CN101264891B - Method for preparing high-strength, low-density silicon dioxide aerogel - Google Patents
Method for preparing high-strength, low-density silicon dioxide aerogel Download PDFInfo
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- CN101264891B CN101264891B CN2008101040195A CN200810104019A CN101264891B CN 101264891 B CN101264891 B CN 101264891B CN 2008101040195 A CN2008101040195 A CN 2008101040195A CN 200810104019 A CN200810104019 A CN 200810104019A CN 101264891 B CN101264891 B CN 101264891B
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Abstract
The invention discloses a new preparation method for silicon dioxide gas gel with high intensity and low density, belonging to inorganic porous material technical field. The concrete preparation procedures comprise: hydrolyzing orthosilicate methyl ester or orthosilicate methyl ester for two to six hours under the pH value between one point five and four point five at the temperature between fifty to eighty DEG C, adding ammonia in drops, then injecting into a mold to form a wet gel monomer in the air, putting the wet gel obtained to a pressure tank, aging for three to ten days in the aging liquid with a certain ratio at the temperature between eighty DEG C to one hundred and fifty DEG C, then obtaining the silicon dioxide gas gel setting material with high intensity and low density through drying. The new preparation method for silicon dioxide gas gel with high intensity and low density has the advantages of having easy operation and simple technology, increasing the intensity of traditional silicon dioxide gas gel material, simultaneously ensuring low density, and promoting the application of silicon dioxide gas gel in setting and insulation product field.
Description
Technical field
The invention belongs to the inorganic porous material technical field, proposed a kind of method for preparing high strength, low-density silicon dioxide aerogel.
Background technology
Along with The development in society and economy and human living standard's raising, increasing to the demand of the energy, traditional Mineral resources such as coal, oil, Sweet natural gas will be faced with exhaustion in the near future.For alleviating energy crisis, except exploitation, research and utilization novel energy such as sun power etc., save energy, reducing power loss also is an importance.Therefore, research and develop porous material and just seem very necessary with excellent heat preservation and insulation.
Aerosil is a kind of special nano-porous materials, has the big (800～1000m of specific surface area
2/ g), the low (0.002～0.8g/cm of density
3), many premium propertiess, particularly its void content very high (up to 99%) such as unreactiveness, thermal conductivity very low (only be air 1/3) is the minimum solid material of present known thermal conductivity.Thereby have great using value in fields such as heat-insulation and heat-preservation, sound insulation, support of the catalyst, particularly in the typing thermal insulation that requires to have definite shape, sound insulation goods Application Areas, as heat-intercepting glass etc.But because the high porosity of this material causes SiO
2The structural strength of aerogel is relatively low, thereby has limited its application aspect typing thermal insulation, sound insulation goods, therefore, improves SiO
2The intensity of aerogel material becomes the focus that Many researchers is paid close attention to.
A.Katti etc. (A.Katti, N.Shimpi, S.Roy, et al.Chem.Mater, 2006,18:285-296) by coating amine-modified SiO with poly-urea
2The skeleton of aerogel has increased particle neck contact area, when having kept the aerogel meso-hole structure, has improved the intensity of material.Studies show that of R.Takahashi etc. (R.Takahashi, S.Sato, T.Sodesawa, et al.Materials Research Bulletin, 2005,40:1148-1156), under the similar situation of macropore content, reduce SiO
2Mesoporous volume content in the aerogel, intensity also can increase.With the crosslinked SiO of poly-hexamethylene vulcabond
2Nano particle in the hydrogel can improve intensity, but the material still very crisp and become opaque (N.Leventis, C.Sotiriou-Leventis, G.Zhang, et al.Nano Letters, 2002,2 (9): 957-960) that obtain.Deng Zhongsheng etc. (Z.S.Deng, J.Wang, A.M Wu.J.Non-Cryst.Solids, 1998, TiO is added in studies show that 225:101-104)
2Powder and mineral binder bond, the intensity of material increases to some extent.K.E.Parmenter etc. add ceramic fiber under lower volume density, can reduce shrinking percentage and can improve material intensity (K.E.Parmenter, F.Milstein.J.Non-Cryst.Solids, 1981,223:179-189).In addition, aging for a long time in all kinds of SOLVENTS under the normal pressure, also can improve material frame strength (G.Reichenauer.J.Non-Crystl.Solids, 2004,350:189-195).
Yet, these methods have also been brought a series of problem when having improved the strength of materials, or have reduced the void content of material, and perhaps the intensity of material improves not obvious, perhaps need the long aging work period, perhaps need miscellaneous exchange of solvent process etc.Therefore seek and both can improve intensity, the preparation method that can not have much impact to the porosity characteristic of material is particularly important again.
Aging condition is to SiO
2The structure of aerogel and performance important influence.Structure and performance that the composition of temperature, pressure and aging liquid when adjustment is aging can be regulated material.
Summary of the invention
The object of the present invention is to provide a kind of at raising SiO
2In the time of aerogel intensity, keep the method for its high porosity, low density advantage, by adopting with SiO
2Wet gel is High Temperature High Pressure aged method in the mother liquor of certain proportioning, the SiO of preparation high strength, high porosity
2Aerogel.
This method is the SiO that will obtain
2The wet gel monomer before the drying in the aging liquid of certain proportioning High Temperature High Pressure aging, concrete processing step is as follows:
With silicon precursor at silicon precursor: dehydrated alcohol: deionized water: the mol ratio of hydrolyst is 1: 2.5～8.5: 3.0～6.0: 3.0～9.0 * 10
-4Mixing solutions in hydrolysis; (1～5wt.%) also stirs dropping ammonia, and this moment, the pH of solution was 7.5～9.0, injects mould and leaves standstill, and makes its gel under air at room temperature then.In dehydrated alcohol, soak the demoulding behind 6～48h, take out silica wet gel; Silica wet gel put into 5～40vol.% silicon precursor is housed, 59～94vol.% dehydrated alcohol, 0.5vol.% deionized water and 0.5vol.% ammoniacal liquor (in 1～5wt.%) the pressure pan, then 80～150 ℃ aging 3～10 days down; Carry out drying afterwards, obtain the aerosil shaping material.
Hydrolysising condition is that pH is controlled at 1.5～4.5,50～80 ℃ of water-baths, insulation 1～6h.
Described silicon precursor is methyl silicate (TMOS) or tetraethoxy (TEOS).
Described hydrolyst is the hydrochloric acid of 0.1～3.0mol/l or the sulfuric acid of 0.1～8.0mol/l.
Drying process is room temperature constant pressure and dry or supercritical drying.The solvent of supercritical drying is any in carbonic acid gas, ethanol, acetone, methyl alcohol, n-propyl alcohol, benzene, butanols, amylalcohol, the octane.
The present invention is with SiO
2Wet gel is aging in the mother liquor of High Temperature High Pressure, and tetramethoxysilance in the mother liquor or tetraethoxy turn into grafting in SiO by hydrolysis-esterification
2The small curvature radius place of wet gel network skeleton as the contact neck between offspring, thereby strengthens skeleton.On the other hand, with respect to the particle of long radius bigger solubleness will be arranged according to the offspring of minor radius, under certain conditions, small-particle will dissolve and under the neck of macroparticle surface or offspring deposition, thereby improves material frame strength (dissolving-PRECIPITATION MECHANISM).The environment of High Temperature High Pressure will quicken the carrying out of these processes, thereby has shortened digestion period.Because two kinds of strengthening mechanisms work at the same time, thereby the raising of the strength of materials is very obvious.Void content height, intensity height, block materials that specific surface area is high are easy to get when aerogel is dry.The ultimate compression strength of gained aerogel block body material has improved 3～5 times at 0.45～0.6MPa than the intensity without the High Temperature High Pressure aged samples.This moment, void content was 88～95%, and density is 0.17～0.28g/cm
3, be 70～85% without the void content of High Temperature High Pressure aged samples, density is 0.30～0.65g/cm
3
The present invention is under the situation of not introducing extraneous hotchpotch, and is only that the wet gel monomer is aging under the High Temperature High Pressure in mother liquor, relies on the variation of himself can obviously improve the strength of materials.This method is easy and simple to handle, and technology is simple, and cost is low, and when especially producing in enormous quantities, benefit is particularly evident.It efficiently solves long-term puzzlement silica aerogel material when improving the strength of materials, the series of negative effect problem of being brought, as reduced the void content of material and performance decrease such as the material heat-insulation and heat-preservation that causes, sound insulation.The present invention has also shortened the aging work period simultaneously.Adopt the present invention will make SiO
2Aerogel becomes possibility in the application aspect heat-intercepting glass, typing insulating product, the typing sound insulation goods, can make building energy-saving and cost-reducing on the one hand, can improve the performance characteristics of high-temperature service device on the other hand.
Embodiment
Embodiment one:
Methyl silicate (TMOS): deionized water: dehydrated alcohol: the vitriolic mol ratio is 1: 2.6: 5.8: 3.05 * 10
-4After the sulfuric acid of TMOS, deionized water, dehydrated alcohol and 0.35mol/l mixed, place 80 ℃ of water-baths, insulation 1h hydrolysis.Dropping ammonia (1.0wt.%) and stirring then, the pH ≈ 8 of this moment.Be injected in the mould afterwards and leave standstill, under air at room temperature, become glue.In dehydrated alcohol, soak 24h (at this moment, room temperature is 20 ℃) the back demoulding, take out wet gel, put into the pressure pan that 10vol.%TMOS, 89vol.% dehydrated alcohol, 0.5vol.% deionized water and 0.5vol.% ammoniacal liquor (1.0wt.%) are housed, wore out 10 days down at 80 ℃ then.Carry out supercritical CO afterwards
2Dry (temperature: 45 ℃, pressure: 12MPa) get final product.
The volume density of gained sample is 0.23g/cm
3The sample size of compressive strength test is φ 16 * 20mm, tests on the RGM electronic universal tester, and loading rate is 0.5mm/min.Compressive strength is 0.54MPa.
Embodiment two:
Methyl silicate (TMOS): deionized water: dehydrated alcohol: the mol ratio of hydrochloric acid is 1: 2.6: 5.8: 6.1 * 10
-4With the mixed in hydrochloric acid of TMOS, deionized water, dehydrated alcohol and 0.35mol/l evenly after, place 60 ℃ of water-baths, insulation 2h hydrolysis.Dropping ammonia (1.5wt.%) and stirring then, the pH ≈ 8 of this moment.Be injected in the mould afterwards and leave standstill, under air at room temperature, become glue.In dehydrated alcohol, soak 24h (at this moment, room temperature is 20 ℃) the back demoulding, take out wet gel, put into 20vol.%TMOS is housed, the 79vol.% dehydrated alcohol in the pressure pan of 0.5vol.% deionized water and 0.5vol.% ammoniacal liquor (1.5wt.%), wore out 3 days down at 150 ℃ then.Dry (temperature: 20 ℃) gets final product at normal temperatures and pressures afterwards.
The volume density of gained sample is 0.26g/cm
3The sample size of compressive strength test is φ 16 * 20mm, tests on the RGM electronic universal tester, and loading rate is 0.5mm/min.Compressive strength is 0.48MPa.
Embodiment three:
Tetraethoxy (TEOS): deionized water: dehydrated alcohol: the vitriolic mol ratio is 1: 8.0: 4.5: 4.2 * 10
-4After the sulfuric acid of TEOS, deionized water, dehydrated alcohol and 0.35mol/l mixed, place 80 ℃ of water-baths, insulation 1.5h hydrolysis.Dropping ammonia (1.0wt.%) and stirring then, the pH ≈ 8 of this moment.Be injected in the mould afterwards and leave standstill, under air at room temperature, become glue.In dehydrated alcohol, soak the 89vol.% demoulding of 36h (at this moment, room temperature is 15 ℃) back, take out wet gel, put into 10vol.%TEOS is housed, the 89vol.% dehydrated alcohol in the pressure pan of 0.5vol.% deionized water and 0.5vol.% ammoniacal liquor (1.0wt.%), wore out 8 days down at 90 ℃ then.Normal temperature and pressure drying (temperature: 15 ℃) gets final product afterwards.
The volume density of gained sample is 0.25g/cm
3The sample size of compressive strength test is φ 16 * 20mm, tests on the RGM electronic universal tester, and loading rate is 0.5mm/min.Compressive strength is 0.50MPa.
Embodiment four:
Tetraethoxy (TEOS): deionized water: dehydrated alcohol: the mol ratio of hydrochloric acid is 1: 8.0: 3.5: 8.4 * 10
-4With the mixed in hydrochloric acid of TEOS, deionized water, dehydrated alcohol and 0.35mol/l evenly after, place 60 ℃ of water-baths, insulation 2h hydrolysis.Dropping ammonia (1.5wt.%) and stirring then, the pH ≈ 8 of this moment.Be injected in the mould afterwards and leave standstill, under air at room temperature, become glue.In dehydrated alcohol, soak 36h (15 ℃ of room temperatures) the back demoulding, take out wet gel, put into 20vol.%TEOS is housed, the 79vol.% dehydrated alcohol, in the pressure pan of 0.5vol.% deionized water and 0.5vol.% ammoniacal liquor (1.5wt.%), wore out 5 days down at 100 ℃ then.Carry out supercritical CO afterwards
2Dry (temperature: 45 ℃, pressure: 12MPa) get final product.
The volume density of gained sample is 0.18g/cm
3The sample size of compressive strength test is φ 16 * 20mm, tests on the RGM electronic universal tester, and loading rate is 0.5mm/min.Compressive strength is 0.60MPa.
Embodiment five:
Tetraethoxy (TEOS): deionized water: dehydrated alcohol: the mol ratio of hydrochloric acid is 1: 6.0: 3.5: 8.4 * 10
-4With the mixed in hydrochloric acid of TEOS, deionized water, dehydrated alcohol and 0.35mol/l evenly after, place 50 ℃ of water-baths, insulation 6h hydrolysis.Dropping ammonia (1.5wt.%) and stirring afterwards, the pH ≈ 8 of this moment.Be injected in the mould afterwards and leave standstill, under air at room temperature, become glue.In dehydrated alcohol, soak 36h (15 ℃ of room temperatures) the back demoulding, take out wet gel, put into 20vol.%TEOS is housed, the 79vol.% dehydrated alcohol, in the pressure pan of 0.5vol.% deionized water and 0.5vol.% ammoniacal liquor (1.5wt.%), wore out 3 days down at 120 ℃ then.Carry out afterwards the Supercritical Ethanol drying (temperature: 260 ℃, pressure: 7.5MPa) get final product.
The volume density of gained sample is 0.17g/cm
3The sample size of compressive strength test is φ 16 * 20mm, tests on the RGM electronic universal tester, and loading rate is 0.5mm/min.Compressive strength is 0.56MPa.
Claims (6)
1. the preparation method of a high strength, low-density silicon dioxide aerogel is characterized in that, with the silica wet gel of preparation before the drying in mother liquor burin-in process under the high-temperature and high-pressure conditions, concrete preparation process is as follows:
A, with silicon precursor at silicon precursor: dehydrated alcohol: deionized water: the mol ratio of hydrolyst is 1: 2.5～8.5: 3.0～6.0: 3.0～9.0 * 10
-4Mixing solutions in hydrolysis;
B, dropping ammonia also stir, and form colloidal sol, inject mould, leave standstill, make its gel under air at room temperature, in alcohol, soak the demoulding behind 6～48h, take out silica wet gel, the concentration of ammoniacal liquor is 1～5wt.%, and the pH of solution is 7.5～9.0 after the dropping ammonia.
C, silica wet gel put into 5～40vol.% silicon precursor is housed, 59～94vol.% dehydrated alcohol, in the pressure pan of 0.5vol.% deionized water and 0.5vol.% ammoniacal liquor, then 80～150 ℃ aging 3～10 days down;
D, the sample drying after will wearing out.
2. preparation method as claimed in claim 1 is characterized in that, described silicon precursor is methyl silicate or tetraethoxy.
3. preparation method as claimed in claim 1 is characterized in that, described hydrolyst is the sulfuric acid of 0.1～3.0mol/L hydrochloric acid or 0.1～8.0mol/L.
4. preparation method as claimed in claim 1 is characterized in that the pH of hydrolysis is controlled at 1.5～4.5 among the step a, and temperature is 50～80 ℃, and soaking time is 1～6h.
5. preparation method as claimed in claim 1 is characterized in that, the drying in the steps d is room temperature constant pressure and dry or supercritical drying.
6. preparation method as claimed in claim 6 is characterized in that, the solvent of supercritical drying is any in carbonic acid gas, ethanol, acetone, methyl alcohol, n-propyl alcohol, benzene, butanols, amylalcohol, the octane.
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| DE112017001567T5 (en) | 2016-09-14 | 2018-12-20 | Nano Technology Co., Ltd. | A rapid production process for an airgel with a microemulsion precursor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112017001567T5 (en) | 2016-09-14 | 2018-12-20 | Nano Technology Co., Ltd. | A rapid production process for an airgel with a microemulsion precursor |
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