A vacuum insulation panel according to claim 1 wherein said core material is selected from at least one of silica powder or chopped glass fiber, long-chopped glass fiber, glass wool.
5. A vacuum insulation panel according to claim 4 wherein said silica powder has a particle size in the range of 15 to 100 nm;
the filament diameter of the short-cut glass fiber is 6-11 mu m, and the length of the short-cut glass fiber is 9-11 mm;
the diameter of the glass wool is 0.5-4 mu m, and the length of the glass wool is more than 11 mm.
6. The vacuum insulation panel according to claim 1, wherein the getter is a barium-lithium getter and a calcium oxide composite getter, the barium-lithium getter and the calcium oxide are compounded at any ratio, the barium-lithium getter and the calcium oxide are sealed and dried during compounding, the compounding temperature is 70 ℃, and the drying time is more than 1 h.
7. A vacuum insulation panel according to claim 1 wherein said vacuum insulation panel has a thickness of from 8 to 30mm and said aerogel blanket has a thickness of from 0.5 to 5 mm.
8. The preparation method of the aerogel vacuum insulation panel is characterized by comprising the following steps: the outer surface of the vacuum heat-insulating plate is coated with an aerogel composite membrane, and the aerogel composite membrane sequentially comprises an aerogel felt and a film-coated material from outside to inside relative to the vacuum heat-insulating plate;
attaching the aerogel composite membrane to the surface of the vacuum insulation panel, and drying to prepare the aerogel vacuum insulation panel;
the aerogel felt comprises organosilicon aerogel prepared from graphene oxide modified by aminosilane coupling agent;
the organic silicon aerogel is prepared by mixing an amino silane coupling agent modified graphene oxide with an organic silicon precursor, and performing hydrolysis, sol-gel and drying; the aminosilane coupling agent modified graphene oxide is prepared from an aminosilane coupling agent and graphene oxide, wherein the reaction amount of the aminosilane coupling agent is 10-100 times of the mass of the graphene oxide; the organic silicon precursor is selected from at least one of ethyl orthosilicate and silicon tetrachloride.
9. The preparation method of the aerogel vacuum insulation panel is characterized by comprising the following steps: the outer surface of the vacuum insulation panel is coated with aerogel felt;
attaching the aerogel felt to the outer surface of the vacuum insulation panel, and drying to prepare the aerogel vacuum insulation panel;
the aerogel felt comprises organosilicon aerogel prepared from graphene oxide modified by aminosilane coupling agent;
the organic silicon aerogel is prepared by mixing an amino silane coupling agent modified graphene oxide with an organic silicon precursor, and performing hydrolysis, sol-gel and drying; the aminosilane coupling agent modified graphene oxide is prepared from an aminosilane coupling agent and graphene oxide, wherein the reaction amount of the aminosilane coupling agent is 10-100 times of the mass of the graphene oxide; the organic silicon precursor is selected from at least one of ethyl orthosilicate and silicon tetrachloride.
10. The method for preparing the aerogel vacuum insulation panel according to claim 8, wherein the step of attaching the aerogel composite film on the vacuum insulation panel specifically comprises the following steps:
s1, preparing aminosilane coupling agent modified graphene oxide;
s2, dispersing the modified graphene oxide in a solvent, adding an organic silicon precursor, and performing a sol-gel-drying process to prepare the modified graphene oxide modified aerogel felt;
s3, compounding the aerogel felt and the film-coating material by a wet sticking method or a hot melting method to prepare an aerogel composite film;
s4, attaching the aerogel composite membrane to a vacuum insulation panel;
and S5, drying to obtain the aerogel vacuum insulation panel.
11. The method for preparing an aerogel vacuum insulation panel according to claim 9, wherein the aerogel blanket is attached to the surface of the vacuum insulation panel by painting or spraying.
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