CN103755152A - Preparation method for super-hydrophobic SiO2 aerogel film - Google Patents

Preparation method for super-hydrophobic SiO2 aerogel film Download PDF

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CN103755152A
CN103755152A CN201310695739.4A CN201310695739A CN103755152A CN 103755152 A CN103755152 A CN 103755152A CN 201310695739 A CN201310695739 A CN 201310695739A CN 103755152 A CN103755152 A CN 103755152A
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sio
aerogel
super
preparation
hydrophobic
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CN103755152B (en
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汪雷
张艳蓉
王明昂
戴准
庄重源
李斯
郭春林
周海锋
杨德仁
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention relates to a preparation method for a super-hydrophobic SiO2 aerogel film. Specifically, a mixed solution of hydrochloric acid and hexamethyl disiloxane is employed to perform hydrophobic modification on a SiO2 film, and concentrated sulfuric acid is used as a catalyst to accelerate rightward proceeding of reaction so as to generate more trimethylchlorosilane. The more the trimethylchlorosilane is, the stronger the activity is during modification, so that the trimethylchlorosilane can diffuse into the film, thus reducing the capillary force in the material, and realizing complete modification of the film from the inside out. Compared with the existing hydrophobic modification methods, the method provided by the invention omits the expensive solvent replacement step, greatly simplifies the process, is easy to realize industrial production, and causes small environmental pollution, thus having attractive application prospects.

Description

A kind of super-hydrophobic SiO 2the preparation method of aerogel
Technical field
The present invention relates to thin film technique field, relate in particular to a kind of super-hydrophobic SiO 2the preparation method of aerogel.
Background technology
Hydrophobic glass can be widely used in the surface of various waterproof, frost prevention and efflorescence prevention, as the glassworks such as automobile and aircraft windshield, building doors and windows glass, cladding glass, mirror and glasses all exist the difficult problem of waterproof and cleaning.The daily life of using Hydrophobic glass to be greatly convenient for people to, and can create larger economic benefit.Mostly use at present both at home and abroad the method that is coated with thin film at material surface to obtain Hydrophobic glass.
SiO 2aerogel is a kind of novel nano-porous materials, is a kind of hydrophobic film that has utilization prospect.Secondly, SiO 2aerogel also has the characteristics such as low thermal conductivity, high light transmittance, high porosity and low density, at coating one deck SiO on glass 2aerogel is one of effective way improving the heat insulation and preservation effects such as energy saving building window glass and windshield.Therefore, SiO 2the research of aerogel has become a study hotspot in domestic and international inorganic functional heat-insulating heat-preserving material field.
SiO 2the hydrophobicity of the aerogel network structure inner with it with thermal insulation is relevant, and due to SiO 2in aerogel network internal structure, exist to ambient moisture and moisture-sensitive-OH hydrophilic radical, make the moisture of film in absorbed air, even there is crackle in the contraction that causes film, damage its porous network structure, thereby the heat-proof quality that worsens film, heat-proof quality is also relevant with hydrophobicity to a certain extent.Therefore, can improve SiO 2the hydrophobicity of aerogel is the emphasis of studying at present.
When constant pressure and dry, the condensation meeting between hydroxyl causes aerogel serious contraction to occur, cave in and the situation such as broken, thereby affecting it obtains the excellent properties such as low density, high-specific surface area, therefore, adopts hydrophobically modified agent to SiO 2aerogel oh group carries out modifying and decorating, keeps the porous network structure of film, effectively improves its hydrophobic performance.
Publication number is the preparation method that CN103359954 discloses a kind of hexa-methyldisilazane graft modified silicon sol and super-hydrophobic silica film, it utilize intermolecular dehydration reaction by hexamethyldisilazane-Si(CH 3) 3group is grafted in silicon sol molecule, makes the be covered with-Si(CH of micelle surface of silicon sol 3) 3group, obtains the hydrophobic colloidal silica of modification, is finally coated in matrix surface.But the properties-correcting agent that this method is used is hexamethyldisilazane, and environmental pollution is larger.
Military people (the super-hydrophobic type SiO that water glass is source that waits of the Liu Guang of Tongji University 2aerogel block body preparation and sign, silicate journal, the 40th the 1st phase of volume, in January, 2012) adopt the mixed solution modification wet gel of hexamethyldisiloxane (HMDSO) and a small amount of hydrochloric acid to prepare SiO 2aerogel block body, gained aerogel block body surface contact angle can reach more than 150 °, and this method of modifying adopts the mixing solutions of hydrochloric acid and hexamethyldisiloxane, and modified effect is good, and environmental pollution is little.But this method of modifying speed of response is gentleer, and modification efficiency is low, when to block modification, properties-correcting agent is difficult to be diffused into block inside, so must, through shifting to an earlier date solvent replacing step, replace SiO with the ethanol that surface tension is little 2the water that aerogel block body internal table surface tension is large, avoids the effect due to capillary force in drying process to there will be the phenomenon of caving in.
Summary of the invention
For the deficiencies in the prior art, of the present inventionly provide a kind of super-hydrophobic SiO 2the preparation method of aerogel.
A kind of super-hydrophobic SiO 2the preparation method of aerogel, comprises the following steps:
(1) alkaline silicon solution is prepared to acidic silicasol by ion exchange resin, then with basic solution, regulating pH value is 5.0-6.0, obtains SiO 2colloidal sol;
(2) utilize described SiO 2colloidal sol, adopts dipping-pulling method on substrate, to prepare SiO 2wet gel film;
(3) SiO step (2) being prepared 2in wet gel film immersion deionized water, carry out aging;
(4) by the SiO after aging 2in the mixed solution that is soaked in hexamethyldisiloxane and hydrochloric acid of wet gel film, add the vitriol oil as catalyzer, carry out hydrophobically modified;
(5) by the SiO carrying out after hydrophobically modified 2wet gel film is dry 24h at normal temperatures, forms super-hydrophobic SiO 2aerogel.
Hydrochloric acid occurs in the aqueous solution with hexamethyldisiloxane to react as follows:
(CH 3) 3SiOSi(CH 3) 3+2HCl—2(CH 3) 3SiCl+2H 2O。
Because reaction is from left to right thermo-negative reaction, so hydrochloric acid (HCl) and hexamethyldisiloxane ((CH 3) 3siOSi (CH 3) 3) reaction generation trimethylchlorosilane ((CH 3) 3siCl) efficiency is very low, and trimethylchlorosilane is the Main Function agent of hydrophobically modified, so adopt hydrochloric acid and the modification of hexamethyldisiloxane mixing solutions to need certain temperature and longer time could realize hydrophobically modified more completely, and be difficult to be deep into block inter-modification.
The present invention adopts the mixing solutions of hydrochloric acid and hexamethyldisiloxane to SiO 2film carries out hydrophobically modified, and use the vitriol oil as catalyzer, promote reaction to carry out from left to right, generate more properties-correcting agent (trimethylchlorosilane), properties-correcting agent is more, and during modification, activity is stronger, thereby makes properties-correcting agent can be spread to film inside (film thickness is at micron order), reduce the capillary force of material internal, realized film complete modification from inside to outside.With respect to existing hydrophobically modified method, the present invention saves expensive solvent replacing step, has greatly simplified technique, easily realize industrialization and produce, and environmental pollution is little, has tempting application prospect.
The pH value of acidic silicasol is 1.0～3.0 in described step (1), and then by basic solution adjusting pH value, making the PH of the solution that finally obtains is 5.0～6.0, obtains SiO 2silicon sol (SiO 2colloidal sol).
The present invention also can directly adopt the silicon sol of purchase.
In described step (2), prepare before wet gel film on substrate, substrate need be through cleaning, drying treatment, and described substrate can be common slide glass.
In described step (2), adopt dipping-pulling method to prepare SiO 2during wet gel film, first substrate immersed in silicon sol and keep 10～50s, then the speed with 2.0～3.0cm/s lifts out by substrate, thereby prepares SiO on substrate 2wet gel film.The speed lifting has determined the SiO of preparation 2the thickness of aerogel.
In described step (3), digestion time is 4～48h.
In mixed solution in described step (4), the volume ratio of hexamethyldisiloxane and hydrochloric acid is 2～8:1, and the mass percent concentration of described hydrochloric acid is 36%～38%.As preferably, in mixed solution, the volume ratio of hexamethyldisiloxane and hydrochloric acid is 2:1.
Described vitriol oil mass percent concentration is 70%～99%.The vitriol oil that general employing percentage concentration is 98%.
The volume ratio of the described vitriol oil and described mixing solutions is 0.1%～5%.When the vitriol oil is more, reacts faster, but react too fast, can reduce the quality of the aerogel preparing.Generally, the volume ratio of the vitriol oil and described mixing solutions is less than 5%.As preferably, the volume ratio of the vitriol oil and described mixing solutions is 5%.
The mixing solutions that adopts hydrochloric acid and hexamethyldisiloxane is during as the properties-correcting agent of hydrophobically modified, reaction conditions is gentle, but need certain temperature, after adding catalyzer, just can carry out modification at normal temperatures, for accelerating hydrophobically modified efficiency, can under heating condition, carry out.Therefore, as preferably, in described step (4), the temperature of hydrophobically modified is 25～80 ℃.
As preferably, in described step (4), the time of hydrophobically modified is 4～48h.
Due to water glass (Na 2siO 3) wide material sources, can reduce preparation cost.Therefore, described step (1) neutral and alkali silicon solution is Na 2siO 3the aqueous solution.
Alkalescence silicon solution filters water glass (Na by ion exchange resin 2siO 3) wide material sources, and Na 2during the excessive concentration of SiO3, viscosity is strong, be difficult for by ion exchange resin, and concentration is when lower, and viscosity is inadequate, cannot form network-like gel structure again.So as preferred, described Na 2siO 3the mass percent concentration of the aqueous solution is 5%～22%.
For avoiding introducing impurity in preparation process, the basic solution in described step (1) is aqueous sodium hydroxide solution or ammoniacal liquor.Because ammoniacal liquor can volatilize, water-soluble being easy to of sodium ion removed, and therefore, as preferred aqueous sodium hydroxide solution or ammoniacal liquor, can not bring a lot of impurity in final product aerogel into.
The present invention also provides the super-hydrophobic SiO being prepared by this preparation method 2aerogel, this super-hydrophobic SiO 2the thickness of aerogel is 100nm～30 μ m, visible light transmissivity 80%～96%, and surface contact angle is 120 °～153 °.
Compared with prior art, the invention has the advantages that:
One, adopt technical grade water glass as silicon source, by ion exchange method, prepare silicon dioxide gel, raw materials cost is low, technical maturity, simple.
Two, adopt deionized water aging, effect is better, and has omitted common solvent exchange step.
Three, in hydrophobically modified process, adopt the mixing solutions of hydrochloric acid and hexamethyldisiloxane as modifier, and using the vitriol oil as catalyzer, other modifier environmental pollutions are little relatively, and can recycle and reuse, and greatly reduce costs.
Four, dry under normal temperature and pressure under air atmosphere, when reducing costs, risk is lower, easily operation, and applicability is strong, is applicable to large-scale industrialization and produces.
Five, SiO 2aerogel shows after tested to possess higher transmitance, in certain temperature range, has more stable ultra-hydrophobicity.
Accompanying drawing explanation
Fig. 1 is the super-hydrophobic SiO that has of embodiment 1 preparation 2the SEM image of aerogel, its magnification is * 50K;
Fig. 2 is the super-hydrophobic SiO that has of embodiment 1 preparation 2the glass static contact angle photo of aerogel.
Embodiment
Below in conjunction with the drawings and specific embodiments, describe technical scheme of the present invention in detail, but the present invention is not limited to embodiment, those skilled in the art can adjust according to practical situation.
Embodiment 1
(1) prepare SiO 2colloidal sol
The Na that is 10% by mass percent 2siO 3pH after the aqueous solution filters by ion exchange resin is that 1.5(is acidic silicasol), then use aqueous sodium hydroxide solution (in the present embodiment, the mass percent concentration of aqueous sodium hydroxide solution is 8%) to regulate pH value to 5.0(, sodium hydroxide solution dropwise to be splashed in acidic silicasol), can obtain silicon sol;
(2) plated film
Adopt dipping-pulling method the dried slide glass of wash clean is immersed in silicon sol and keep 30s, then with the speed of 2.2cm/s, lifted out and obtain wet gel film;
(3) wet gel is aging
The slide glass that has applied wet gel film is immersed and in deionized water, carries out aging 12h;
(4) wet gel modification
The slide glass that has applied the wet gel film after aging is soaked in the mixed solution (being that methyl two silicon ethers and hydrochloric acid volume ratio are 2:1) of the hydrochloric acid that 30ml hexamethyldisiloxane and 15ml mass percent are 37%, and to add 2ml mass percent be 98% vitriol oil, carry out the modification of wet gel film surface, at 60 ℃, modify 24h;
(5) Air drying
Finally, sample is dried to 24h at normal temperatures, obtains super-hydrophobic SiO 2aerogel.
The super-hydrophobic SiO that the present embodiment prepares 2the thickness of aerogel is 113nm, and the transmitance of visible ray is 92%.
Fig. 1 is this super-hydrophobic SiO 2the SEM image of aerogel, can find out, this super-hydrophobic SiO 2the surface uniform of aerogel.
Fig. 2 is this super-hydrophobic SiO 2the glass static contact angle photo of aerogel, can find out this super thin SiO 2the contact angle of aerogel is 153.0 °.
Embodiment 2
Step (1) mesosilicic acid na concn is 15%, and all the other are identical with example 1.
The super thin SiO preparing in the present embodiment 2the super-hydrophobic SiO of aerogel 2the thickness of aerogel is 113nm, and the transmitance of visible ray is 93%, and contact angle is 143 °.
Embodiment 3
In step (2), pull rate is 2.8cm/s, and all the other are identical with example 1.
The super thin SiO preparing in the present embodiment 2the super-hydrophobic SiO of aerogel 2the thickness of aerogel is 100nm, and the transmitance of visible ray is 91%, and contact angle is about 134 °.
Embodiment 4
Step (3) digestion time is 20h, and all the other are identical with example 1.
The super thin SiO preparing in the present embodiment 2the super-hydrophobic SiO of aerogel 2the thickness of aerogel is 115nm, and the transmitance of visible ray is 92%, and contact angle is 140 °.
Embodiment 5
In step (4), modification temperature is 27 ℃, and modification time is 36h, and all the other are with example 1.
The super thin SiO preparing in the present embodiment 2the super-hydrophobic SiO of aerogel 2the thickness of aerogel is 112nm, and the transmitance of visible ray is 90%, and contact angle is 151.1 °.

Claims (9)

1. a super-hydrophobic SiO 2the preparation method of aerogel, is characterized in that, comprises the following steps:
(1) alkaline silicon solution is prepared to acidic silicasol by ion exchange resin, then with basic solution, regulating pH value is 5.0-6.0, obtains SiO 2colloidal sol;
(2) utilize described SiO 2colloidal sol, adopts dipping-pulling method on substrate, to prepare SiO 2wet gel film;
(3) SiO step (2) being prepared 2in wet gel film immersion deionized water, carry out aging;
(4) by the SiO after aging 2wet gel film is soaked in the mixed solution of hexamethyldisiloxane and hydrochloric acid, adds the vitriol oil as catalyzer, carries out hydrophobically modified;
(5) by the SiO carrying out after hydrophobically modified 2wet gel film is dry 24h at normal temperatures, forms super-hydrophobic SiO 2aerogel.
2. super-hydrophobic SiO as claimed in claim 1 2the preparation method of aerogel, is characterized in that, in the mixed solution in described step (4), the volume ratio of hexamethyldisiloxane and hydrochloric acid is 2～8:1, and the mass percent concentration of described hydrochloric acid is 36%～38%.
3. super-hydrophobic SiO as claimed in claim 2 2the preparation method of aerogel, is characterized in that, described vitriol oil mass percent concentration is 70%～99%.
4. super-hydrophobic SiO as claimed in claim 3 2the preparation method of aerogel, the volume ratio of the described vitriol oil and described mixing solutions is 0.1%～5%.
5. super-hydrophobic SiO as claimed in claim 4 2the preparation method of aerogel, is characterized in that, in described step (4), the temperature of hydrophobically modified is 25～80 ℃.
6. super-hydrophobic SiO as claimed in claim 5 2the preparation method of aerogel, is characterized in that, in described step (4), the time of hydrophobically modified is 4～48h.
7. super-hydrophobic SiO as claimed in claim 6 2the preparation method of aerogel, is characterized in that, described step (1) neutral and alkali silicon solution is Na 2siO 3the aqueous solution.
8. super-hydrophobic SiO as claimed in claim 7 2the preparation method of aerogel, is characterized in that, described Na 2siO 3the mass percent concentration of the aqueous solution be 5%～22%.
9. super-hydrophobic SiO as claimed in claim 8 2the preparation method of aerogel, is characterized in that, the basic solution in described step (1) is aqueous sodium hydroxide solution or ammoniacal liquor.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111515107A (en) * 2020-04-22 2020-08-11 江苏百瑞尔包装材料有限公司 Oxide film with ultrahigh transparent barrier and preparation method thereof
CN114315248A (en) * 2021-12-29 2022-04-12 上海暖丰保温材料有限公司 Concrete block and preparation method thereof
CN115003642A (en) * 2020-10-15 2022-09-02 株式会社Lg化学 Method of making aerogel blankets and aerogel blankets made thereby

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0490011A1 (en) * 1990-12-14 1992-06-17 Foret, S.A. A process to obtain zeolite 4A starting from bauxite
CN1865136A (en) * 2005-05-19 2006-11-22 同济大学 Surface activity adjustable nano porous silicon dioxide aerogel and its preparation method
CN103359954A (en) * 2012-04-01 2013-10-23 比亚迪股份有限公司 Preparation method of silicon dioxide super-hydrophobic thin film and super-hydrophobic material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0490011A1 (en) * 1990-12-14 1992-06-17 Foret, S.A. A process to obtain zeolite 4A starting from bauxite
CN1865136A (en) * 2005-05-19 2006-11-22 同济大学 Surface activity adjustable nano porous silicon dioxide aerogel and its preparation method
CN103359954A (en) * 2012-04-01 2013-10-23 比亚迪股份有限公司 Preparation method of silicon dioxide super-hydrophobic thin film and super-hydrophobic material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘光武等: "水玻璃为源的超疏水型SiO2气凝胶块体制备与表征", 《硅酸盐学报》, vol. 40, no. 1, 31 January 2012 (2012-01-31), pages 160 - 164 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111515107A (en) * 2020-04-22 2020-08-11 江苏百瑞尔包装材料有限公司 Oxide film with ultrahigh transparent barrier and preparation method thereof
CN115003642A (en) * 2020-10-15 2022-09-02 株式会社Lg化学 Method of making aerogel blankets and aerogel blankets made thereby
CN114315248A (en) * 2021-12-29 2022-04-12 上海暖丰保温材料有限公司 Concrete block and preparation method thereof

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