CN102515181A - Method for improving strength of aerogel composite material - Google Patents
Method for improving strength of aerogel composite material Download PDFInfo
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- CN102515181A CN102515181A CN201110379865XA CN201110379865A CN102515181A CN 102515181 A CN102515181 A CN 102515181A CN 201110379865X A CN201110379865X A CN 201110379865XA CN 201110379865 A CN201110379865 A CN 201110379865A CN 102515181 A CN102515181 A CN 102515181A
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Abstract
The invention relates to a method for improving the strength of a silica aerogel composite material, particularly to an ageing composition for ageing silicon wet gel, an ageing method for silicon wet gel and a method for preparing a fibre composite silicon aerogel material by the ageing method. The ageing composition contains silica-alkoxides and a catalyst, especially an alkalescent catalyst. The ageing method may be performed in conditions such as repeated heating. The fibre composite silicon aerogel material prepared by the method disclosed by the invention has the advantages of being good in thermal stability and high in strength of aerogel composite material. Moreover, the method is simple in process, high in safety, as well as low in equipment demand and investment.
Description
Technical field
The present invention relates to technical field of material, be specifically related to aerogel material and preparation method thereof.
Background technology
Aerogel material is the best solid material of finding up to now of heat-proof quality; It is to assemble the network porous material that forms each other by nanoparticle; Its hole is a nanometer scale, less than the air molecule free path, can suppress gaseous exchange to greatest extent and conduct heat; Its nanostructure characteristic then causes low thermal conduction, and therefore aerogel material has lower thermal conductivity, low-density characteristics, is a kind of efficient and light weight lagging material.Aerogel material is widely used at aerospace field as lagging material, and Russia " peace " number space station and U.S.'s " courage " number mars exploration car all carry out thermal isolation with it.And at home, the use of novel nanoporous aerogel heat-insulation composite material has become the dominant direction of aerospacecraft high efficiency heat insulation material.
As the inner thermal insulator of aerospacecraft, require that heat-insulating efficiency is high, density is low, under the high temperature releaser few, can carry, quality controllability is high.Pure gas gel intensity is very low, and (16kPa, density is 0.1g/cm
3), be difficult to directly on engineering, use, must adopt fiber to strengthen, obtain fibre-reinforced aerogel matrix material (abbreviation aerogel composite).Research at present and application are the aerogel composite of silicon oxide system more widely, but because its cellular structure causes intensity lower, do not reach the requirement that lagging material carries.And because its flexibility is excessive, and the product size thickness fluctuation is bigger, deforms easily, brings difficulty to production quality control, therefore how to guarantee under the prerequisite of aerogel material density, improve the focus that aerogel material intensity becomes research.
A.Katti etc. (A.Katti, N.Shimpi, S.Roy.et al.Chem.Mater, 2006,285-296) gather urea and coat amine-modified SiO through use
2The gas gel skeleton has increased particle neck contact area, when having kept the gas gel meso-hole structure, has improved the intensity of aerogel material.This method can reduce the temperature tolerance of aerogel material owing to organic adding.After the organic decomposition that high temperature coats down, gas gel intensity can descend rapidly.Zhao Hailei etc. (patent: CN200810104019.5) through adding the aging two-step gelation of liquid under HTHP, utilize dissolving-sedimentation principle with the ester salt hydrolysis after grafting at wet gel network skeleton place, reinforcement skeleton structure, thereby raising aerogel material intensity.This method that in gelinite, increases ester hydrolysis; Can bring the increase of composite density; Be unfavorable for the control of lagging material weight, the reaction conditions of 80～150 ℃ of HTHPs surpasses inflammable and explosive organic solvent boiling point simultaneously; The device security controllability is required height, be unfavorable for large-scale industrial production.
Aerosil mainly obtains through the sol gel reaction of organo-silicon ester.The gel structure intensity that has just formed is relatively poor, and the increase gel that need wear out is further crosslinked, strengthens gel skeleton intensity, prevents in drying process subsequently, to ftracture.Although weathering process is thorough more, the shrinking percentage of gel drying process is more little, if digestion time is long, gel can produce excessive bulk and shrink.Therefore the short effect of skeleton chap that then do not reach of aged at room temperature time, the time is oversize then to be shunk easily.And the present invention will utilize the circulation heating condition to carry out the aged process; To shorten digestion time; Through increasing multiple catalyst type reaction solution, wherein weakly alkaline catalyzer promotes the carrying out of organo-silicon ester hydrolysis-condensation reaction, improves the reactive polymeric degree simultaneously; Under the prerequisite that does not increase aerogel composite density, improve the intensity of matrix material.
Summary of the invention
The present invention realizes through following technical scheme:
1, a kind of aging compsn that is used for aging silicon wet gel, said aging compsn comprises silicon alkoxide and catalyzer.
2, like technical scheme 1 described aging compsn, wherein, the mol ratio of said silicon alkoxide and catalyzer is 1: 0.0002～1.0.
3, like technical scheme 1 or 2 described aging compsns, wherein, said silicon alkoxide is one or more the combination that is selected from the group of being made up of tetraethyl silicate, methyl silicate and silicic acid propyl ester, preferably tetraethoxy.
4, like technical scheme 1 to 3 each described aging compsn, wherein, said catalyzer is a basic catalyst, is preferably the weakly alkaline catalyzer.
5, like technical scheme 4 described aging compsns; Wherein said basic catalyst is an organic ammonium; Preferably; Said organic amine is selected from one or more the combination in the group of being made up of TMAH, six methynes, four ammoniums, quadrol, triethylamine and thanomin, most preferably is TMAH.
6, a kind of aging method of silicon wet gel, wherein, said method is included in 40 ℃～70 ℃ temperature condition to the silicon wet gel aging step that heats up.
7, like technical scheme 6 described methods, wherein, the aging step of said intensification was carried out 48 hours to 144 hours.
8, like technical scheme 6 or 7 described methods, wherein, said aging steps in sequence comprises carries out following steps to said silicon wet gel:
1) carries out 24～72 hours the first aging step that heats up at 40 ℃～70 ℃ temperature condition;
2) carry out 48 hours～96 hours aged at room temperature step in room temperature; With
3) carry out 24～72 hours the second aging step that heats up at 40 ℃～70 ℃ temperature condition.
9, like technical scheme 6 to 8 each described methods, wherein, the silicon wet gel fiber composite form of said silicon wet gel for adopting silicon sol dipping fortifying fibre to obtain through gelation step then.
10, like technical scheme 6 to 9 described methods, wherein, the silicon sol that is used to prepare said silicon wet gel is through with silicon alkoxide: alcoholic solvent: deionized water: catalyzer is in molar ratio: 1: 3～20: 3～20: 0.0002～1.0 ratio makes.
11, like technical scheme 10 described methods, wherein, said gelation step is carried out in room temperature.
12, like technical scheme 6 to 11 each described methods, wherein, said method adopts technical scheme 1 to 5 each described aging compsn to carry out.
13, a kind of method for preparing fiber composite silica aerogel material, wherein, said method adopts technical scheme 6 to 12 each described methods that the silicon wet gel is worn out.
14, like technical scheme 13 described methods, wherein, said method comprises the steps:
1) silicon sol preparation process;
2) impregnation steps: use said silicon sol dipping fortifying fibre, obtain silicon sol-fortifying fibre mixture;
3) gelation step: in room temperature said silicon sol-fortifying fibre mixture is carried out gelation, obtain silicon wet gel-fortifying fibre complex body;
4) aging step: adopt technical scheme 6 to 13 each described methods that said silicon wet gel-fortifying fibre complex body is worn out;
5) solvent swap step: be present in the solvent in the said silicon wet gel-fortifying fibre complex body after aging with the replacement solvent displacement; With
6) drying step: adopt supercritical fluid drying that the said silicon wet gel-fortifying fibre complex body behind solvent exchange is carried out drying.
Beneficial effect of the present invention: the aging compsn that comprises silicon alkoxide and catalyzer is adopted in (1), can rapidly, effectively improve the intensity of matrix material; (2) adopt under the heating condition, in aging liquid, carry out aerogel material enhanced method, overcome the too short hardening effect that do not reach of aged at room temperature time, oversize and gas gel is prone to shrinkage problems; (3) adding of weakly alkaline aging liquid has effectively promoted the carrying out of organo-silicon ester hydrolysis-condensation reaction, improves the reactive polymeric degree, has also avoided reacting the too much problem of the too fast small molecules that brings, and under the prerequisite that guarantees density, has improved the intensity of material.(4) aerogel composite that improves through intensity can make its ultimate compression strength greater than 2MPa.(5) can satisfy the mechanical workout requirement, improve the thickness and precision of aerogel material, enlarge use range.(6) aging technique is simple, and required equipment is simple.Only need to prepare the fibre-reinforced aerogel material and be dipped in the aging liquid, under the condition of gentleness, heat, be beneficial to large-scale industrial production and practical applications.
Embodiment
As stated, the invention provides a kind of aging compsn that is used for aging silicon wet gel, silicon wet gel aging method, adopt this method to prepare the method and the thus obtained fiber composite silica aerogel material thereof of fiber composite silica aerogel material.
According to a first aspect of the invention, a kind of aging compsn that is used for aging silicon wet gel is provided, said aging compsn comprises silicon alkoxide and catalyzer.
The present invention has no particular limits silicon alkoxide.But according to preferred implementations more of the present invention, said silicon alkoxide is one or more the combination that is selected from the group of being made up of tetraethyl silicate, methyl silicate and silicic acid propyl ester, more preferably tetraethoxy.
According to other preferred implementation of the present invention, said silicon alkoxide is and the preparation used identical silicon alkoxide of silicon alkoxide of silicon gel to be aging.
Said catalyzer can be an an acidic catalyst for example, is preferably acidulous catalyst.But more preferably, the catalyzer in the aging compsn is a basic catalyst, further is preferably the weakly alkaline catalyzer.Owing to adopt the aging compsn that comprises the weakly alkaline catalyzer; Therefore can promote the carrying out of organo-silicon ester hydrolysis-condensation reaction effectively; Thereby improve the reactive polymeric degree; Also avoid reacting the too much problem of the too fast small molecules that brings simultaneously, reached under the prerequisite that guarantees density, improved the intensity of material.
According to certain embodiments of the present invention, the catalyzer in the aging compsn be used for catalyzer that prepare silicon colloidal sol uses for a kind of catalyzer; According to other embodiment of the present invention, the catalyzer in the aging compsn is different from and is used for the catalyzer that prepare silicon colloidal sol is used.But generally speaking, the acid-basicity of the catalyzer in the aging compsn is preferably identical with the acid-basicity that is used for the catalyzer that prepare silicon colloidal sol uses, and for example is all an acidic catalyst or is all basic catalyst.
According to preferred especially wet type mode more of the present invention; Said catalyzer in the aging compsn is a basic catalyst; More preferably the weakly alkaline catalyzer further is preferably organic amine, and said organic amine is preferably one or more the combination that is selected from the group that TMAH, six methynes, four ammonium ethylenediamines, triethylamine and thanomin form; Wherein preferably TMAH and quadrol most preferably are TMAH.Said six methynes, four ammoniums can for example adopt the form of the aqueous solution to use, and for example use with the form of the aqueous solution of 1 volumetric molar concentration.
According to preferred implementations more of the present invention; The mol ratio of said silicon alkoxide and catalyzer is 1: 0.0002～1.0; For example be 1: 0.0002,1: 0.0005,1: 0.001,1:: 0002,1: 0.005,1: 0.01,1: 0.015,1: 0.02,1: 0.03,1: 0.05,1: 0.08,1: 0.1,1: 0.2,1: 0.3,1: 0.5,1: 0.8 or 1: 1.0; This mol ratio more preferably 1: 0.001～0.1, more preferably 1: 0.01～0.2.If the shared ratio of said catalyzer is excessive, then speed of response is too fast, uncontrollable speed of response, and organo-silicon ester itself can be decomposed into small molecules rapidly, causes density to increase; If the shared ratio of said catalyzer is too small, then the organo-silicon ester reaction is slow or even can't react, and does not reach the purpose that improves intensity.
According to a second aspect of the invention, a kind of aging method of silicon wet gel is provided, said method is included in 40 ℃～70 ℃ temperature condition to the silicon gel aging step that heats up.Said temperature condition for example can be 40 ℃, 41 ℃, 42 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃, is preferably 45 ℃ to 65 ℃, more preferably 50 ℃ to 60 ℃.If temperature is too high, then cause the volatilization of the solvent in the silicon wet gel easily; If temperature is low excessively, then digestion time is long, causes the excess shrinkage of silica aerogel.Do not hope to receive the constraint of any theory; But according to thinking, adopt intensification aged mode, can in weathering process, strengthen the intensity of aerogel material; Overcome the too short hardening effect that do not reach of aged at room temperature time thus, long and the problem that aerogel material is shunk easily of digestion time;
According to preferred implementations more of the present invention; The aging time of carrying out 48 hours to 144 hours of under heating condition, carrying out is for example for carrying out 48 hours, 50 hours, 55 hours, 60 hours, 65 hours, 70 hours, 75 hours, 80 hours, 85 hours, 90 hours, 95 hours, 100 hours, 105 hours, 110 hours, 115 hours, 120 hours, 125 hours, 130 hours, 135 hours, 140 hours or 144 hours; More preferably 72 hours to 120 hours; Further be preferably 80 hours to 100 hours.If said overlong time, then sample is long under heating condition, can cause sample rate to increase; If the said time is too short, then do not reach the effect that improves material hardness.
According to preferred implementations more of the present invention, said aging steps in sequence is carried out as follows:
1) carries out 24～72 hours the first aging step that heats up at 40 ℃～70 ℃ temperature condition;
2) carry out 48 hours～96 hours aged at room temperature step in room temperature; With
3) carry out 24～72 hours the second aging step that heats up at 40 ℃～70 ℃ temperature condition.
According to certain embodiments of the present invention, the aging step of said first intensification can be carried out for example 24 hours, 30 hours, 36 hours, 42 hours, 48 hours, 54 hours, 60 hours, 66 hours or 72 hours; More preferably carried out 36 hours to 60 hours, further preferably carried out 42 to 54 hours.If carry out the long time, then can cause sample rate to increase; If carry out the too short time, then do not reach the effect that improves material hardness.
According to preferred implementations more of the present invention, said aged at room temperature step can be carried out for example 48 hours, 54 hours, 60 hours, 66 hours, 72 hours, 78 hours, 84 hours, 90 hours or 96 hours.More preferably carried out 60 hours to 78 hours, further preferably carried out 66 to 72 hours.If carry out the long time, then can cause sample rate to increase; If carry out the too short time, then do not reach the effect that improves material hardness.
According to preferred implementations more of the present invention, the aging step of said second intensification can be carried out for example 24 hours, 30 hours, 36 hours, 42 hours, 48 hours, 54 hours, 60 hours, 66 hours or 72 hours; More preferably carried out 36 hours to 60 hours, further preferably carried out 42 to 54 hours.If carry out the long time then can cause sample rate to increase; If carry out the too short time, then do not reach the effect that improves material hardness.According to the inventor's experimental result, adopt the multistage to heat up and to improve the intensity of silica aerogel material better.
According to preferred implementations more of the present invention, the wet type silicon sol fiber composite form of said silicon wet gel for adopting silicon sol dipping fortifying fibre to obtain through gelation step then.
The present invention is to the not special restriction of fortifying fibre, gets final product so long as be suitable for strengthening the filamentary material of gas gel.According to preferred implementations more of the present invention; Said fortifying fibre is an inorganic fibers, and this inorganic fibers is for example for being selected from the filamentary material of the one or more kinds of combinations in the group of being made up of silica fiber, high silica fiber, aluminum silicate fiber, spun glass, sapphire whisker, Zirconium oxide fibre, boron nitride fibre, basalt fibre and mullite fiber.
The present invention is to the not special restriction of the form of said fortifying fibre, for example can be for being selected from one or more the combination in the group of being made up of fibre felt, cellucotton, tapetum fibrosum, wad, fiber folded piece, fiber preform and prefab complex body.
According to preferred implementations more of the present invention, when with silicon sol fortifying fibre being flooded, can carry out through following mode: (1) directly is placed with the silicon sol adding in the mould of fortifying fibre, relies on gravity to flood; Or (2) use silicon sol dipping fortifying fibre, and will, the fortifying fibre of dipping re-use silicon sol and further infiltrate in pack mould into.When fortifying fibre during, preferably adopt mode (2) to carry out impregnation for big and thick filamentary material form.
What those skilled in the art understood is that the silicon wet gel is obtained through gelation by silicon sol.According to preferred implementations more of the present invention, said silicon sol is through with silicon alkoxide: alcoholic solvent: deionized water: catalyzer is in molar ratio: 1: 3～20: 3～20: 0.0002～1.0 ratio makes.
The mol ratio of said silicon alkoxide and said alcoholic solvent is as being 1: 3,1: 5,1: 8,1: 10,1: 15,1: 18 or 1: 20, this mol ratio more preferably 1: 5～15.
The mol ratio of said silicon alkoxide and said deionized water is as being 1: 3,1: 5,1: 8,1: 10,1: 15,1: 18 or 1: 20, this mol ratio more preferably 1: 5～15.
The mol ratio of said silicon alkoxide and catalyzer is as being 1: 0.0002,1: 0.0005,1: 0.001,1:: 0002,1: 0.005,1: 0.01,1: 0.015,1: 0.02,1: 0.03,1: 0.05,1: 0.08,1: 0.1,1: 0.2,1: 0.3,1: 0.5,1: 0.8 or 1: 1.0; This mol ratio more preferably 1: 0.001～0.1, more preferably 1: 0.01～0.2.
The present invention carries out gel to the not special restriction of the gelling temp that is formed the silicon wet gel by silicon sol but be preferably in room temperature.
The present invention has no particular limits the catalyzer that is used to prepare silicon sol, for example can be strongly acidic catalyst or acidulous catalyst; But more preferably basic catalyst further is preferably the weakly alkaline catalyzer, those weakly alkaline catalyzer of mentioning when for example in first part of the present invention, addressing the catalyzer in the aging compsn.
According to more of the present invention especially preferred embodiment, said aging method adopts the described aging compsn of first aspect present invention to carry out.Each characteristic about employed aging compsn repeats no more at this, but except as otherwise noted, otherwise these characteristics can be individually or be a plurality of in combination as in the preferred or optional technical scheme.
According to a third aspect of the invention we, a kind of method for preparing fiber composite silica aerogel material is provided, wherein, said method adopts the described aging method of second section of the present invention that the silicon wet gel is worn out.
According to certain embodiments of the present invention, the said method for preparing fiber composite silica aerogel material comprises the steps:
1) silicon sol preparation process;
2) impregnation steps: use said silicon sol dipping fortifying fibre, obtain silicon sol-fortifying fibre mixture;
3) gelation step: in room temperature said silicon sol-fortifying fibre mixture is carried out gelation, obtain silicon wet gel-fortifying fibre complex body;
4) aging step: adopt described aging compsn of first part of the present invention or the described aging method of second section of the present invention that said silicon wet gel-fortifying fibre complex body is worn out;
5) solvent swap step: be present in the solvent in the said silicon wet gel-fortifying fibre complex body after aging with the replacement solvent displacement; With
6) drying step: adopt supercritical fluid drying that the said silicon wet gel-fortifying fibre complex body behind solvent exchange is carried out drying.
About the preparation of silicon sol, in second aspect of the present invention, specific descriptions were arranged, for example can be through with silicon alkoxide: alcoholic solvent: deionized water: catalyzer is in molar ratio: 1: 3～20: 3～20: 0.0002～1.0 ratio makes.
About impregnation steps, gelation step and aging step, this specification sheets had had specific descriptions hereinbefore, therefore repeated no more.
The present invention can adopt conventional method to carry out the displacement of solvent, and carry out the drying of gas gel through the ordinary method of for example supercritical fluid drying solvent swap step and the not special restriction of drying step.
According to a forth aspect of the invention, provide by the fiber composite silica aerogel material that makes in the described method of third aspect present invention.This fiber composite silica aerogel material owing to used the aging compsn that comprises silicon alkoxide and catalyzer, therefore can rapidly, effectively improve the intensity of matrix material in the preparation process.And in some embodiments, the present invention is employed under the heating condition, in the aging liquid by aging compsn preparation of the present invention, carries out the aging of silicon gel, has overcome the too short hardening effect that do not reach of aged at room temperature time, and is oversize and gas gel is prone to shrinkage problems; And contain aging compsn especially add adopting by the weakly alkaline catalyzer; Promoted the carrying out of organo-silicon ester hydrolysis-condensation reaction effectively; Improve the reactive polymeric degree, also avoided reacting the too much problem of the too fast small molecules that brings, under the prerequisite that guarantees density; Improved the intensity of material, for example the ultimate compression strength of the fiber composite silica aerogel material that makes of the present invention is greater than 2MPa.Therefore, the fiber composite silica aerogel that adopts method of the present invention to make all has significant improvement in density, shrinking percentage especially intensity.The material that is made by method of the present invention can satisfy the mechanical workout requirement, has improved the thickness and precision of aerogel material, enlarges use range.And aging technique is simple, and required equipment is simple.Only need to prepare the fibre-reinforced aerogel material and be dipped in the aging liquid, under the condition of gentleness, heat, be beneficial to large-scale industrial production and practical applications.
In this article, except as otherwise noted, otherwise term " is selected from by ... the combination of one or more in the group " and is meant and is selected from any one of said group, or two or more arbitrary combination arbitrarily in said group.
Except as otherwise noted, otherwise in the term used herein " two or more " " more than " comprise given figure, promptly comprise two kinds situation and more than two kinds situation.
Except as otherwise noted, otherwise described herein and numerical range comprise the arbitrary value between end value and the endpoints thereof (being upper and lower bound).
Embodiment
Hereinafter will be described further the present invention with the form of embodiment.Yet these embodiment just are illustrated with regard to preferred implementation of the present invention, and protection scope of the present invention should not be construed as and only limits to these embodiment.In addition, the chemical reagent that embodiment adopted is available from Beijing chemical reagents corporation, and inorganic fibers is available from Shandong Luyang share co.,ltd.
Embodiment 1
With tetraethoxy, absolute ethyl alcohol, deionized water, ammoniacal liquor 1: 10: 3 in molar ratio: 0.0002 was configured to silicon sol, and the back is compound with the spun glass that uses as fortifying fibre, at the room temperature gel; The molar ratio that places tetraethoxy, TMAH then is 1: 0.0002 an aging liquid; After 24 hours, room temperature was placed 24 hours in 60 ℃ of heating, then 70 ℃ of heating 72 hours; After adopting ethanol to carry out solvent exchange, carry out supercritical CO again
2Drying obtains silicon dioxide silica aerogel composite material.Through measuring, this fiber composite silica aerogel material 2MPa compressive strength at room temperature is 5% (method according to GJB 1585A-2004 is carried out), and density is 0.25g/cm
3(method according to GB/T13350-2000 is carried out).
Except the note content of the back of content and table 1 shown in the table 1, adopt and carry out other embodiment and comparative example with embodiment 1 identical mode, the result is as shown in table 1.
Annotate: "-" expression does not exist, does not carry out or do not record; Catalyzer 1 is the catalyzer in the aging compsn; * silicon alkoxide is the silicon alkoxide in the aging compsn; Catalyzer 2 is the catalyzer of silicon sol preparation usefulness; Ratio 1 is the silicon alkoxide in the aging compsn and the mol ratio of catalyzer 1; Ratio 2 is a silicon alkoxide: alcoholic solvent: deionized water: the mol ratio of catalyzer 2; The data layout of aging temperature and digestion time is corresponding, and aging temperature is a * b * c, and digestion time is d * e * f; The meaning of expression is at a ℃ of aging d hour, then at b ℃ of aging e hour, again at c ℃ of aging f hour; For example: aging temperature is 60 * 25 * 70, and digestion time is 24 * 24 * 72, and the meaning of expression is to wear out 24 hours at 60 ℃; Wore out 24 hours at 25 ℃ then, wore out 72 hours at 70 ℃ again; Therefore embodiment 20 can't measure the data of 2MPa compressive strength and density because ethanol does not form gel very little; Therefore embodiment 22 can't measure the data of 2MPa compressive strength and density because water does not form gel very little; Embodiment 30 is without overaging.
Can find out from last table, adopt method of the present invention can obtain the 2MPa compressive strength below 10% (this per-cent is more little, and the intensity of illustrative material is big more) and the aerogel material of density below 0.25g/cm3.
Embodiment described herein illustrates what the preferred embodiments of the present invention were done.Person of ordinary skill in the field of the present invention can content disclosed according to the present invention carry out various modifications to described embodiment, but revises thus and the technical scheme that does not depart from essence of the present invention that obtains still drops within the appended claims institute restricted portion.
Claims (14)
1. aging compsn that is used for aging silicon wet gel, said aging compsn comprises silicon alkoxide and catalyzer.
2. aging compsn as claimed in claim 1, wherein, the mol ratio of said silicon alkoxide and catalyzer is 1: 0.0002～1.0.
3. according to claim 1 or claim 2 aging compsn, wherein, said silicon alkoxide is one or more the combination that is selected from the group of being made up of tetraethyl silicate, methyl silicate and silicic acid propyl ester, preferably tetraethoxy.
4. like each described aging compsn of claim 1 to 3, wherein, said catalyzer is a basic catalyst, is preferably the weakly alkaline catalyzer.
5. aging compsn as claimed in claim 4; Wherein said basic catalyst is an organic ammonium; Preferably; Said organic amine is selected from one or more the combination in the group of being made up of TMAH, six methynes, four ammoniums, quadrol, triethylamine and thanomin, most preferably is TMAH.
6. the aging method of a silicon wet gel, wherein, said method is included in 40 ℃～70 ℃ temperature condition to the silicon wet gel aging step that heats up.
7. method as claimed in claim 6, wherein, the aging step of said intensification was carried out 48 hours to 144 hours.
8. like claim 6 or 7 described methods, wherein, said aging steps in sequence comprises carries out following steps to said silicon wet gel:
1) carries out 24～72 hours the first aging step that heats up at 40 ℃～70 ℃ temperature condition;
2) carry out 48 hours～96 hours aged at room temperature step in room temperature; With
3) carry out 24～72 hours the second aging step that heats up at 40 ℃～70 ℃ temperature condition.
9. like each described method of claim 6 to 8, wherein, said silicon wet gel floods the silicon wet gel fiber composite form that fortifying fibre obtains through gelation step then for adopting silicon sol.
10. like the described method of claim 6 to 9, wherein, the silicon sol that is used to prepare said silicon wet gel is through with silicon alkoxide: alcoholic solvent: deionized water: catalyzer is in molar ratio: 1: 3～20: 3～20: 0.0002～1.0 ratio makes.
11. method as claimed in claim 10, wherein, said gelation step is carried out in room temperature.
12. like each described method of claim 6 to 11, wherein, said method adopts each described aging compsn of claim 1 to 5 to carry out.
13. a method for preparing fiber composite silica aerogel material, wherein, said method adopts each described method of claim 6 to 12 that the silicon wet gel is worn out.
14. method as claimed in claim 13, wherein, said method comprises the steps:
1) silicon sol preparation process;
2) impregnation steps: use said silicon sol dipping fortifying fibre, obtain silicon sol-fortifying fibre mixture;
3) gelation step: in room temperature said silicon sol-fortifying fibre mixture is carried out gelation, obtain silicon wet gel-fortifying fibre complex body;
4) aging step: adopt each described method of claim 6 to 13 that said silicon wet gel-fortifying fibre complex body is worn out;
5) solvent swap step: be present in the solvent in the said silicon wet gel-fortifying fibre complex body after aging with the replacement solvent displacement; With
6) drying step: adopt supercritical fluid drying that the said silicon wet gel-fortifying fibre complex body behind solvent exchange is carried out drying.
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| CN201110379865.XA CN102515181B (en) | 2011-11-25 | 2011-11-25 | Method for improving strength of aerogel composite material |
| CN201510084677.2A CN104787771B (en) | 2011-11-25 | 2011-11-25 | A kind of method for improving silicon dioxide silica aerogel composite material intensity |
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| CN104787771A (en) * | 2011-11-25 | 2015-07-22 | 航天特种材料及工艺技术研究所 | Method for increasing strength of silica aerogel composite material |
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| CN113358548A (en) * | 2021-06-16 | 2021-09-07 | 厦门多彩光电子科技有限公司 | Quality evaluation method of ultraviolet LED packaging adhesive |
| CN115744921A (en) * | 2022-11-22 | 2023-03-07 | 安徽科昂纳米科技有限公司 | Silicon dioxide aerogel based on mixed silicon source of sodium methylsilicate and sodium silicate and preparation method thereof |
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| CN104787771B (en) * | 2011-11-25 | 2017-07-11 | 航天特种材料及工艺技术研究所 | A kind of method for improving silicon dioxide silica aerogel composite material intensity |
| CN103694390A (en) * | 2013-11-18 | 2014-04-02 | 航天特种材料及工艺技术研究所 | Organic-inorganic hybrid light transmission aerogel material and preparation method thereof |
| CN105016350A (en) * | 2015-07-07 | 2015-11-04 | 北京林业大学 | Preparation method for fiber reinforced silica aerogel oil absorbing sponge |
| CN108290744A (en) * | 2016-10-12 | 2018-07-17 | 株式会社Lg化学 | Aerogel blanket, its manufacturing method and its construction method for superhigh temperature |
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| JP2019503952A (en) * | 2016-10-12 | 2019-02-14 | エルジー・ケム・リミテッド | Airgel blanket for ultra-high temperature, its manufacturing method and its construction method |
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| US10464816B2 (en) | 2016-10-12 | 2019-11-05 | Lg Chem, Ltd. | Aerogel blanket for ultra-high temperature, production method thereof, and construction method thereof |
| CN108290744B (en) * | 2016-10-12 | 2021-08-24 | 株式会社Lg化学 | Aerogel blanket for ultra high temperature, method of making same and method of constructing same |
| CN113358548A (en) * | 2021-06-16 | 2021-09-07 | 厦门多彩光电子科技有限公司 | Quality evaluation method of ultraviolet LED packaging adhesive |
| CN115744921A (en) * | 2022-11-22 | 2023-03-07 | 安徽科昂纳米科技有限公司 | Silicon dioxide aerogel based on mixed silicon source of sodium methylsilicate and sodium silicate and preparation method thereof |
| CN115744921B (en) * | 2022-11-22 | 2024-01-09 | 安徽科昂纳米科技有限公司 | Silicon dioxide aerogel based on mixed silicon source of sodium methyl silicate and sodium silicate and preparation method thereof |
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| CN104787771A (en) | 2015-07-22 |
| CN102515181B (en) | 2015-04-22 |
| CN104787771B (en) | 2017-07-11 |
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