CN113583389A - Preparation method of SiO2 aerogel supporting structure with ultrahigh strength and low heat conductivity coefficient - Google Patents
Preparation method of SiO2 aerogel supporting structure with ultrahigh strength and low heat conductivity coefficient Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 68
- 229910052681 coesite Inorganic materials 0.000 title claims abstract description 63
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 63
- 229910052682 stishovite Inorganic materials 0.000 title claims abstract description 63
- 229910052905 tridymite Inorganic materials 0.000 title claims abstract description 63
- 239000004964 aerogel Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 52
- 239000002131 composite material Substances 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001723 curing Methods 0.000 claims abstract description 24
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000012686 silicon precursor Substances 0.000 claims abstract description 5
- 238000001879 gelation Methods 0.000 claims abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 239000003365 glass fiber Substances 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 35
- 239000004744 fabric Substances 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- 230000029936 alkylation Effects 0.000 claims description 4
- 238000005804 alkylation reaction Methods 0.000 claims description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- 238000002210 supercritical carbon dioxide drying Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 238000000352 supercritical drying Methods 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 6
- 239000011152 fibreglass Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000035939 shock Effects 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000007493 shaping process Methods 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention provides SiO with ultrahigh strength and low heat conductivity coefficient2A method of making an aerogel support structure, comprising the steps of: 1) stirring and hydrolyzing the silicon precursor and the alcohol solution to form SiO2Sol; 2) in SiO2Adding an alkaline catalyst into the sol and uniformly mixing to obtain SiO2A pre-gel solution; 3) mixing SiO2Injecting the pre-gel solution into an aerogel mold filled with the base material A, and carrying out integral gelation to obtain SiO2Alcohol gel composite paper; 4) mixing SiO2Hydrophobic modification and drying of alcohol gel composite paper to obtain SiO2An aerogel composite; 5) the substrate B and SiO2The aerogel composite material is cross-stacked and then injected with epoxy resin solutionPressing and curing, and then heat-treating to constant weight to obtain SiO2An aerogel support structure. The SiO2 aerogel support structure prepared by the invention has the performances of high strength, low heat conductivity coefficient, cold insulation, heat insulation, shock absorption and the like, solves the problems of high heat conductivity coefficient and large heat leakage of the traditional glass fiber reinforced plastic support structure, and has convenient construction and long service life; the method can be applied to the fields of LNG tank boxes, liquid nitrogen, liquid hydrogen storage tanks and the like.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of an ultrahigh-strength low-thermal conductivity SiO2 aerogel support structure.
Background
The aerogel is a light nano porous solid material with a controllable structure, has nano skeleton particles (4-10 nm), high porosity (up to-99.8%), extremely low density (as low as 3kg/m 3), and low thermal conductivity (as low as 0.013W/m.K at normal temperature), and has a wide application prospect in the fields of novel aerospace crafts, missiles, naval vessels, weapons, petrochemical engineering, thermal engineering, new energy automobile batteries, energy-saving buildings and the like.
Although aerogel materials have many excellent characteristics, their unique porous network structure and low density, etc. result in poor mechanical properties of aerogels. The poor mechanical properties limit the application of aerogels in high strength, low thermal conductivity application scenarios. In the prior art, for the fields requiring materials with high compression resistance and low heat conductivity coefficient, such as LNG tank container supporting structures, liquid nitrogen and liquid hydrogen storage tank application fields, epoxy glass fiber reinforced plastics, refractory bricks, hollow glass beads/epoxy resin composite materials and the like are generally adopted as heat insulation, cold insulation and structural materials. Although the material has excellent mechanical properties, the thermal conductivity coefficient of the material is higher and is usually more than 0.4W/m.K, and the high thermal conductivity can reduce the cold insulation effect and increase the heat leakage path.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing an ultra-high strength low thermal conductivity SiO2 aerogel support structure. The method has the advantages of simple materials and process, good controllability of microstructure, high compressive strength, low heat conductivity coefficient, shock absorption and the like of the prepared aerogel support structure, is beneficial to large-scale industrial production, and solves the problem of high heat conductivity coefficient of the traditional glass fiber reinforced plastic support structure.
The specific technical scheme is as follows:
SiO with ultrahigh strength and low heat conductivity coefficient2A method of making an aerogel support structure, comprising the steps of:
1) stirring and hydrolyzing the silicon precursor and the alcohol solution to form SiO2And (3) sol.
2) In SiO2Adding an alkaline catalyst into the sol and uniformly mixing to obtain SiO2A pre-gel solution.
3) Mixing SiO2Injecting the pre-gel solution into an aerogel mold filled with the base material A, and carrying out integral gelation to obtain SiO2Alcohol gel composite paper.
4) Mixing SiO2Hydrophobic modification and drying of alcohol gel composite paper to obtain SiO2An aerogel composite.
5) The substrate B and SiO2The aerogel composite material is crossly stacked, then injected with epoxy resin solution for hot press molding and curing, and then is subjected to heat treatment until the weight is constant, thus preparing the SiO2An aerogel support structure.
Wherein, the epoxy resin solution is prepared by uniformly mixing a diluent, epoxy resin and a curing agent in proportion.
Further, the silicon precursor in the step 1) is tetraethoxysilane; the alcoholic solution is one or a combination of two of methanol, ethanol and butanol; the temperature of the hydrolysis reaction is 40-60 ℃, and the stirring time is 0.5-1.5 h.
Further, the alkaline catalyst in the step 2) is one or a combination of two of ammonia water, ammonium fluoride, ethylenediamine, sodium hydroxide and tetraethylammonium hydroxide, and the mass ratio of the alkaline catalyst: SiO22Sol =1:25-1:50, and the gel time is controlled within 50min-70 min.
Further, step 3) the SiO2Injecting the pre-gel solution into the aerogel mold by using a peristaltic pump or a pneumatic pump, and performing pneumatic circulation after injection, wherein the pneumatic circulation time is 55-75 min.
Further, step 4) the SiO2The hydrophobic modification of the alcogel composite paper adopts an alkylation method, uses a modifier comprising one of trimethylchlorosilane, hexamethyldisilazane, methyltriethoxysilane and methyltrimethoxysilane for polymerizing surface hydroxyl, and grafts methyl on the surface of the alcogel.
Further, step 4) the SiO2Alcohol coagulationDrying the glue composite paper by using hydrophobic modified SiO2The alcohol gel composite paper adopts supercritical CO2Drying of the CO2The temperature of the supercritical state is 40-60 ℃, and the pressure is 10-16 MPa; CO 22The flow rate of the supercritical fluid passing through the supercritical drying kettle is 1500-3500 kg/h, and the drying time is 8-16 h.
Further, the preparation of the epoxy resin solution in the step 5) is carried out by taking one or two of acetone and methanol as a diluent, taking aliphatic amine as a curing agent, and mixing the components according to the following ratio: epoxy resin: the curing agent =1 (1-5) to (0.5-1.5) are mixed uniformly.
Further, the curing time of the step 5) is 20-50 hours.
Further, the heat treatment according to step 5) is to cure the cured SiO2And (3) putting the aerogel support structure into an oven, heating and treating for 24-48 hours at 50-100 ℃, and drying to constant weight.
Further, the substrate A and the substrate B are respectively any one of glass fiber paper, glass fiber cloth, glass fiber needled felt, glass fiber centrifugal cotton, glass fiber laminated board, quartz fiber needled felt, carbon fiber woven felt, polyester fiber needled felt and ceramic fiber felt; for lifting SiO2The anti-stretching capacity of the aerogel supporting structure is that a plurality of strip-shaped blocks made of the same material as the base material A are transversely fixed on the upper surface of the base material A, and a plurality of strip-shaped blocks made of the same material as the base material A are also longitudinally fixed on the lower surface of the base material A; a plurality of strip-shaped blocks made of the same material as the base material B are longitudinally fixed on the upper surface of the base material B; a plurality of strip-shaped blocks made of the same material as the base material B are also transversely fixed on the lower surface of the base material B; the strip-shaped blocks on the upper surface of the base material B can be mutually spliced with the strip-shaped blocks on the lower surface of the base material A; the bar-shaped blocks on the lower surface of the base material B can be mutually spliced with the bar-shaped blocks on the upper surface of the base material A.
Compared with the prior art, the invention has the following advantages: the SiO2 aerogel support structure prepared by the invention has the heat conductivity coefficient as low as 0.03W/m.K which is far less than the heat conductivity coefficient of 0.4W/m.K of the traditional glass fiber reinforced plastic support structure, the compressive strength of the structure can reach 180Mpa, the structure has the characteristics of high compressive property and low heat conductivity coefficient, and has excellent cold insulation, heat insulation, shock absorption and other properties, the problems of high heat conductivity coefficient and large heat leakage of the traditional glass fiber reinforced plastic support structure are solved, the construction is convenient, and the service life is long. The preparation method of the invention fully utilizes the low heat-conducting property of the aerogel material, and can realize the application of the aerogel composite material in the application fields of tank boxes, storage tanks and the like by applying the epoxy resin curing method.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure. The described embodiments are only some embodiments of the invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
SiO with ultrahigh strength and low heat conductivity coefficient2A method of making an aerogel support structure, comprising the steps of:
1） SiO2preparing sol: dissolving ethyl orthosilicate in methanol water solution, adding a small amount of acid, stirring and reacting for 30min, and performing hydrolysis reaction to form SiO2Sol; wherein the temperature of the hydrolysis reaction is controlled at 40-60 ℃.
2） SiO2Preparing a pre-sol: in SiO2Adding ammonia water solution into the sol and mixing evenly to obtain SiO2A pre-gel solution. Wherein the mass ratio of the ammonia water solution is as follows: SiO22Sol =1:50, gel time controlled for 60 min.
3） SiO2Preparing alcohol gel composite paper: mixing SiO2Injecting the pre-gel solution into an aerogel mold (adopting an aerogel mold commonly used in the field) filled with glass fiber paper by using a peristaltic pump or a pneumatic pump, and performing pneumatic circulation after injection, wherein the pneumatic circulation time is 60min, and the SiO is obtained by using the whole gel2Alcohol gel composite paper. A plurality of strip-shaped blocks made of the same material as the glass fiber paper are transversely fixed on the upper surface of the glass fiber paper, and a plurality of strip-shaped blocks made of the same material as the glass fiber paper are longitudinally fixed on the lower surface of the glass fiber paperThe bar block of (1).
4) Hydrophobic modification and drying: mixing SiO2The alcohol gel composite paper is prepared by an alkylation method, soaking in ethanol solution, adding hexamethyldisilazane for surface alkylation modification, polymerizing surface hydroxyl, and grafting methyl on the surface of alcohol gel. After the modification is finished, SiO is added2Directly placing the alcogel composite paper into a drying kettle for supercritical CO2Drying at supercritical temperature of 48 deg.C and pressure of 12 MPa; CO 22The flow rate passing through the drying kettle is 1500kg/h, the drying is carried out for 10h, fluid is collected from a liquid outlet below the drying kettle until no solution is discharged, the machine is stopped, and the prepared SiO is taken out2An aerogel composite.
5) Molding, curing and heat treatment: mixing glass fiber cloth (reinforcing material) with SiO2Cutting aerogel composite material into 300 x 300mm sample blocks respectively, each 20 blocks, then alternately stacking after the shaping dish (make the bar blocks on the upper and lower surfaces of the two splice together mutually), injecting epoxy resin solution into the shaping dish and carrying out hot pressing, getting rid of air and clearance of aerogel paper in the middle of the reinforcing material, subsequently carrying out solidification curing time for 24 hours, then putting the aerogel supporting structure of solidification molding into an oven to carry out heat treatment, to constant weight, namely, making finished product SiO2An aerogel support structure. The oven temperature was set at 80 ℃ for 24 hours. A plurality of strip-shaped blocks made of the same material as the glass fiber cloth are longitudinally fixed on the upper surface of the glass fiber cloth; a plurality of strip-shaped blocks made of the same material as the glass fiber cloth are also transversely fixed on the lower surface of the glass fiber cloth; the strip-shaped blocks on the upper surface of the glass fiber cloth can be mutually spliced with the strip-shaped blocks on the lower surface of the glass fiber paper (the strip-shaped blocks on the upper surface of the glass fiber cloth can be spliced into the grooves among the strip-shaped blocks on the lower surface of the glass fiber paper, otherwise, the strip-shaped blocks on the lower surface of the glass fiber paper are also spliced into the grooves among the strip-shaped blocks on the upper surface of the glass fiber cloth); the strip-shaped blocks on the lower surface of the glass fiber cloth can be mutually spliced with the strip-shaped blocks on the upper surface of the glass fiber paper (the strip-shaped blocks on the lower surface of the glass fiber cloth can be spliced into the grooves between the strip-shaped blocks on the upper surface of the glass fiber paper, otherwise, the strip-shaped blocks on the upper surface of the glass fiber paper are also spliced into the grooves between the strip-shaped blocks on the lower surface of the glass fiber cloth).
Wherein the epoxy resin solution is prepared by mixing a diluent, epoxy resin and a curing agent in a mass ratio of 2:2:1 and stirring for 20min to mix the components uniformly; the epoxy resin used was bisphenol a type epoxy resin (commercially available), the curing agent was aliphatic amine type curing agent (commercially available), and the diluent was acetone (commercially available).
And measuring related performance data: the heat conductivity coefficient at normal temperature is 0.0226W/m.K, and the compressive strength is 160MPa (the compressive deformation is 14.5%).
Example two:
SiO with ultrahigh strength and low heat conductivity coefficient2A method of making an aerogel support structure, comprising the steps of:
1） SiO2preparing sol: dissolving ethyl orthosilicate in methanol water solution, adding a small amount of acid, stirring and reacting for 30min, and performing hydrolysis reaction to form SiO2Sol; wherein the temperature of the hydrolysis reaction is controlled at 40-60 ℃.
2） SiO2Preparing a pre-sol: in SiO2Adding ammonia water solution into the sol and mixing evenly to obtain SiO2A pre-gel solution. Wherein the mass ratio of the ammonia water solution is as follows: SiO22Sol =1:75, gel time controlled for 60 min.
3） SiO2Preparing alcohol gel composite paper: mixing SiO2Injecting the pre-gel solution into an aerogel mold (adopting an aerogel mold commonly used in the field) filled with glass fiber paper by using a peristaltic pump or a pneumatic pump, and performing pneumatic circulation after injection, wherein the pneumatic circulation time is 70min, and the SiO is obtained by using the whole gel2Alcohol gel composite paper. A plurality of strip-shaped blocks made of the same material as the glass fiber paper are transversely fixed (sewn or bonded) on the upper surface of the glass fiber paper, and a plurality of strip-shaped blocks made of the same material as the glass fiber paper are also longitudinally fixed on the lower surface of the glass fiber paper.
4) Hydrophobic modification and drying: mixing SiO2The alcohol gel composite paper is soaked in methanol solution and then surface alkylated with hexamethyldisilazane for surface hydroxyl polymerization and methyl grafting onto the surface of alcohol gel. After the modification is finished, SiO is added2The alcohol gel composite paper is directly put into the dryerDrying kettle for supercritical CO2Drying at supercritical temperature of 52 deg.C and pressure of 12 MPa; CO 22The flow rate passing through the drying kettle is 2000kg/h, the drying is carried out for 6h, fluid is collected from a liquid outlet below the drying kettle until no solution is discharged, the machine is stopped, and the prepared SiO is taken out2An aerogel composite.
5) Molding, curing and heat treatment: mixing glass fiber cloth (reinforcing material) with SiO2Cutting aerogel composite material into 300 x 300mm sample blocks respectively, each 20 blocks, then alternately stacking after the shaping plate (making the bar blocks on the upper and lower surfaces of the two spliced together), injecting epoxy resin solution into the shaping plate for hot pressing, removing air and gaps in the middle of the reinforced material, then carrying out curing and curing for 28 hours, then putting the aerogel supporting structure for curing and forming into an oven for heat treatment, till constant weight, namely, manufacturing a finished product of SiO (silicon dioxide) material2An aerogel support structure. The oven temperature was set at 60 ℃ for 30 hours. A plurality of strip-shaped blocks made of the same material as the glass fiber cloth are longitudinally fixed on the upper surface of the glass fiber cloth; a plurality of strip-shaped blocks made of the same material as the glass fiber cloth are also transversely fixed on the lower surface of the glass fiber cloth; the strip-shaped blocks on the upper surface of the glass fiber cloth can be mutually spliced with the strip-shaped blocks on the lower surface of the glass fiber paper (the strip-shaped blocks on the upper surface of the glass fiber cloth can be spliced into the grooves among the strip-shaped blocks on the lower surface of the glass fiber paper, otherwise, the strip-shaped blocks on the lower surface of the glass fiber paper are also spliced into the grooves among the strip-shaped blocks on the upper surface of the glass fiber cloth); the strip-shaped blocks on the lower surface of the glass fiber cloth can be mutually spliced with the strip-shaped blocks on the upper surface of the glass fiber paper (the strip-shaped blocks on the lower surface of the glass fiber cloth can be spliced into the grooves between the strip-shaped blocks on the upper surface of the glass fiber paper, otherwise, the strip-shaped blocks on the upper surface of the glass fiber paper are also spliced into the grooves between the strip-shaped blocks on the lower surface of the glass fiber cloth).
Wherein the epoxy resin solution is prepared by mixing a diluent, epoxy resin and a curing agent in a mass ratio of 1:2:1 and stirring for 20min to mix the components uniformly; the epoxy resin used was bisphenol a type epoxy resin (commercially available), the curing agent was aliphatic amine type curing agent (commercially available), and the diluent was acetone (commercially available).
And measuring related performance data: the heat conductivity coefficient at normal temperature is 0.036W/m.K, and the compressive strength is 180MPa (the compressive deformation is 19.5%).
It is to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The scope of the present invention is not limited to the technical solutions disclosed in the embodiments, and any modifications, equivalent substitutions, improvements, etc. made to the above embodiments according to the technical spirit of the present invention fall within the scope of the present invention.
Claims (10)
1. SiO with ultrahigh strength and low heat conductivity coefficient2The preparation method of the aerogel support structure is characterized by comprising the following steps of:
1) stirring and hydrolyzing the silicon precursor and the alcohol solution to form SiO2Sol; 2) in SiO2Adding an alkaline catalyst into the sol and uniformly mixing to obtain SiO2A pre-gel solution;
3) mixing SiO2Injecting the pre-gel solution into an aerogel mold filled with the base material A, and carrying out integral gelation to obtain SiO2Alcohol gel composite paper;
4) mixing SiO2Hydrophobic modification and drying of alcohol gel composite paper to obtain SiO2An aerogel composite;
5) the substrate B and SiO2The aerogel composite material is crossly stacked, then injected with epoxy resin solution for hot press molding and curing, and then is subjected to heat treatment until the weight is constant, thus preparing the SiO2An aerogel support structure;
wherein, the epoxy resin solution is prepared by uniformly mixing a diluent, epoxy resin and a curing agent in proportion.
2. SiO as in claim 12The preparation method of the aerogel support structure is characterized by comprising the following steps: the silicon precursor in step 1)Is tetraethoxysilane; the alcoholic solution is one or a combination of two of methanol, ethanol and butanol; the temperature of the hydrolysis reaction is 40-60 ℃, and the stirring time is 0.5-1.5 h.
3. SiO as in claim 12The preparation method of the aerogel support structure is characterized by comprising the following steps: the alkaline catalyst in the step 2) is one or a combination of two of ammonia water, ammonium fluoride, ethylenediamine, sodium hydroxide and tetraethyl ammonium hydroxide, and the alkaline catalyst is prepared from the following components in percentage by mass: SiO22Sol =1:25-1:50, and the gel time is controlled within 50min-70 min.
4. SiO as in claim 12The preparation method of the aerogel support structure is characterized by comprising the following steps: step 3) SiO2Injecting the pre-gel solution into the aerogel mold by using a peristaltic pump or a pneumatic pump, and performing pneumatic circulation after injection, wherein the pneumatic circulation time is 55-75 min.
5. SiO as in claim 12The preparation method of the aerogel support structure is characterized by comprising the following steps: step 4) SiO2The hydrophobic modification of the alcogel composite paper adopts an alkylation method, uses a modifier comprising one of trimethylchlorosilane, hexamethyldisilazane, methyltriethoxysilane and methyltrimethoxysilane for polymerizing surface hydroxyl, and grafts methyl on the surface of the alcogel.
6. SiO as in claim 12The preparation method of the aerogel support structure is characterized by comprising the following steps: step 4) SiO2Drying the alcohol gel composite paper by using hydrophobic modified SiO2The alcohol gel composite paper adopts supercritical CO2Drying of the CO2The temperature of the supercritical state is 40-60 ℃, and the pressure is 10-16 MPa; CO 22The flow rate of the supercritical fluid passing through the supercritical drying kettle is 1500-3500 kg/h, and the drying time is 8-16 h.
7. SiO as in claim 12Aerogel support tieThe preparation method of the structure is characterized by comprising the following steps: step 5) the preparation of the epoxy resin solution takes one or two of acetone and methanol as a diluent, takes aliphatic amine as a curing agent, and comprises the following steps: epoxy resin: the curing agent =1 (1-5) to (0.5-1.5) are mixed uniformly.
8. SiO as in claim 12The preparation method of the aerogel support structure is characterized by comprising the following steps: the curing time of the step 5) is 20-50 hours.
9. SiO as in claim 12The preparation method of the aerogel support structure is characterized by comprising the following steps: the heat treatment according to step 5) is to cure the cured SiO2And (3) putting the aerogel support structure into an oven, heating and treating for 24-48 hours at 50-100 ℃, and drying to constant weight.
10. SiO according to any of claims 1 to 92The preparation method of the aerogel support structure is characterized by comprising the following steps: the substrate A and the substrate B are respectively any one of glass fiber paper, glass fiber cloth, a glass fiber needled felt, glass fiber centrifugal cotton, a glass fiber laminated board, a quartz fiber needled felt, a carbon fiber woven felt, a polyester fiber needled felt and a ceramic fiber felt; a plurality of strip-shaped blocks made of the same material as the base material A are transversely fixed on the upper surface of the base material A, and a plurality of strip-shaped blocks made of the same material as the base material A are also longitudinally fixed on the lower surface of the base material A; a plurality of strip-shaped blocks made of the same material as the base material B are longitudinally fixed on the upper surface of the base material B; a plurality of strip-shaped blocks which are made of the same material as the upper surface of the base material B are also transversely fixed on the lower surface of the base material B; the strip-shaped blocks on the upper surface of the base material B can be mutually spliced with the strip-shaped blocks on the lower surface of the base material A; the bar-shaped blocks on the lower surface of the base material B can be mutually spliced with the bar-shaped blocks on the upper surface of the base material A.
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