CN107216114A - A kind of TiO2The normal pressure fast preparation method of doping silicon dioxide aerogel composite - Google Patents

A kind of TiO2The normal pressure fast preparation method of doping silicon dioxide aerogel composite Download PDF

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Publication number
CN107216114A
CN107216114A CN201710479770.2A CN201710479770A CN107216114A CN 107216114 A CN107216114 A CN 107216114A CN 201710479770 A CN201710479770 A CN 201710479770A CN 107216114 A CN107216114 A CN 107216114A
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tio
aerogel composite
silicon dioxide
powder
waterglass
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张和平
周婷
程旭东
龚伦伦
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/158—Purification; Drying; Dehydrating
    • C01B33/1585—Dehydration into aerogels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/16—Preparation of silica xerogels
    • 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

Abstract

The present invention relates to a kind of TiO2The normal pressure fast preparation method of doping silicon dioxide aerogel composite, specifically, the present invention are that, using cheap industrial waterglass as silicon source, adulterate TiO2Powder, using a step acid-catalyzed sol gel technique, added in sol-gel process after heat-insulated felt pan and the aerogel composite of obtained low thermal conductivity, high mechanical properties, high thermal stability is dried by aging, exchange of solvent, surface modification and normal pressure classification.

Description

A kind of TiO2The normal pressure fast preparation method of doping silicon dioxide aerogel composite
Technical field
The present invention relates to insulation material technical field, more particularly to a kind of TiO2Doping silicon dioxide aerogel composite Normal pressure fast preparation method.Specifically, the present invention is that, using cheap industrial waterglass as silicon source, adulterate TiO2Powder, profit With a step acid-catalyzed sol-gel technology, added in sol-gel process after heat-insulated felt pan by aging, exchange of solvent, table Face is modified and obtained low thermal conductivity, high mechanical properties, the aerogel composite of high thermal stability are dried in normal pressure classification.
Background technology
Silica (SiO2) aeroge is a kind of low-density, lower thermal conductivity, low-refraction, high-specific surface area, high hole The nanoporous new material of rate (80%~99.8%), has extensively in insulation material, efficient high energy electrode, field of aerospace Application prospect.It is generally many using tetraethyl orthosilicate as raw material that aerosil is prepared both at home and abroad, using sol-gel process, It is made through supercritical drying.It is dangerous big but the cost of supercritical drying is high, be not suitable for large-scale industrial production, therefore Constant pressure and dry turns into the focus of research.
Chinese patent CN101503195A, which is disclosed, uses tetraethyl orthosilicate for silicon source, by aging, exchange of solvent and Surface is modified, and last normal pressure classification is dried to obtain hydrophobicity SiO2The method of aeroge, but dioxy is prepared using constant pressure and dry SiClx aeroge is typically to obtain powder or mechanical strength very low block, constrains its application.
Chinese patent CN102701700B refer to a kind of SiO2Aerogel/inorganic cotton compound thermal insulation felt and preparation side Method.Described method is to be combined silica sol and inorganic cotton, is then aged, modified and solvent replacement processing, Constant pressure and dry processing, obtains SiO2Aerogel/inorganic cotton compound thermal insulation felt.In CN102701700B method, in order to Aeroge is prepared, industrial waterglass first must will carry out ion exchange by cationic ion-exchange resin, and operating process is complex.
The thermal conductivity factor of aerosil at normal temperatures as little as 0.02W/ (mK), but when environment temperature rise, surpass Infrared radiation heat transfer aggravates when crossing 500 DEG C, because pure silicon aeroge has to infrared ray through acting on, so radiation thermal conductivity factor Sharply increase, limit its application in high temperature environments.Chinese patent CN1749214A discloses a kind of aerogel heat-insulating and answered Heat insulation composite material in condensation material and preparation method thereof, this method, which is constituted, includes aerosil, infrared light screening agent two Titanium oxide, reinforcing fiber, obtained material has good iris action to solid heat transfer and cross-ventilation heat transfer, while can have again Effect ground barrier infrared radiation heat transfer, but in CN1749214A method, the drying means of use is supercritical fluid drying, Autoclave is needed to use, complex process, cost is high, and with certain risk.
The content of the invention
For disadvantages mentioned above present in prior art, the present inventor is concentrated on studies, and existing process is improved, first First, aerosil is prepared by using a step acid catalyzed process, eliminates industrial waterglass in existing process and pass through tree Fat carries out the process of ion exchange, can shorten manufacturing cycle, realizes quick prepare；Secondly, present invention selection has to infrared Scatter the opacifier TiO of assimilation effect2Aerosil is doped, the hyperthermia radiation heat transfer of material can be reduced, Obtain high thermal stability；In addition, aerosil is combined with heat insulation felt, its mechanical strength is improved.
It is therefore an object of the present invention to provide a kind of TiO2The normal pressure of doping silicon dioxide aerogel composite is quickly made Preparation Method, this method is based on a step acid-catalyzed sol-gel technology, using cheap industrial waterglass as silicon source, using acid solution to urge Agent, adulterate TiO2Powder, added in sol-gel process after heat-insulated felt pan by aging, exchange of solvent, surface modification with And obtained low thermal conductivity, high mechanical properties, the aerogel composite of high thermal stability are dried in normal pressure classification.
Specifically, the present invention provides the following：
1. a kind of TiO2The preparation method of doping silicon dioxide aerogel composite, the described method comprises the following steps：
(1) waterglass and water are mixed and stirred for uniformly, obtaining mixed liquor；
(2) mixed liquor obtained in step (1) is added in acid solution, adds TiO thereto afterwards2Powder, is stirred Mix and disperse, obtain well mixed Ludox；
(3) heat insulation felt is dipped into the Ludox obtained in step (2), be then taken out, or by step (2) Obtained Ludox is poured into the mould containing heat insulation felt, after aging after gel；
(4) TiO obtained into step (3)2-SiO2Alcoholic solution is added in aerogel composite and non-polar solven enters Row exchange of solvent；
(5) TiO after the exchange of solvent that will be obtained in step (4)2-SiO2Aerogel composite is placed in by nonpolar molten Surface modification treatment is carried out in the mixed liquor of agent and silane coupler composition；With
(6) by the TiO after surface modification treatment in step (5)2-SiO2Aerogel composite carries out normal pressure classification drying, Thus the TiO is obtained2Doping silicon dioxide aerogel composite.
2. the method described in 1 according to more than, wherein in step (1), including any one in following characteristics or its combination：
(a) waterglass is industrial waterglass, and preferably modulus is 2~3.5 industrial waterglass；
(b) water with waterglass formation mixed liquor is deionized water；With
(c) volume ratio of waterglass and water is 1:1~1:8.
3. the method described in 1 according to more than, wherein in step (2), including any one in following characteristics or its combination：
(a) acid solution is selected from hydrochloric acid, sulfuric acid, oxalic acid or acetic acid, preferably hydrochloric acid；
(b) volume ratio of the mixed liquor and the acid solution is 1:(0.04~0.5)；
(c) mixed liquor obtained in step (1) is added in acid solution, afterwards after pH value reaches 4~6 thereto Add TiO2Powder；
(d) it is described to stir and disperse to be by mechanical agitation and ultrasonic disperse progress, preferably mechanical agitation speed respectively For 200~700rpm；With
(e) TiO2Powder is rutile TiO2Powder, preferably its particle diameter are more preferably mixed in 0.1~3 μ m Miscellaneous TiO2The mass fraction of powder is 1%~20%.
4. the method described in 1 according to more than, wherein in step (3), including any one in following characteristics or its combination：
(a) one kind of heat insulation felt in glass mat, ceramic fiber blanket, rock wool blanket, mineral wool felt, inorganic cotton described in Or it is several；
(b) mould is the mould of anti-corrosion impermeable material, is preferably selected from what glass, nylon or polytetrafluoroethylene (PTFE) were made Mould；With
(c) after gel at 30~60 DEG C aging 4~8 hours.
5. the method described in 1 according to more than, wherein in step (4), including any one in following characteristics or its combination：
(a) exchange of solvent is carried out in 40~60 DEG C of water baths；
(b) non-polar solven is alkane solvents, is preferably selected from n-hexane, hexamethylene, normal heptane or its combination；
(c) alcoholic solution is selected from methanol, ethanol, isopropanol, acetone or its combination；With
(d) TiO2-SiO2Aerogel composite respectively exchanges 6~12 by the non-polar solven and the alcoholic solution Hour.
6. the method described in 1 according to more than, wherein in step (5), including any one in following characteristics or its combination：
(a) surface modification treatment is carried out in 40~60 DEG C of water baths, is preferably carried out 12~24 hours；
(b) silane coupler is trim,ethylchlorosilane (TMCS), HMDS (HMDZ), the silicon of hexamethyl two One or more in oxygen alkane (HMDSO), APTES；With
(c) non-polar solven is alkane solvents, is preferably selected from n-hexane, hexamethylene, normal heptane or its combination.
7. the method described in 1 according to more than, wherein in step (6), the normal pressure classification drying is first by the airsetting Glue composite is placed at 60 DEG C and dried 6 hours, is then placed at 80 DEG C and dries 6 hours, is finally dried 4 hours at 120 DEG C.
8. the method according to any one of above 1-7, it also includes reclaiming in step (4) and step (5) respectively Waste liquid.
9. the TiO as obtained by the method according to any one of above 1-82Doping silicon dioxide aeroge is combined Material.
10. the TiO described in 9 according to more than2Doping silicon dioxide aerogel composite, its density is 0.10~0.30g/ cm3, and/or thermal conductivity factor is 0.020~0.045W/ (mK).
Brief description of the drawings
Fig. 1 is the preparation TiO involved by a specific embodiment of the invention2Doping silicon dioxide aerogel composite Flow chart；
Fig. 2 is SiO prepared by the embodiment of the present invention 12The N that aeroge passes through U.S.'s Micromeritics Instrument measurings2Inhale Attached desorption isothermal curve figure, wherein abscissa are relative pressure (p/p0), ordinate is volumetric adsorption (cm3/g STP)；It can see Go out curve and belong to IV types, be the adsorption curve (bibliography of adsorption/desorption assay method of typical mesoporous material:The determination of pore volume and area distributions in porous substances.Computations from nitrogen isotherms.Journal of the American Chemical Society,73(1),373–380)；
Fig. 3 is the SEM figures of aerogel composite prepared by the embodiment of the present invention 2；
Fig. 4 is the pictorial diagram of aerogel composite prepared by the embodiment of the present invention 3.
Embodiment
To achieve these goals, technical scheme is as follows：A kind of TiO2Doping silicon dioxide aeroge is combined The normal pressure fast preparation method of material, comprises the following steps：
(1) take appropriate waterglass and deionized water to be mixed evenly according to a certain percentage, obtain mixed liquor A.
(2) solution A is added in the acid solution of a certain amount of high-speed stirred.Add and claim in advance after pH value reaches 4~6 The TiO of amount2Powder, mechanical agitation 5min, 1~5min of ultrasonic disperse, obtains well mixed Ludox.
(3) heat insulation felt is dipped into the Ludox that step (2) is obtained, colloidal sol has just been submerged heat insulation felt and then has been taken Go out, or the Ludox configured in step (2) poured into the mould containing heat-insulated felt pan, after after gel at 30~60 DEG C 4~8h of aging.
(4) TiO obtained to step (3)2-SiO2Added in aerogel composite non-polar solven, alcoholic solution 40~ Exchange of solvent, Recycling of waste liquid are carried out in 60 DEG C of water baths.
(5) by described TiO2-SiO2Aerogel composite is placed in by mixing that non-polar solven and silane coupler are constituted Liquid is closed, surface modification treatment, 12~24h of modification time, Recycling of waste liquid are carried out in 40~60 DEG C of water baths.
(6) modified TiO2-SiO2Aerogel composite is classified drying using normal pressure.
Preferably, the silicon source described in step (1) is the industrial waterglass that modulus is 2~3.5；Solution A be waterglass with Deionized water by volume 1:1~1:8 dilution gained.
Preferably, the acid solution described in step (2) is one kind in hydrochloric acid, sulfuric acid, oxalic acid or acetic acid, more preferably Hydrochloric acid；The solution A and the volume ratio of acid solution are 1:(0.04~0.5).
Preferably, the rutile TiO in step (2) from particle diameter in 0.1~3 μ m2Powder is used as infrared screening Photo etching, the mass fraction of doping is 1%~20%.
Preferably, mechanical agitation speed is 200~700r/min in step (2).
Preferably, the heat insulation felt described in step (3) be selected from glass mat, ceramic fiber blanket, rock wool blanket, mineral wool felt, One or more in inorganic cotton；The mould is the mould of anti-corrosion impermeable material, can select glass, nylon or polytetrafluoro Ethene.The present invention aeroge composite fibre felt pan in, fiber is added in colloidal sol, using sol-gel process make its into For an entirety, wherein fiber is as skeletal support aeroge matrix, so that activeness and quietness aeroge.
Preferably, the non-polar solven described in step (4) is alkane solvents, preferably from n-hexane, hexamethylene, just One kind in heptane.
Preferably, the alcoholic solution described in step (4) is one kind in methanol, ethanol, isopropanol or acetone, more preferably second Alcohol.
Preferably, the TiO described in step (4)2-SiO2Aerogel composite is respectively handed over by non-polar solven and alcoholic solution Change 6~12h.
Preferably, the silane coupler in step (5) is trim,ethylchlorosilane (TMCS), HMDS (HMDZ), the one or more in HMDO (HMDSO), APTES, mixed liquor total amount It is preferred so that all gels can be submerged.
Preferably, aging, exchange of solvent and Process of Surface Modification are carried out in constant temperature water bath, temperature control 40~ 60 DEG C, more preferably 45 DEG C.
Preferably, step 6) described in normal pressure classification dryings be that aerogel composite is first placed at 60 DEG C drying 6h, is then placed at 80 DEG C and dries 6h, and 4h is finally dried at 120 DEG C.
The invention discloses a kind of TiO2The normal pressure fast preparation method of doping silicon dioxide aerogel composite, this hair Bright is silicon source from cheap industrial waterglass, using a step acid-catalyzed sol-gel technology, by adding rutile TiO2 Powder, to improve its heat endurance, to strengthen its mechanical strength, is combined, by old as infrared light screening agent with heat insulation felt Change, exchange of solvent, surface are modified and normal pressure classification dry obtained low thermal conductivity, high mechanical properties, the gas of high thermal stability Gel complex material.There are following features with the sample that the present invention is prepared：
1) a step acid-catalyzed sol-gel method compares soda acid two-step catalysis method, eliminates the ion exchange process of complexity, saves Shi Shengli, is SiO2The large-scale production of aeroge is provided convenience condition.Simultaneously using cheap industrial waterglass as silicon source, into Originally it is greatly reduced.
2) composite heat-insulated material obtained by the present invention not only farthest remains the thermodynamic property of aeroge, leads Hot coefficient also enhances its mechanical performance at 0.020-0.045W/ (mK).
3) doped rutile type TiO is passed through2Powder, can be effectively reduced infrared transmittivity, improve its thermostability energy.
4) drying mode involved in the present invention is normal pressure classification drying, compared to the supercritical drying of high risk, often Not high dry reaction temperature, mild condition, energy-conserving and environment-protective are pressed dry, are more suitable for industrialized production.
5) the invention provides a kind of fast preparation method, manufacturing cycle is substantially reduced, from starting to be prepared into dry knot The whole preparation time of beam is no more than 3 days.
Embodiment
Following embodiments are further illustrating to be used as the elaboration to the technology of the present invention content to present invention.
Embodiment 1
1) industrial waterglass and 90ml deionized water that the mass concentration for being 3.5 by 30ml moduluses is 34% are mixed Uniform (volume ratio 1:3)；
2) water glass solution after dilution is taken to be added in the concentrated hydrochloric acid of high-speed stirred, after controlling the speed of addition first fast Slowly, when the pH of solution reaches 5 or so, the rutile TiO for accounting for mixed liquor 5%wt is added in quick stirring2Powder (Aladdin). Mechanical agitation 5min, ultrasonic disperse 3min, makes TiO2Powder is dispersed in colloidal sol, and soilless sticking occurs.
3) the colloidal sol 100ml prepared is taken to pour into 80mm × 50mm × 20mm mould, layer overlay glass in mould Fibrofelt (Chemical Reagent Co., Ltd., Sinopharm Group), makes colloidal sol just submerge glass mat, waits gel.
4) after gel in 45 DEG C of water baths aging 4h.
5) take out step 4) aerogel composite be put into beaker, add ethanol exchanged in 45 DEG C of water baths 8h, ethanol is exchanged terminate after, then with n-hexane 8h, Recycling of waste liquid are exchanged in 45 DEG C of water baths.
6) 30ml trim,ethylchlorosilane (TMCS) and 200ml n-hexane mixed liquor, 45 DEG C of water-baths are added into beaker Surface is modified 12h, Recycling of waste liquid in environment.
7) aerogel composite is placed at 60 DEG C and dries 6h, be then placed at 80 DEG C and dry 6h, finally at 120 DEG C 4h is dried, drying box is then switched off, as drying box is cooled to room temperature, produces TiO2Doping silicon dioxide aeroge composite wood Material.
The density for measuring sample by tap density meter is 0.233g/cm3, in hydrophobicity, surveyed by contact angle tester It is 144 degree to obtain hydrophobic angle, measures thermal conductivity factor for 0.0256W/mK by thermal conductivity factor instrument, is built according to GB14402-1993 The combustion heat value that material combustion calorimeter test method measures sample is 3909J/g.
Embodiment 2
1) industrial waterglass of the mass concentration 34% of 20ml moduluses 3.5 and 100ml deionized water are mixed equal Even (volume ratio 1:5)；
2) water glass solution after dilution is taken to be added in the concentrated hydrochloric acid of high-speed stirred, after controlling the speed of addition first fast Slowly, when the pH of solution reaches 5 or so, the rutile TiO for accounting for mixed liquor 5%wt is added in quick stirring2Powder (Aladdin). Mechanical agitation 5min, ultrasonic disperse 3min, makes TiO2Powder is dispersed in colloidal sol, and soilless sticking occurs.
3) the colloidal sol 100ml prepared is taken to pour into 80mm × 50mm × 20mm mould, layer overlay glass in mould Fibrofelt, makes colloidal sol just submerge glass mat, waits gel.
4) after gel in 45 DEG C of water baths aging 4h.
5) take out step 4) aerogel composite be put into beaker, add ethanol exchanged in 45 DEG C of water baths 8h, ethanol is exchanged terminate after, then with n-hexane 8h, Recycling of waste liquid are exchanged in 45 DEG C of water baths.
6) 30ml trim,ethylchlorosilane (TMCS) and 200ml n-hexane mixed liquor, 45 DEG C of water-baths are added into beaker Surface is modified 12h, Recycling of waste liquid in environment.
7) aerogel composite is placed at 60 DEG C and dries 6h, be then placed at 80 DEG C and dry 6h, finally at 120 DEG C 4h is dried, drying box is then switched off, as drying box is cooled to room temperature, produces TiO2Doping silicon dioxide aeroge composite wood Material.
According to the detection method of embodiment 1, the density of obtained sample is 0.168g/cm3, in hydrophobicity, hydrophobic angle is 148 degree, thermal conductivity factor is 0.0250W/mK, and combustion heat value is 3720J/g.
Embodiment 3
1) industrial waterglass of the mass concentration 34% of 20ml moduluses 3.5 and 100ml deionized water are mixed equal Even (volume ratio 1:5)；
2) water glass solution after dilution is taken to be added in the concentrated hydrochloric acid of high-speed stirred, after controlling the speed of addition first fast Slowly, when the pH of solution reaches 5 or so, the rutile TiO for accounting for mixed liquor 10%wt is added in quick stirring2Powder (Aladdin). Mechanical agitation 5min, ultrasonic disperse 5min, makes TiO2Powder is dispersed in colloidal sol, and soilless sticking occurs.
3) the colloidal sol 100ml prepared is taken to pour into 80mm × 50mm × 20mm mould, layer overlay glass in mould Fibrofelt, makes colloidal sol just submerge glass mat, waits gel.
4) after gel in 45 DEG C of water baths aging 4h.
5) take out step 4) aerogel composite be put into beaker, add ethanol exchanged in 45 DEG C of water baths 8h, ethanol is exchanged terminate after, then with n-hexane 8h, Recycling of waste liquid are exchanged in 45 DEG C of water baths.
6) 30ml trim,ethylchlorosilane (TMCS) and 200ml n-hexane mixed liquor, 45 DEG C of water-baths are added into beaker Surface is modified 12h, Recycling of waste liquid in environment.
7) aerogel composite is placed at 60 DEG C and dries 6h, be then placed at 80 DEG C and dry 6h, finally at 120 DEG C 4h is dried, drying box is then switched off, as drying box is cooled to room temperature, produces TiO2Doping silicon dioxide aeroge composite wood Material.
According to the detection method of embodiment 1, the density of obtained sample is 0.200g/cm3, in hydrophobicity, hydrophobic angle is 146 degree, thermal conductivity factor is 0.0258W/mK, and combustion heat value is 3815J/g.
Embodiment 4
1) industrial waterglass of the mass concentration 34% of 20ml moduluses 3.5 and 100ml deionized water are mixed equal Even (volume ratio 1:5)；
2) water glass solution after dilution is taken to be added in the concentrated hydrochloric acid of high-speed stirred, after controlling the speed of addition first fast Slowly, when the pH of solution reaches 5 or so, the rutile TiO for accounting for mixed liquor 15%wt is added in quick stirring2Powder (Aladdin). Mechanical agitation 5min, ultrasonic disperse 5min, makes TiO2Powder is dispersed in colloidal sol, and soilless sticking occurs.
3) the colloidal sol 100ml prepared is taken to pour into 80mm × 50mm × 20mm mould, layer overlay glass in mould Fibrofelt, makes colloidal sol just submerge glass mat, waits gel.
4) after gel in 45 DEG C of water baths aging 4h.
5) take out step 4) aerogel composite be put into beaker, add ethanol exchanged in 45 DEG C of water baths 8h, ethanol is exchanged terminate after, then with n-hexane 8h, Recycling of waste liquid are exchanged in 45 DEG C of water baths.
6) 30ml trim,ethylchlorosilane (TMCS) and 200ml n-hexane mixed liquor, 45 DEG C of water-baths are added into beaker Surface is modified 12h, Recycling of waste liquid in environment.
7) aerogel composite is placed at 60 DEG C and dries 6h, be then placed at 80 DEG C and dry 6h, finally at 120 DEG C 4h is dried, drying box is then switched off, as drying box is cooled to room temperature, produces TiO2Doping silicon dioxide aeroge composite wood Material.
According to the detection method of embodiment 1, the density of obtained sample is 0.216g/cm3, in hydrophobicity, hydrophobic angle is 146 degree, thermal conductivity factor is 0.0260W/mK, and combustion heat value is 3869J/g.
Embodiment 5
1) industrial waterglass of the mass concentration 34% of 20ml moduluses 3.5 and 120ml deionized water are mixed equal Even (volume ratio 1:6)；
2) water glass solution after dilution is taken to be added in the concentrated hydrochloric acid of high-speed stirred, after controlling the speed of addition first fast Slowly, when the pH of solution reaches 5 or so, the rutile TiO for accounting for mixed liquor 5%wt is added in quick stirring2Powder (Aladdin). Mechanical agitation 5min, ultrasonic disperse 5min, makes TiO2Powder is dispersed in colloidal sol, and soilless sticking occurs.
3) the colloidal sol 100ml prepared is taken to pour into 80mm × 50mm × 20mm mould, layer overlay glass in mould Fibrofelt, makes colloidal sol just submerge glass mat, waits gel.
4) after gel in 45 DEG C of water baths aging 4h.
5) take out step 4) aerogel composite be put into beaker, add ethanol exchanged in 45 DEG C of water baths 8h, ethanol is exchanged terminate after, then with n-hexane 8h, Recycling of waste liquid are exchanged in 45 DEG C of water baths.
6) 30ml trim,ethylchlorosilane (TMCS) and 200ml n-hexane mixed liquor, 45 DEG C of water-baths are added into beaker Surface is modified 12h, Recycling of waste liquid in environment.
7) aerogel composite is placed at 60 DEG C and dries 6h, be then placed at 80 DEG C and dry 6h, finally at 120 DEG C 4h is dried, drying box is then switched off, as drying box is cooled to room temperature, produces TiO2Doping silicon dioxide aeroge composite wood Material.
According to the detection method of embodiment 1, the density of obtained sample is 0.193g/cm3, in hydrophobicity, hydrophobic angle is 150 degree, thermal conductivity factor is 0.0251W/mK, and combustion heat value is 3510J/g.
What the present invention was not disclosed in detail partly belongs to techniques known.
Although illustrative embodiment of the invention is described above, in order to the technology of the art Personnel understand the present invention, it should be apparent that the invention is not restricted to the scope of embodiment, to the common skill of the art For art personnel, as long as various change is in the spirit and scope of the present invention that appended claim is limited and is determined, these Change is it will be apparent that all utilize the innovation and creation of present inventive concept in the row of protection.

Claims (10)

1. a kind of TiO2The preparation method of doping silicon dioxide aerogel composite, the described method comprises the following steps：
(1) waterglass and water are mixed and stirred for uniformly, obtaining mixed liquor；
(2) mixed liquor obtained in step (1) is added in acid solution, adds TiO thereto afterwards2Powder, stirs and divides Dissipate, obtain well mixed Ludox；
(3) heat insulation felt is dipped into the Ludox obtained in step (2), be then taken out, or will obtained in step (2) Ludox pour into the mould containing heat insulation felt, after aging after gel；
(4) TiO obtained into step (3)2-SiO2Alcoholic solution is added in aerogel composite and non-polar solven progress is molten Agent is exchanged；
(5) TiO after the exchange of solvent that will be obtained in step (4)2-SiO2Aerogel composite be placed in by non-polar solven and Surface modification treatment is carried out in the mixed liquor of silane coupler composition；With
(6) by the TiO after surface modification treatment in step (5)2-SiO2Aerogel composite carries out normal pressure classification drying, thus Obtain the TiO2Doping silicon dioxide aerogel composite.
2. according to the method described in claim 1, wherein in step (1), including any one in following characteristics or its combination：
(a) waterglass is industrial waterglass, and preferably modulus is 2~3.5 industrial waterglass；
(b) water with waterglass formation mixed liquor is deionized water；With
(c) volume ratio of waterglass and water is 1:1~1:8.
3. according to the method described in claim 1, wherein in step (2), including any one in following characteristics or its combination：
(a) acid solution is selected from hydrochloric acid, sulfuric acid, oxalic acid or acetic acid, preferably hydrochloric acid；
(b) volume ratio of the mixed liquor and the acid solution is 1:(0.04~0.5)；
(c) mixed liquor obtained in step (1) is added in acid solution, added thereto after pH value reaches 4~6 afterwards TiO2Powder；
(d) described to stir and disperse to be carried out by mechanical agitation and ultrasonic disperse respectively, preferably mechanical agitation speed is 200 ~700rpm；With
(e) TiO2Powder is rutile TiO2Powder, preferably its particle diameter more preferably adulterate in 0.1~3 μ m TiO2The mass fraction of powder is 1%~20%.
4. according to the method described in claim 1, wherein in step (3), including any one in following characteristics or its combination：
(a) one kind or several of heat insulation felt in glass mat, ceramic fiber blanket, rock wool blanket, mineral wool felt, inorganic cotton described in Kind；
(b) mould is the mould of anti-corrosion impermeable material, is preferably selected from the mould that glass, nylon or polytetrafluoroethylene (PTFE) are made Tool；With
(c) after gel at 30~60 DEG C aging 4~8 hours.
5. according to the method described in claim 1, wherein in step (4), including any one in following characteristics or its combination：
(a) exchange of solvent is carried out in 40~60 DEG C of water baths；
(b) non-polar solven is alkane solvents, is preferably selected from n-hexane, hexamethylene, normal heptane or its combination；
(c) alcoholic solution is selected from methanol, ethanol, isopropanol, acetone or its combination；With
(d) TiO2-SiO2Aerogel composite is respectively exchanged 6~12 hours by the non-polar solven and the alcoholic solution.
6. according to the method described in claim 1, wherein in step (5), including any one in following characteristics or its combination：
(a) surface modification treatment is carried out in 40~60 DEG C of water baths, is preferably carried out 12~24 hours；
(b) silane coupler is trim,ethylchlorosilane (TMCS), HMDS (HMDZ), HMDO (HMDSO), the one or more in APTES；With
(c) non-polar solven is alkane solvents, is preferably selected from n-hexane, hexamethylene, normal heptane or its combination.
7. according to the method described in claim 1, wherein in step (6), the normal pressure classification drying is first by the airsetting Glue composite is placed at 60 DEG C and dried 6 hours, is then placed at 80 DEG C and dries 6 hours, is finally dried 4 hours at 120 DEG C.
8. the method according to any one of claim 1-7, it also includes reclaiming in step (4) and step (5) respectively Waste liquid.
9. the TiO as obtained by the method according to any one of claim 1-82Doping silicon dioxide aeroge is combined Material.
10. TiO according to claim 92Doping silicon dioxide aerogel composite, its density is 0.10~0.30g/ cm3, and/or thermal conductivity factor is 0.020~0.045W/ (mK).
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CN109503116A (en) * 2018-12-17 2019-03-22 山东鲁阳节能材料股份有限公司 A kind of preparation method of aeroge compound insulating material
CN109574622A (en) * 2019-01-15 2019-04-05 冷水江三A新材料科技有限公司 A kind of preparation method of high temperature resistant silicon dioxide aeroge insulation quilt
CN111635175A (en) * 2020-06-15 2020-09-08 中建材科创新技术研究院(山东)有限公司 Aerogel light mineral wool heat insulation plate and preparation method thereof
CN112060719A (en) * 2019-06-11 2020-12-11 江苏泛亚微透科技股份有限公司 High silica glass fiber cloth-wrapped doped modified silica aerogel felt product for lithium ion power battery of electric automobile and manufacturing method thereof
CN112592149A (en) * 2020-12-31 2021-04-02 山东大学 Method for rapidly preparing silicon dioxide aerogel composite material by taking water glass as raw material through single solvent exchange
CN115368110A (en) * 2022-09-09 2022-11-22 贵州航天乌江机电设备有限责任公司 Method for carrying out powder doping on aerogel paper

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109503116A (en) * 2018-12-17 2019-03-22 山东鲁阳节能材料股份有限公司 A kind of preparation method of aeroge compound insulating material
CN109574622A (en) * 2019-01-15 2019-04-05 冷水江三A新材料科技有限公司 A kind of preparation method of high temperature resistant silicon dioxide aeroge insulation quilt
CN112060719A (en) * 2019-06-11 2020-12-11 江苏泛亚微透科技股份有限公司 High silica glass fiber cloth-wrapped doped modified silica aerogel felt product for lithium ion power battery of electric automobile and manufacturing method thereof
CN111635175A (en) * 2020-06-15 2020-09-08 中建材科创新技术研究院(山东)有限公司 Aerogel light mineral wool heat insulation plate and preparation method thereof
CN112592149A (en) * 2020-12-31 2021-04-02 山东大学 Method for rapidly preparing silicon dioxide aerogel composite material by taking water glass as raw material through single solvent exchange
CN115368110A (en) * 2022-09-09 2022-11-22 贵州航天乌江机电设备有限责任公司 Method for carrying out powder doping on aerogel paper

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Application publication date: 20170929