CN105693267A - Preparation method of germanium oxide aerogel composite material - Google Patents
Preparation method of germanium oxide aerogel composite material Download PDFInfo
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- CN105693267A CN105693267A CN201610066741.9A CN201610066741A CN105693267A CN 105693267 A CN105693267 A CN 105693267A CN 201610066741 A CN201610066741 A CN 201610066741A CN 105693267 A CN105693267 A CN 105693267A
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- germanium oxide
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- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 title claims abstract description 119
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000004964 aerogel Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 3
- 230000008595 infiltration Effects 0.000 claims description 24
- 238000001764 infiltration Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052732 germanium Inorganic materials 0.000 claims description 19
- -1 germanium alkoxide Chemical class 0.000 claims description 17
- 150000001298 alcohols Chemical class 0.000 claims description 14
- 239000007822 coupling agent Substances 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000012756 surface treatment agent Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- QMMBZOSZCYBCDC-UHFFFAOYSA-N NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC QMMBZOSZCYBCDC-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical group [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 238000000352 supercritical drying Methods 0.000 abstract description 11
- 230000018109 developmental process Effects 0.000 abstract description 4
- 238000001879 gelation Methods 0.000 abstract 1
- 238000004381 surface treatment Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 4
- 239000011343 solid material Substances 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1051—Organo-metallic compounds; Organo-silicon compounds, e.g. bentone
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
- C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a preparation method of a germanium oxide aerogel composite material. The method comprises the following steps: impregnating a prepared germanium oxide sol into a treated inorganic fiber material, carrying out gelation and sufficient aging, and carrying out supercritical drying with ethanol or carbon dioxide, thereby obtaining the germanium oxide aerogel composite material. The preparation technique provided by the technical scheme is simple and easy to operate, and can be used for preparing the germanium oxide aerogel with excellent properties for the first time. The high-specific-area low-density high-porosity germanium oxide aerogel prepared by the technical scheme has excellent properties: the specific area is 200-280 m<2>/g, the density is 0.13-0.20 g/m<3>, and the porosity is 90-95%. The thermal conductivity of the germanium oxide aerogel composite material at 1000 DEG C is less than 0.035 W/m.K, and the shrinkage is less than 3.4%. The technical scheme provided by the invention widens the development and application range of the germanium oxide material.
Description
Technical field
The preparation method that the present invention relates to a kind of aeroge, specifically, the preparation method relating to a kind of germanium oxide aerogel composite。
Background technology
Aeroge refers to that the nanoporous network mutually assembling composition with nano-particle is skeleton, and is full of the lightweight nano solid material of gaseous state disperse medium in network skeleton hole。Aeroge is as a kind of nano material, except the characteristic with nano material, also there are other excellent properties, as: high porosity, high-specific surface area, extremely low density, low thermal conductivity and low sound transmission speed etc., in catalysis, space flight, medicine, the energy, building and metallurgy etc., there is huge application prospect。
American scientist Kistler has invented aerosil first in 1931, this is the nano-meter porous amorphous state solid material of a kind of low-density, high porosity, light transmittance is higher, also known as " blue smoke ", hole is full of gaseous state disperse medium, there is continuous print nanoscale three-dimensional network structure and hole, the solid material that the density being known in the world at present is minimum and heat conductivity is minimum。
Now, aerosil is widely applied in fields such as Aero-Space, building and chemical industry, simultaneously, aeroge kind have also been obtained extreme enrichment, such as metal aerogel, organic aerogel and carbon aerogels, so far increasing Novel air gel is progressively developed。
Germanium oxide can be widely used for making high pure metal germanium, germanium compound, chemical catalyst, medical industry, PET resin, electronic device etc.；Such as, the glass containing germanium oxide has higher refractive index and dispersion, can as pantoscope and microscope camera lens。The preparation method that the present invention will set forth the germanium oxide aerogel composite with unique texture and performance first, can better promote development and the application of such material, widen the kind of aeroge simultaneously, has promoted the development of aeroge science and technology。
Summary of the invention
The preparation method that it is an object of the invention to provide the little germanium oxide aerogel composite of a kind of high-specific surface area, low-density, high porosity, low heat conduction and shrinkage factor；Technical scheme processing technology provided by the invention simply, easily operate, and prepares the germanium oxide aeroge of excellent performance first。
Realize the object of the invention technical scheme as follows:
The preparation method of a kind of germanium oxide aerogel composite, described composite includes germanium oxide aeroge and inorganic fibers, and described preparation method comprises the steps:
1) process of inorganic fibers: at 150～200 DEG C, dry inorfil 4～6 hours；After inorfil is immersed the surface treatment agent solution by inorfil, distilled water, surfactant and proportions that coupling agent weight ratio is 1:2～4:0.004～0.008:0.012～0.02, dry 1～3 hour at 160～220 DEG C, cool down to obtain inorfil after surface treatment；
2) preparation of germanium oxide colloidal sol: be 1:4～20:4～10:10 according to mol ratio by germanium alkoxide, alcohols material, deionized water and catalyst-4～10-2Proportions mixed liquor, stirring 10～20min stand after, obtain germanium oxide colloidal sol；
3) infiltration: by step 2) germanium oxide colloidal sol infiltrate through step 1) process after inorganic fibers；
4) prepare germanium oxide aerogel composite: at 50～80 DEG C, make step 3) gained infiltration thing in germanium oxide colloidal sol generation gelling, obtain germanium oxide gel；After 20～50 DEG C of aging 20～50h, obtain germanium oxide aerogel composite through ethanol or carbon dioxide supercritical fluid drying。
Further, described inorfil includes following component by mass percentage: Al2O3, 30～45%；SiO2, 10～25%；Na2O, 3～15%；CaO, 20～40%。
Further, described germanium alkoxide is methoxyl group germanium or ethyoxyl germanium。
Further, described alcohols material is methanol, ethanol, propanol or butanol。
Further, described catalyst is hydrochloric acid, sulphuric acid, phosphoric acid, formic acid, acetic acid, ethanedioic acid or Fluohydric acid.。
Further, described coupling agent is gamma-aminopropyl-triethoxy-silane, N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, MTMS or vinyltrimethoxy silane。
Further, described surfactant is dodecyl dimethyl benzyl ammonium chloride, dodecylbenzene sodium sulfonate, dimethyl dodecyl amine oxide, dodecyl-dimethyl amine second lactone or glycerin polyoxyethylene ether。
Further, germanium oxide gel specific surface area 200～280m that prepared by described method2/ g, porosity 90～95%；The germanium oxide aerogel composite that described method is prepared thermal conductivity at 1000 DEG C is less than 0.035w/m k, and shrinkage factor is less than 3.4%。
With immediate prior art ratio, technical scheme provided by the invention has following excellent effect:
1, technical scheme preparation technology provided by the invention is simply, easily operate, and is suitable for large-scale production, and prepares the germanium oxide aeroge of excellent performance first。
2, technical scheme provided by the invention prepares the germanium oxide aeroge of high-specific surface area, low-density, high porosity, and its excellent properties is specific surface area 200～280m2/ more than g, density 0.13～0.20g/m3, porosity 90～95%。
3, the germanium oxide aerogel composite that technical scheme provided by the invention is prepared thermal conductivity at 1000 DEG C is less than 0.035w/m k, and shrinkage factor is less than 3.4%。
4, technical scheme provided by the invention, has widened development and the application of germanium oxide material。
Detailed description of the invention
Further technical scheme is clearly and completely described below in conjunction with the embodiment of the present invention, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments。Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain, broadly fall into the scope of protection of the invention。
Embodiment 1
1) process of inorganic fibers: at 150 DEG C, dry inorfil 6 hours；After inorfil is immersed the surface treatment agent solution by inorfil, distilled water, surfactant and proportions that coupling agent weight ratio is 1:2:0.008:0.02, dry 3 hours at 220 DEG C, cool down to obtain inorfil after surface treatment；
2) preparation of germanium oxide colloidal sol: be 1:20:10:10 according to mol ratio by germanium alkoxide, alcohols material, deionized water and catalyst-2Proportions mixed liquor, stirring 20min stand after, obtain germanium oxide colloidal sol；
3) infiltration: by step 2) germanium oxide colloidal sol infiltrate through step 1) process after inorganic fibers；
4) prepare germanium oxide aerogel composite: at 80 DEG C, make step 3) gained infiltration thing in germanium oxide colloidal sol generation gelling, obtain germanium oxide gel；After 50 DEG C of aging 50h, obtain germanium oxide aerogel composite through supercritical drying。
Embodiment 2
1) process of inorganic fibers: at 1200 DEG C, dry inorfil 4 hours；After inorfil is immersed the surface treatment agent solution by inorfil, distilled water, surfactant and proportions that coupling agent weight ratio is 1:2:0.004:0.012, dry 3 hours at 160 DEG C, cool down to obtain inorfil after surface treatment；
2) preparation of germanium oxide colloidal sol: be 1:4:4:10 according to mol ratio by germanium alkoxide, alcohols material, deionized water and catalyst-4Proportions mixed liquor, stirring 10min stand after, obtain germanium oxide colloidal sol；
3) infiltration: by step 2) germanium oxide colloidal sol infiltrate through step 1) process after inorganic fibers；
4) prepare germanium oxide aerogel composite: at 50 DEG C, make step 3) gained infiltration thing in germanium oxide colloidal sol generation gelling, obtain germanium oxide gel；After 20 DEG C of aging 20h, obtain germanium oxide aerogel composite through supercritical drying。
Embodiment 3
1) process of inorganic fibers: at 160 DEG C, dry inorfil 5 hours；After inorfil is immersed the surface treatment agent solution by inorfil, distilled water, surfactant and proportions that coupling agent weight ratio is 1:3:0.005:0.015, dry 2 hours at 180 DEG C, cool down to obtain inorfil after surface treatment；
2) preparation of germanium oxide colloidal sol: be 1:6:5:10 according to mol ratio by germanium alkoxide, alcohols material, deionized water and catalyst-4Proportions mixed liquor, stirring 15min stand after, obtain germanium oxide colloidal sol；
3) infiltration: by step 2) germanium oxide colloidal sol infiltrate through step 1) process after inorganic fibers；
4) prepare germanium oxide aerogel composite: at 60 DEG C, make step 3) gained infiltration thing in germanium oxide colloidal sol generation gelling, obtain germanium oxide gel；After 30 DEG C of aging 30h, obtain germanium oxide aerogel composite through supercritical drying。
Embodiment 4
1) process of inorganic fibers: at 180 DEG C, dry inorfil 5 hours；After inorfil is immersed the surface treatment agent solution by inorfil, distilled water, surfactant and proportions that coupling agent weight ratio is 1:3:0.007:0.018, dry 1 hour at 200 DEG C, cool down to obtain inorfil after surface treatment；
2) preparation of germanium oxide colloidal sol: be 1:16:9:10 according to mol ratio by germanium alkoxide, alcohols material, deionized water and catalyst-3Proportions mixed liquor, stirring 18min stand after, obtain germanium oxide colloidal sol；
3) infiltration: by step 2) germanium oxide colloidal sol infiltrate through step 1) process after inorganic fibers；
4) prepare germanium oxide aerogel composite: at 70 DEG C, make step 3) gained infiltration thing in germanium oxide colloidal sol generation gelling, obtain germanium oxide gel；After 40 DEG C of aging 40h, obtain germanium oxide aerogel composite through supercritical drying。
Embodiment 5
1) process of inorganic fibers: at 170 DEG C, dry inorfil 6 hours；After inorfil is immersed the surface treatment agent solution by inorfil, distilled water, surfactant and proportions that coupling agent weight ratio is 1:4:0.006:0.014, dry 1 hour at 220 DEG C, cool down to obtain inorfil after surface treatment；
2) preparation of germanium oxide colloidal sol: be 1:19:7:10 according to mol ratio by germanium alkoxide, alcohols material, deionized water and catalyst-4Proportions mixed liquor, stirring 15min stand after, obtain germanium oxide colloidal sol；
3) infiltration: by step 2) germanium oxide colloidal sol infiltrate through step 1) process after inorganic fibers；
4) prepare germanium oxide aerogel composite: at 60 DEG C, make step 3) gained infiltration thing in germanium oxide colloidal sol generation gelling, obtain germanium oxide gel；After 50 DEG C of aging 30h, obtain germanium oxide aerogel composite through supercritical drying。
Embodiment 6
1) process of inorganic fibers: at 160 DEG C, dry inorfil 4 hours；After inorfil is immersed the surface treatment agent solution by inorfil, distilled water, surfactant and proportions that coupling agent weight ratio is 1:2:0.004:0.012, dry 2 hours at 220 DEG C, cool down to obtain inorfil after surface treatment；
2) preparation of germanium oxide colloidal sol: be 1:10:6:10 according to mol ratio by germanium alkoxide, alcohols material, deionized water and catalyst-2Proportions mixed liquor, stirring 14min stand after, obtain germanium oxide colloidal sol；
3) infiltration: by step 2) germanium oxide colloidal sol infiltrate through step 1) process after inorganic fibers；
4) prepare germanium oxide aerogel composite: at 65 DEG C, make step 3) gained infiltration thing in germanium oxide colloidal sol generation gelling, obtain germanium oxide gel；After 40 DEG C of aging 30h, obtain germanium oxide aerogel composite through supercritical drying。
Embodiment 7
1) process of inorganic fibers: at 180 DEG C, dry inorfil 4 hours；After inorfil is immersed the surface treatment agent solution by inorfil, distilled water, surfactant and proportions that coupling agent weight ratio is 1:3:0.005:0.013, dry 2 hours at 185 DEG C, cool down to obtain inorfil after surface treatment；
2) preparation of germanium oxide colloidal sol: be 1:16:7:10 according to mol ratio by germanium alkoxide, alcohols material, deionized water and catalyst-4Proportions mixed liquor, stirring 16min stand after, obtain germanium oxide colloidal sol；
3) infiltration: by step 2) germanium oxide colloidal sol infiltrate through step 1) process after inorganic fibers；
4) prepare germanium oxide aerogel composite: at 60 DEG C, make step 3) gained infiltration thing in germanium oxide colloidal sol generation gelling, obtain germanium oxide gel；After 40 DEG C of aging 50h, obtain germanium oxide aerogel composite through supercritical drying。
Embodiment 8
1) process of inorganic fibers: at 200 DEG C, dry inorfil 4 hours；After inorfil is immersed the surface treatment agent solution by inorfil, distilled water, surfactant and proportions that coupling agent weight ratio is 1:4:0.004:0.02, dry 3 hours at 200 DEG C, cool down to obtain inorfil after surface treatment；
2) preparation of germanium oxide colloidal sol: be 1:20:10:10 according to mol ratio by germanium alkoxide, alcohols material, deionized water and catalyst-2Proportions mixed liquor, stirring 20min stand after, obtain germanium oxide colloidal sol；
3) infiltration: by step 2) germanium oxide colloidal sol infiltrate through step 1) process after inorganic fibers；
4) prepare germanium oxide aerogel composite: at 65 DEG C, make step 3) gained infiltration thing in germanium oxide colloidal sol generation gelling, obtain germanium oxide gel；After 45 DEG C of aging 35h, obtain germanium oxide aerogel composite through supercritical drying。
Embodiment 9
1) process of inorganic fibers: at 175 DEG C, dry inorfil 5 hours；After inorfil is immersed the surface treatment agent solution by inorfil, distilled water, surfactant and proportions that coupling agent weight ratio is 1:2:0.007:0.017, dry 2.5 hours at 195 DEG C, cool down to obtain inorfil after surface treatment；
2) preparation of germanium oxide colloidal sol: be 1:17:6:10 according to mol ratio by germanium alkoxide, alcohols material, deionized water and catalyst-3Proportions mixed liquor, stirring 17min stand after, obtain germanium oxide colloidal sol；
3) infiltration: by step 2) germanium oxide colloidal sol infiltrate through step 1) process after inorganic fibers；
4) prepare germanium oxide aerogel composite: at 55 DEG C, make step 3) gained infiltration thing in germanium oxide colloidal sol generation gelling, obtain germanium oxide gel；After 30 DEG C of aging 40h, obtain germanium oxide aerogel composite through supercritical drying。
Embodiment 10
1) process of inorganic fibers: at 185 DEG C, dry inorfil 5.5 hours；After inorfil is immersed the surface treatment agent solution by inorfil, distilled water, surfactant and proportions that coupling agent weight ratio is 1:3.5:0.005:0.018, dry 1 hour at 220 DEG C, cool down to obtain inorfil after surface treatment；
2) preparation of germanium oxide colloidal sol: be 1:15:6:10 according to mol ratio by germanium alkoxide, alcohols material, deionized water and catalyst-4Proportions mixed liquor, stirring 14min stand after, obtain germanium oxide colloidal sol；
3) infiltration: by step 2) germanium oxide colloidal sol infiltrate through step 1) process after inorganic fibers；
4) prepare germanium oxide aerogel composite: at 65 DEG C, make step 3) gained infiltration thing in germanium oxide colloidal sol generation gelling, obtain germanium oxide gel；After 45 DEG C of aging 25h, obtain germanium oxide aerogel composite through supercritical drying。
The raw materials used kind of embodiment and ratio thereof are listed in the table below 1。
Table 1
In embodiment, gained properties of sample is listed in the table below 2。
Table 2
Above example is only in order to illustrate that technical scheme is not intended to limit; those of ordinary skill in the field are to be understood that; the specific embodiment of the present invention can being modified with reference to above-described embodiment or equivalent replacement, these are all being applied within the claims awaited the reply without departing from any amendment or equivalent replacement of spirit and scope of the invention。
Claims (9)
1. the preparation method of a germanium oxide aerogel composite, it is characterised in that described composite includes germanium oxide aeroge and inorganic fibers, and described preparation method comprises the steps:
1) process of inorganic fibers: at 150～200 DEG C, dry inorfil 4～6 hours；Inorfil is immersed after processing by weight the surface treatment agent solution for the preparation of the inorfil of ratio of 1:2～4:0.004～0.008:0.012～0.02, distilled water, surfactant and coupling agent, dry 1～3 hour at 160～220 DEG C, cooling；
2) preparation of germanium oxide colloidal sol: be 1:4～20:4～10:10 according to mol ratio by germanium alkoxide, alcohols material, deionized water and catalyst-4～10-2Proportions mixed liquor, stirring 10～20min stand to obtain germanium oxide colloidal sol；
3) infiltration: by step 2) germanium oxide colloidal sol infiltrate through step 1) process after inorganic fibers；
4) prepare germanium oxide aerogel composite: at 50～80 DEG C, make step 3) gained infiltration thing in germanium oxide colloidal sol generation gelling, obtain germanium oxide gel；At 20～50 DEG C after aging 20～50h, obtain germanium oxide aerogel composite through ethanol or carbon dioxide supercritical fluid drying。
2. the preparation method of a kind of germanium oxide aerogel composite as claimed in claim 1, it is characterised in that described inorfil includes following component by mass percentage: Al2O3, 30～45%；SiO2, 10～25%；Na2O, 3～15%；CaO, 20～40%。
3. the preparation method of a kind of germanium oxide aerogel composite as claimed in claim 1, it is characterised in that described germanium alkoxide is methoxyl group germanium or ethyoxyl germanium。
4. the preparation method of a kind of germanium oxide aerogel composite as claimed in claim 1, it is characterised in that described alcohols material is methanol, ethanol, propanol or butanol。
5. the preparation method of a kind of germanium oxide aerogel composite as claimed in claim 1, it is characterised in that described catalyst is hydrochloric acid, sulphuric acid, phosphoric acid, formic acid, acetic acid, ethanedioic acid or Fluohydric acid.。
6. the preparation method of a kind of germanium oxide aerogel composite as claimed in claim 1, it is characterized in that, described coupling agent is gamma-aminopropyl-triethoxy-silane, N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, MTMS or vinyltrimethoxy silane。
7. the preparation method of a kind of germanium oxide aerogel composite as claimed in claim 1, it is characterized in that, described surfactant is dodecyl dimethyl benzyl ammonium chloride, dodecylbenzene sodium sulfonate, dimethyl dodecyl amine oxide, dodecyl-dimethyl amine second lactone or glycerin polyoxyethylene ether。
8. such as the preparation method of the claim 1～7 germanium oxide aerogel composite as described in any one, it is characterised in that germanium oxide gel specific surface area 200～280m prepared by described method2/ g, porosity 90～95%。
9. such as the preparation method of the claim 1～7 germanium oxide aerogel composite as described in any one, it is characterised in that the germanium oxide aerogel composite that described method is prepared thermal conductivity at 1000 DEG C is less than 0.035w/m k, and shrinkage factor is less than 3.4%。
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