阅读说明：本技术 利用磁控溅射法制备二氧化硅-二氧化钛复合气凝胶靶材及刚性膜制备方法 (Method for preparing silicon dioxide-titanium dioxide composite aerogel target material and rigid film by magnetron sputtering method ) 是由 张鼎昊 孙晔 姜佩 陈建伟 白凤祥 韩连山 曹艳军 吴娜 刘鹏 张鼎新 于 2021-03-03 设计创作，主要内容包括：本发明提供了一种利用磁控溅射法制备二氧化硅-二氧化钛复合气凝胶靶材及刚性膜制备方法,涉及玻璃隔热膜技术领域,包括：将钛源溶液和第一改性剂溶液混合,滴加磷酸铵水溶液,完全凝胶后陈化、置换,干燥、研磨,得到粒径200～2200nm的纳米TiO-2气凝胶芯材；将硅源溶液和第二改性剂溶液混合,加入纳米TiO-2气凝胶芯材,混合后滴加磷酸铵水溶液,完全凝胶后陈化、置换,干燥、研磨,得到粒径300～2300nm的复合气凝胶靶材。本分明改变了传统磁控溅射靶材为实心结构,利用气凝胶制备技术及材料复合技术获得SiO-2-TiO-2气凝胶结构靶材。通过研磨工艺获得纳米粒子,通过磁控溅射技术获得刚性气凝胶膜。(The invention provides a method for preparing a silicon dioxide-titanium dioxide composite aerogel target material and a rigid film by utilizing a magnetron sputtering method, which relate to the technical field of glass heat insulation films and comprise the following steps: mixing a titanium source solution and a first modifier solution, dropwise adding an ammonium phosphate aqueous solution, completely gelling, aging, replacing, drying and grinding to obtain the nano TiO with the particle size of 200-2200 nm 2 An aerogel core material; mixing the silicon source solution and the second modifier solution, and adding the nano TiO 2 And (3) mixing the aerogel core materials, then dropwise adding an ammonium phosphate aqueous solution, completely gelling, then aging, replacing, drying and grinding to obtain the composite aerogel target material with the particle size of 300-2300 nm. The invention is a clear improvementChanges the traditional magnetron sputtering target material into a solid structure, and utilizes aerogel preparation technology and material composite technology to obtain SiO 2 ‑TiO 2 Aerogel structure target material. The nano particles are obtained by a grinding process, and the rigid aerogel film is obtained by a magnetron sputtering technology.)

1. SiO (silicon dioxide)₂-TiO₂The preparation method of the composite aerogel target material is characterized by comprising the following steps:

(a) obtaining the nano TiO₂Aerogel core material: mixing the titanium source solution and the first modifier solution, dripping ammonium phosphate aqueous solution with the pH value of 4.5-6.0, completely gelling, aging, replacing, drying and grinding to obtain the titanium-modified aluminum-based alloyNano TiO with particle size of 200-2200 nm₂An aerogel core material;

(b) preparation of SiO₂-TiO₂Composite aerogel target material: mixing a silicon source solution and a second modifier solution, and adding the nano TiO obtained in the step (a)₂Uniformly mixing an aerogel core material, dropwise adding ammonium phosphate aqueous solution with the pH value of 4.5-6.0, completely gelling, aging, replacing, drying and grinding to obtain SiO with the particle size of 300-2300 nm₂Aerogel coated nano TiO₂SiO of aerogel core material₂-TiO₂Compounding an aerogel target material;

wherein the first modifier solution and the second modifier solution each independently comprise an alkylsiloxane compound.

2. The method according to claim 1, wherein in the step (a), the titanium source solution comprises a titanium source and a solvent; the titanium source comprises at least one of n-butyl titanate, tetraisopropyl titanate, titanyl sulfate, titanium sulfate or titanium tetrachloride; the solvent comprises at least one of alcohols, esters, ketones or nitriles;

preferably, the mass concentration of the titanium source solution is 20-100%;

preferably, the first modifier solution comprises an alkyl siloxane compound and a solvent; the alkyl siloxane compound comprises at least one of methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, triethylmethoxysilane, triethylethoxysilane, diethyldiethoxysilane or ethyltriethoxysilane; the solvent comprises at least one of alcohols, esters, ketones or nitriles;

preferably, the mass concentration of the first modifier solution is 1-10%;

preferably, the mass ratio of the titanium source solution to the first modifier solution is 10: 0.1 to 5;

preferably, the temperature for mixing the titanium source solution and the first modifier solution is-15 ℃ to 20 ℃.

3. The method according to claim 1, wherein in step (a), the amount of the aqueous ammonium phosphate solution added is 1-5% of the mixed solution;

preferably, the aging temperature is 10-30 ℃, and the aging time is 6-12 h;

preferably, the solvent used for replacement is an alcohol solvent, the temperature of replacement is 10-60 ℃, and the time of replacement is 12-24 h;

preferably, the drying is supercritical drying.

4. The method according to claim 1, wherein in step (b), the silicon source solution comprises a silicon source and a solvent; the silicon source comprises at least one of methyl silicate, tetraethyl orthosilicate or silica sol; the solvent comprises at least one of ethanol, acetonitrile, isopropanol, acetone or n-butanol;

preferably, the mass concentration of the silicon source solution is 20-50%;

preferably, the second modifier solution comprises an alkylsiloxane compound and a solvent; the alkyl siloxane compound comprises at least one of methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, triethylmethoxysilane, triethylethoxysilane, diethyldiethoxysilane or ethyltriethoxysilane; the solvent comprises at least one of alcohols, esters, ketones or nitriles;

preferably, the mass concentration of the second modifier solution is 2-10%;

preferably, the silicon source solution and the second modifier solution are mixed in a mass ratio of 10: 0.1 to 5;

preferably, the temperature at which the silicon source solution and the second modifier solution are mixed is normal temperature.

5. The method according to any one of claims 1 to 4, wherein in the step (b), the nano TiO is₂The addition amount of the aerogel core material is 0.1-10% of the mass of the silicon source;

preferably, the adding amount of the ammonium phosphate aqueous solution is 1-5%.

6. The method according to any one of claims 1 to 4, wherein the aging temperature is 10 to 30 ℃ and the aging time is 6 to 12 hours;

preferably, the solvent used for replacement is an alcohol solvent, the temperature of replacement is 10-60 ℃, and the time of replacement is 12-24 h;

preferably, the drying is supercritical drying.

7. SiO (silicon dioxide)₂-TiO₂The composite aerogel target material is characterized by being prepared by the preparation method of any one of claims 1 to 6;

the SiO₂-TiO₂The composite aerogel target material comprises nano TiO₂Aerogel core and outer SiO layer₂Aerogels, SiO₂Aerogel coated nano TiO₂An aerogel core material; the SiO₂-TiO₂The particle size of the composite aerogel target material is 300-2300 nm, and the nano TiO₂The particle size of the aerogel core material is 200-2200 nm.

8. A method for preparing a heat-insulating film, which is characterized in that glass is used as a substrate, and a magnetron sputtering method is adopted to prepare the heat-insulating film, wherein the SiO 2 of claim 7 is used as a target material for magnetron sputtering₂-TiO₂And (3) compounding the aerogel target material.

9. The method of claim 8, wherein the magnetron sputtering parameters include:

the vacuum degree is 200-800 Pa, the radio frequency is 1.4-2.4 KV, the sputtering argon gas pressure is 0.3-0.8 Pa, the substrate preheating temperature is 60-80 ℃, and the sputtering time is 15-25 minutes.

10. A heat insulating film produced by the method for producing a heat insulating film according to claim 8 or 9; the thickness of the heat insulation film is 0.3-10 mu m;

preferably, the thermal conductivity of the thermal insulation film is 0.001-0.01 w/(mk); the ultraviolet blocking rate is 90-99.5%; the infrared blocking rate is 80-95%; the visible light blocking rate is 10-30%; film adhesion 5B; the membrane drainage angle is 90-150 degrees; the pencil hardness is 2H; the cold-heat cycle aging resistance is not less than 3000 hours without change.

Technical Field

The invention relates to the technical field of glass heat insulation films, in particular to a method for preparing a silicon dioxide-titanium dioxide composite aerogel target material and a rigid film by using a magnetron sputtering method.

Background

Glass insulating films were originally developed to control the imbalance of heating and cooling caused by solar loads, and early films only had the ability to reflect solar radiation out of the glazing or absorb heat to prevent an increase in heat from the inner surface of the glass.

The existing glass heat insulation film is widely applied to curtain wall glass of large buildings and window glass of automobiles, for example, most of automobile window glass is pasted with the heat insulation film, the heat insulation film reduces the damage of ultraviolet rays to human bodies and interior ornaments of automobiles, slows down the aging of facilities in the automobiles, reduces the temperature of the environment in the automobiles, improves the riding environment of drivers and passengers, reduces the oil consumption of the automobiles and saves the automobile cost.

Chinese patents (CN201720052999.3, CN201920913523.3, CN201920097348.5, CN202010646618.0, etc.) all disclose aerogel heat-insulating films, mainly made of SiO₂The aerogel layer is compounded with other layer structures,the heat insulation film has brittleness, is only used as an interlayer, is easy to fall off powder, has thicker thickness, and has poor light transmittance, heat insulation effect and service life. Meanwhile, the aerogel layer is usually prepared by a sol-gel method at present, and is rarely prepared by a magnetron sputtering method.

In addition, patent 201310585016.9 discloses a SiO₂Coated TiO₂The material, but not the porous hydrophobic aerogel structure itself, limits its further applications.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

One of the objectives of the present invention is to provide a SiO₂-TiO₂The preparation method of the composite aerogel target material obtains the magnetic control target material with a porous and hydrophobic structure.

The second object of the present invention is to provide a SiO₂-TiO₂And (3) compounding the aerogel target material.

The invention also aims to provide a preparation method of the heat insulation film, which is characterized in that the aerogel composite structure material is formed on glass by utilizing the magnetron sputtering technology to obtain the rigid film consisting of the nano aerogel structure.

The fourth purpose of the invention is to provide a heat insulation film, which is a film material with the characteristics of good light transmission, good heat insulation, hydrophobic and non-brittle aerogel and the like.

The invention uses the internet cross technology (the silicon dioxide gel is a network structure, the titanium dioxide gel is a network structure, when the silicon dioxide gel and the titanium dioxide gel are mixed, the network is interpenetrating and is not a single network structure), the silicon dioxide and the organic titanium form a three-dimensional network structure in the hydrogel stage, and the composite SiO is obtained by adopting a supercritical drying mode₂-TiO₂The magnetron sputtering aerogel structural target material is a rigid porous structural film obtained by a magnetron sputtering technology, has excellent functions of shielding light heat source and heat insulation, has excellent adhesive force with a base material, does not fall powder, does not embrittle and has excellent weather resistance.

In order to achieve the above purpose of the present invention, the following technical solutions are adopted:

the first partyThe invention also provides a SiO₂-TiO₂The preparation method of the composite aerogel target material comprises the following steps:

(a) obtaining the nano TiO₂Aerogel core material: mixing a titanium source solution and a first modifier solution, dropwise adding an ammonium phosphate aqueous solution with the pH value of 4.5-6.0, completely gelling, aging, replacing, drying and grinding to obtain nano TiO with the particle size of 200-2200 nm₂An aerogel core material;

(b) preparation of SiO₂-TiO₂Composite aerogel target material: mixing a silicon source solution and a second modifier solution, and adding the nano TiO obtained in the step (a)₂Uniformly mixing an aerogel core material, dropwise adding ammonium phosphate aqueous solution with the pH value of 4.5-6.0, completely gelling, aging, replacing, drying and grinding to obtain SiO with the particle size of 300-2300 nm₂Aerogel coated nano TiO₂SiO of aerogel core material₂-TiO₂Compounding an aerogel target material;

wherein the first modifier solution and the second modifier solution each independently comprise an alkylsiloxane compound.

Further, in step (a), the titanium source solution comprises a titanium source and a solvent; the titanium source comprises at least one of n-butyl titanate, tetraisopropyl titanate, titanyl sulfate, titanium sulfate or titanium tetrachloride; the solvent comprises at least one of ethanol, acetonitrile, isopropanol, acetone or n-butanol;

preferably, the mass concentration of the titanium source solution is 20-100%;

preferably, the first modifier solution comprises an alkyl siloxane compound and a solvent; the alkyl siloxane compound comprises at least one of methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, triethylmethoxysilane, triethylethoxysilane, diethyldiethoxysilane or ethyltriethoxysilane; the solvent comprises at least one of alcohols, esters, ketones or nitriles;

preferably, the mass concentration of the first modifier solution is 1-10%;

preferably, the mass ratio of the titanium source solution to the first modifier solution is 100: 1-5;

preferably, the temperature for mixing the titanium source solution and the first modifier solution is-15-20 ℃.

Further, in the step (a), the adding amount of the ammonium phosphate aqueous solution is 1-5%;

preferably, the aging temperature is 10-30 ℃, and the aging time is 6-12 h;

preferably, the solvent used for replacement is an alcohol solvent, the replacement temperature is 10-60 ℃, and the replacement time is 12-24 h;

preferably, the drying is supercritical drying.

Further, in the step (b), the silicon source solution comprises a silicon source and a solvent; the silicon source comprises at least one of methyl silicate, tetraethyl orthosilicate or silica sol; the solvent comprises at least one of ethanol, acetonitrile, isopropanol, acetone or n-butanol;

preferably, the mass concentration of the silicon source solution is 20-50%;

preferably, the second modifier solution comprises an alkylsiloxane compound and a solvent; the alkyl siloxane compound comprises at least one of methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, triethylmethoxysilane, triethylethoxysilane, diethyldiethoxysilane or ethyltriethoxysilane; the solvent comprises at least one of alcohols, esters, ketones or nitriles;

preferably, the mass concentration of the second modifier solution is 2-10%;

preferably, the silicon source solution and the second modifier solution are mixed in a mass ratio of 100: 1-5;

preferably, the temperature at which the silicon source solution and the second modifier solution are mixed is normal temperature.

Further, in the step (b), the nano TiO₂The addition amount of the aerogel core material is 0.1-10%.

Preferably, the adding amount of the ammonium phosphate aqueous solution is 1-5%.

Further, the aging temperature is 10-30 ℃, and the aging time is 6-12 h;

preferably, the solvent used for replacement is an alcohol solvent, the replacement temperature is 10-60 ℃, and the replacement time is 12-24 h;

preferably, the drying is supercritical drying.

In a second aspect, the present invention provides a SiO₂-TiO₂The composite aerogel target material is prepared by the preparation method;

the SiO₂-TiO₂The composite aerogel target material comprises nano TiO₂Aerogel core and outer SiO layer₂Aerogels, SiO₂Aerogel coated nano TiO₂An aerogel core material; the SiO₂-TiO₂The particle size of the composite aerogel target material is 300-2300 nm, and the nano TiO₂The particle size of the aerogel core material is 200-2200 nm.

In a third aspect, the invention provides a method for preparing a heat insulation film, which is to prepare the heat insulation film by using glass as a substrate and adopting a magnetron sputtering method, wherein the SiO is used as a target material for magnetron sputtering₂-TiO₂And (3) compounding the aerogel target material.

Further, the parameter conditions of magnetron sputtering include:

the vacuum degree is 200-800 (500) Pa, the radio frequency is 1.4-2.4 KV, the sputtering argon gas pressure is 0.3-0.8 Pa, the substrate preheating temperature is 60-80 ℃, and the sputtering time is 15-25 minutes.

In a fourth aspect, the invention provides a heat insulation film, which is prepared by the preparation method of the heat insulation film; the thickness of the heat insulation film is 0.3-10 mu m.

The SiO provided by the invention₂-TiO₂The composite aerogel target material, the heat insulation film and the preparation method thereof at least have the following beneficial effects:

the invention utilizes a sol-gel method step-by-step method to obtain a porous and hydrophobic nano titanium dioxide aerogel core material and a silicon dioxide aerogel coated titanium dioxide aerogel core material to obtain the magnetic control target material. A rigid aerogel heat-insulating transparent film is obtained by magnetron sputtering.

The heat insulation film obtained by the invention is a film material with good light transmission, good heat insulation, hydrophobic and non-brittle aerogel, and has the following performance parameters:

coefficient of thermal conductivity: 0.001 to 0.01 w/(mk);

ultraviolet blocking ratio: 90-99.5%;

infrared blocking ratio: 80-95%;

visible light blocking ratio: 10-30%;

film adhesion: 5B;

membrane hydrophobic angle: 90-150 degrees;

pencil hardness: 2H;

the cold-hot cycle aging resistance is not changed when the time is more than 3000 hours.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 shows SiO according to an embodiment of the present invention₂-TiO₂A preparation flow chart of the composite aerogel target material and the heat insulation film;

FIG. 2 is a SiO solid solution provided in example 1 of the present invention₂-TiO₂A schematic cross-sectional view of the composite aerogel target;

fig. 3 is an electronic scanning picture of the thermal insulation film provided in example 1 of the present invention at 10 μm.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Aiming at the problems of poor transparency, poor heat insulation effect and short service life of glass heat insulation films in the current market, the invention provides a magnetic control target material with a porous structure prepared by an aerogel technology, and a film is formed on glass by an aerogel composite structure material by a magnetron sputtering technology.

According to a first aspect of the present invention, there is provided a SiO₂-TiO₂The preparation method of the composite aerogel target material comprises the following steps:

(a) obtaining the nano TiO₂Aerogel core material: mixing a titanium source solution and a first modifier solution, dropwise adding an ammonium phosphate aqueous solution with the pH value of 4.5-6.0, completely gelling, aging, replacing, drying and grinding to obtain nano TiO with the particle size of 200-2200 nm₂An aerogel core material;

(b) preparation of SiO₂-TiO₂Composite aerogel target material: mixing a silicon source solution and a second modifier solution, and adding the nano TiO obtained in the step (a)₂Uniformly mixing an aerogel core material, dropwise adding ammonium phosphate aqueous solution with the pH value of 4.5-6.0, completely gelling, aging, replacing, drying and grinding to obtain SiO with the particle size of 300-2300 nm₂Aerogel coated nano TiO₂SiO of aerogel core material₂-TiO₂Compounding an aerogel target material; wherein the first modifier solution and the second modifier solution each independently comprise an alkylsiloxane compound.

Step (a)

The titanium source solution comprises a titanium source and a solvent; titanium sources include, but are not limited to, n-butyl titanate, tetraisopropyl titanate, titanyl sulfate, titanium tetrachloride, or the like; solvents include, but are not limited to, alcohols such as ethanol, methanol, isopropanol, n-butanol, nitriles such as acetonitrile, ketones such as acetone, esters such as ethyl acetate, and the like.

Preferably, the mass concentration of the titanium source solution is 20 to 100%, for example, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%.

In a preferred embodiment, the titanium source solution is a 30% by mass solution of butyl titanate in ethanol.

The first modifier solution comprises an alkyl siloxane compound and a solvent; alkyl siloxane compounds include, but are not limited to, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, triethylmethoxysilane, triethylethoxysilane, diethyldiethoxysilane, ethyltriethoxysilane, or the like; solvents include, but are not limited to, alcohols such as ethanol, methanol, isopropanol, n-butanol, nitriles such as acetonitrile, ketones such as acetone, esters such as ethyl acetate, and the like.

Preferably, the mass concentration of the first modifier solution is 1 to 10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.

In a preferred embodiment, the first modifier solution is a 3% by mass methyltrimethoxysilane-ethanol solution.

Preferably, the mass ratio of the titanium source solution to the first modifier solution is 100: 1 to 5, for example 100: 2. 100, and (2) a step of: 3. 100, and (2) a step of: 4. 100, and (2) a step of: 5;

preferably, the temperature at which the titanium source solution and the first modifier solution are mixed is in the range of-15 ℃ to 20 ℃, for example 15 ℃.

The aqueous ammonium phosphate solution having a pH of 4.5 to 6.0 (e.g., pH 4.5, 5.0, 5.5, 6.0) is added dropwise to the solution to provide ammonium hydrolysis ions as a catalyst, and when the pH is too low, gelation does not occur, and when the pH is too high, gelation does not occur, and thus a good titania aerogel structure cannot be obtained.

Preferably, the amount of aqueous ammonium phosphate solution added is 1-5%, e.g. 1%, 2%, 3%, 4%, 5%.

Preferably, the temperature of aging is 10-30 deg.C (e.g., 15 deg.C, 25 deg.C), and the time of aging is 6-12h (e.g., 6, 7, 8, 9, 10, 11, 12 h);

preferably, the solvent used for the displacement is an alcoholic solvent, the temperature of the displacement is 10-60 ℃ (e.g., 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃), and the time of the displacement is 12-24h (e.g., 12, 14, 16, 18, 20, 22, 24 h);

preferably, the drying is supercritical drying.

Drying to obtain modified titanium dioxide aerogel particles, and grinding to the particle size of 200-2200 (such as 400-2200) nm.

Step (b)

The silicon source solution comprises a silicon source and a solvent; silicon sources include, but are not limited to, methyl silicate, tetraethyl orthosilicate, or silica sol; solvents include, but are not limited to, acetonitrile, isopropanol, acetone, or n-butanol.

Preferably, the mass concentration of the silicon source solution is 20 to 50%, for example, 30%, 40%, 50%.

In a preferred embodiment, the silicon source solution is a 40% by mass ethyl silicate-ethanol solution.

The second modifier solution comprises an alkyl siloxane compound and a solvent; alkyl siloxane compounds include, but are not limited to, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, triethylmethoxysilane, triethylethoxysilane, diethyldiethoxysilane, ethyltriethoxysilane, or the like; solvents include, but are not limited to, alcohols such as ethanol, methanol, isopropanol, n-butanol, nitriles such as acetonitrile, ketones such as acetone, esters such as ethyl acetate, and the like.

Preferably, the second modifier solution has a mass concentration of 1-5%, e.g., 1%, 2%, 3%, 4%, 5%.

In a preferred embodiment, the second modifier solution is a 4% by mass methyltrimethoxysilane-ethanol solution.

Preferably, the mass ratio of the silicon source solution to the second modifier solution is 100: 1-5, e.g. 100: 2. 100, and (2) a step of: 3. 100, and (2) a step of: 4. 100, and (2) a step of: 5;

preferably, the temperature at which the silicon source solution and the second modifier solution are mixed is normal temperature.

Preferably, nano TiO₂The addition amount of the aerogel core material is 0.1-10% of the mass of the silicon source, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% and 9%;

the aqueous ammonium phosphate solution having a pH of 4.5 to 6.0 (e.g., pH 4.5, 5.0, 5.5, 6.0) is added dropwise so that the ammonium phosphate hydrolyzes to release phosphate ions and ammonium ions, the organosilicon hydrolyzes to release silicate ions, and the ammonium ions and the silicate ions undergo a double hydrolysis reaction, so that silica gel occurs, and part of the phosphate and silicate undergo two-dimensional network bonding to form a network colloid structure.

Preferably, the amount of aqueous ammonium phosphate solution added is 1-5%, e.g. 1%, 2%, 3%, 4%, 5%.

Preferably, the aging temperature is 10-30 ℃ (such as 15 ℃, 25 ℃), and the aging time is 6-12h (such as 6, 7, 8, 9, 10, 11, 12 h);

preferably, the solvent used for the replacement is an alcohol solvent, the temperature of the replacement is 10-60 ℃ (for example, 25 ℃, 30 ℃, 40 ℃ and 50 ℃), and the time of the replacement is 12-24h (for example, 12, 14, 16, 18, 20, 22 and 24 h);

preferably, the drying is supercritical drying.

Drying to obtain the modified composite aerogel target material prefabricated particles, and grinding the prefabricated particles to the particle size of 300-2300 (for example, 400-2300) nanometers to obtain the magnetron sputtering target material.

According to a second aspect of the present invention, there is provided a SiO₂-TiO₂The composite aerogel target material prepared by the preparation method comprises nano TiO₂Aerogel core and outer SiO layer₂Aerogels, SiO₂Aerogel coated nano TiO₂An aerogel core material; nano TiO 2₂The particle size of the aerogel core material is 200-2200 nm; SiO 2₂-TiO₂The particle size of the composite aerogel target material is 300-2300 nm, and the thickness of the silicon dioxide is 100-2100 nm.

SiO of the invention₂-TiO₂The preparation of the composite aerogel target material adopts a sol-gel method to obtain a titanium dioxide aerogel core material step by step, and alkyl (methyl) is grafted on titanium dioxide and silicon dioxide molecules respectively by utilizing the characteristic of siloxane hydrolysis to obtain the hydrophobic structure material.

Further by adjusting SiO₂：TiO₂According to the principle of light diffraction, the distance between the titanium dioxide core and the core is controlled within 1-3 times of the wavelength range of visible light (the range of the visible light wave is 400-760) by controlling the gel time, concentration, grinding and other conditions, so that the diameter of the particles controlled by the method is controlled within 200-2200 nanometers, visible light can penetrate through the film layer through over diffraction, the transparency is improved, and infrared rays and ultraviolet rays are blocked.

After supercritical drying of the titanium dioxide gel, the particle size is ground to a controllable particle size range by using a nano grinding device.

Porous titanium dioxide particles are dispersed in a silicon dioxide precursor, the silicon dioxide precursor can enter the titanium dioxide gaps, a network is formed during gelation, the network is penetrated like a string is penetrated through a bead, and the thickness of a film layer outside the titanium dioxide is controlled by the concentration of the silicon dioxide precursor and the gelation time.

The method changes the traditional magnetron sputtering target material into a solid structure, obtains the silicon dioxide-titanium dioxide aerogel structural target material by utilizing an aerogel preparation technology and a material composite technology, obtains nano particles by a grinding process, and obtains a rigid aerogel film by a magnetron sputtering technology in the later stage.

According to a third aspect of the present invention, a method for preparing a thermal insulation film is provided, wherein a glass is used as a substrate, and a magnetron sputtering method is adopted to prepare the thermal insulation film, wherein the SiO is used as a target material for magnetron sputtering₂-TiO₂And (3) compounding the aerogel target material.

Preferably, the parameter conditions of magnetron sputtering include:

the vacuum degree is 200-800 (500) Pa, the radio frequency is 1.4-2.4 KV, the sputtering argon gas pressure is 0.3-0.8 Pa, the substrate preheating temperature is 60-80 ℃, and the sputtering time is 15-25 minutes, for example, in one embodiment, the vacuum degree is 500Pa, the radio frequency is 1.9KV, the sputtering argon gas pressure is 0.5Pa, the substrate preheating temperature is 70 ℃, and the sputtering time is 20 minutes.

According to a fourth aspect of the present invention, there is provided a heat insulating film produced by the above production method for a heat insulating film; the thickness of the heat insulation film is 0.3-10 μm.

The heat conductivity coefficient of the heat insulation film is 0.001-0.01 w/(mk); the ultraviolet blocking rate is 90-99.5%; the infrared blocking rate is 80-95%; the visible light blocking rate is 10-30%; film adhesion 5B; the membrane drainage angle is 90-150 degrees; the pencil hardness is 2H; the cold-heat cycle aging resistance is not less than 3000 hours without change.

The invention preferably adopts the adjustment of magnetron sputtering conditions and Ar (argon) bombardment, thereby obtaining the rigid film formed by the nano aerogel structure body, and the rigid film has the characteristics of good light transmittance, good heat insulation, hydrophobic property, non-brittle aerogel and the like.

A typical method for preparing a heat insulating film, as shown in fig. 1, specifically includes:

s1: preparing a titanium dioxide precursor: pouring organic titanium and a solvent into a reaction tank, and mixing and stirring for 10-15 minutes.

S2: titanium dioxide modified sol-gel: slowly adding the siloxane modifier and the ammonium phosphate solution dropwise at the dropping speed of 0.05ml/s under the stirring state until the titanic acid is completely gelled.

S3: aging: stopping stirring, placing the gel into an open vessel, aging the gel at room temperature, and collecting the volatile organic gases.

S4: supercritical drying: and (3) drying the aged gel in a supercritical reaction kettle with carbon dioxide or ethanol as a medium.

S5: grinding the titanium dioxide aerogel: and (3) grinding the dried titanium dioxide aerogel particles by using a nano grinder, wherein the grinding fineness is controlled to be 200-2200 nm, and the median of the particle size is controlled to be 400-760 nm.

S6：SiO₂Precursor coated TiO₂Aerogel: pouring a silicon source into a reaction kettle, adding titanium dioxide nano aerogel while stirring and dispersing, and uniformly dispersing.

S7: modification of target material sol-gel: dropwise adding organosilane under the stirring state at the speed of 0.05ml/s, and dispersing and stirring for 0.5-3 hours.

S8: aging of the target material: the mixed hydrogel is transferred to a flat plate and is kept stand and aged at room temperature until the gel is completely blocked.

S9: supercritical drying: and (4) transposing the mixed gel block to a supercritical reaction kettle, and starting the supercritical equipment.

S10: grinding the target material: and putting the dried aerogel into a nano grinder, and grinding to the fineness of 300-2300 nm, wherein the median of the particle size is controlled to be 400-760 nm.

S11: magnetron sputtering pretreatment of the target material: sputtering the target material in a bin with the vacuum degree of 0.01-10 Pa for 5-10 minutes by using the radio frequency of 1-2.5 KV.

S12: pretreatment of a magnetron sputtering substrate: the method comprises the following steps of using common glass as a substrate, cleaning the substrate by using a cleaning agent, and washing 3 times by using deionized water. Drying in a clean room. The substrate was mounted in a sputtering chamber.

S13: preparing a film by magnetron sputtering: adjusting parameters of the magnetron sputtering equipment: the vacuum degree is 400-600 Pa, the radio frequency is 1.5-2.4KV, the sputtering argon pressure is 0.3-0.7 Pa, the substrate temperature is preheated to 50-90 ℃, and the sputtering is carried out for 15-40 minutes, so that the film thickness of 1-10 microns is obtained.

S14: cutting and packaging a finished product: cutting the coated glass into the size of a commodity by a glass cutting machine, and packaging.

The invention is further illustrated by the following examples. The materials in the examples are prepared according to known methods or are directly commercially available, unless otherwise specified.

The performance test method of the heat insulation film comprises the following steps:

coefficient of thermal conductivity: the detection method can adopt one of GB/T10294, GB/T10295, ASTM-C177, GB/T17794, GB/T3399, DIN EN 12939, DIN EN 13163 and SRM1450, and adopts GB/T10294: 2008 a test standard.

Ultraviolet blocking ratio: GA/T744-2007 automotive window glass sun shades.

Infrared blocking ratio: GA/T744-2007 automotive window glass sun shades.

Visible light blocking ratio: GA/T744-2007 automotive window glass sun shades.

Film adhesion: GB1720 paint film adhesion test or ASTM D3359 test for adhesion with adhesive tape.

Membrane hydrophobic angle: GB/T30447 nanometer film contact angle measurement method.

Pencil hardness: GB/T6739-2006 color paint and varnish pencil method are used for determining the hardness of the paint film.

And (3) cold-heat cycle aging resistance, namely CNCIA-HG/T0004-.

Example 1

1. 100 parts of butyl titanate solution with the mass content of 30 percent is put into a tank body, 10 parts of methyl trioxasilane with the dropping speed of 0.05ml/s is added dropwise, the mixture is mixed at the low temperature of below 15 ℃, ammonium phosphate aqueous solution with the pH value of 4.5-6.0 is used for titration under stirring, the dropping speed is 0.05ml/s, the using amount is 5 parts, the gel is completely gelled, the aging is carried out for 6-12 hours at the normal temperature, the water in the gel is replaced by excessive absolute ethyl alcohol, the gel is submerged by the ethyl alcohol solution, and the replacing time is 12-24 hours. Supercritical drying is adopted to obtain modified titanium dioxide aerogel particles, and the particles are ground until the particle size is 300 nanometers.

2. 100 parts of ethyl silicate solution with the mass content of 40 percent: 10 parts of methyltrimethoxysilane 4%, uniformly mixing at normal temperature, and slowly adding 5 parts by mass of titanium dioxide aerogel powder into the mixed solution under stirring. After uniform mixing, titrating 5 parts of ammonium phosphate aqueous solution with the pH value of 4.5-6.0 under stirring, completely gelling, aging for 6-12 hours at normal temperature, and replacing water in the gel with excess ethanol for 12-24 hours. And (3) performing supercritical drying to obtain modified composite aerogel target prefabricated particles, and grinding the prefabricated particles to the particle size of 500 nanometers to obtain the magnetron sputtering target.

3. The method comprises the following steps of using common glass as a substrate, cleaning the substrate by using a cleaning agent, and washing 3 times by using deionized water. Drying in a clean room. Sputtering the target material in a bin with the vacuum degree of 0.01-10 Pa for 5-10 minutes by using the radio frequency of 1-2.5 KV. Installing the substrate in a sputtering chamber, and adjusting the parameters of magnetron sputtering equipment: the degree of hollowness is 500Pa, the radio frequency is 1.9KV, the sputtering argon gas pressure is 0.5Pa, the substrate temperature is preheated to 70 ℃, and the sputtering is carried out for 20 minutes to obtain the film thickness of 5 microns.

4. Film thickness characteristics:

coefficient of thermal conductivity: 0.005 w/(mk); ultraviolet blocking ratio: 99.5 percent; infrared blocking ratio: 95 percent; visible light blocking ratio: 10 percent; film adhesion: 5B; membrane hydrophobic angle: not less than 120; pencil hardness: 2H; cold-hot cycle aging resistance: no change after more than 3000 hours.

FIG. 2 is SiO₂-TiO₂A schematic cross-sectional view of the composite aerogel target; figure 3 is an electronic scan picture of a thermal barrier film at 10 microns.

Example 2

1. 100 parts of butyl titanate solution with the mass content of 30 percent is put into a tank body, 10 parts of methyl trioxasilane with the dropping speed of 0.05ml/s is added dropwise, the mixture is mixed at the low temperature of below 15 ℃, ammonium phosphate aqueous solution with the pH value of 4.5-6.0 is used for titration under stirring, the dropping speed is 0.05ml/s, the using amount is 5 parts, the gel is completely gelled, the aging is carried out for 6-12 hours at the normal temperature, the water in the gel is replaced by excessive absolute ethyl alcohol, the gel is submerged by the ethyl alcohol solution, and the replacing time is 12-24 hours. Supercritical drying is adopted to obtain modified titanium dioxide aerogel particles, and the particles are ground until the particle size is 300 nanometers.

2. 100 parts of ethyl silicate solution with the mass content of 40 percent: 10 parts of methyltrimethoxysilane 4%, uniformly mixing at normal temperature, and slowly adding titanium dioxide aerogel powder with the mass fraction of 10 parts into the mixed solution under stirring. After uniform mixing, titrating 5 parts of ammonium phosphate aqueous solution with the pH value of 4.5-6.0 under stirring, completely gelling, aging for 6-12 hours at normal temperature, and replacing water in the gel with excess ethanol for 12-24 hours. And (3) performing supercritical drying to obtain modified composite aerogel target prefabricated particles, and grinding the prefabricated particles to the particle size of 500 nanometers to obtain the magnetron sputtering target.

3. The method comprises the following steps of using common glass as a substrate, cleaning the substrate by using a cleaning agent, and washing 3 times by using deionized water. Drying in a clean room. Sputtering the target material in a bin with the vacuum degree of 0.01-10 Pa for 5-10 minutes by using the radio frequency of 1-2.5 KV. Installing the substrate in a sputtering chamber, and adjusting the parameters of magnetron sputtering equipment: the degree of hollowness is 500Pa, the radio frequency is 1.9KV, the sputtering argon gas pressure is 0.5Pa, the substrate temperature is preheated to 70 ℃, and the sputtering is carried out for 20 minutes to obtain the film thickness of 5 microns.

4. Film thickness characteristics:

coefficient of thermal conductivity: 0.008 w/(mk); ultraviolet blocking ratio: 99.5 percent; infrared blocking ratio: 98 percent; visible light blocking ratio: 20 percent; film adhesion: 5B; membrane hydrophobic angle: not less than 120; pencil hardness: 2H; cold-hot cycle aging resistance: no change after more than 3000 hours.

Example 3

1. 100 parts of butyl titanate solution with the mass content of 30 percent is put into a tank body, 10 parts of methyl trioxasilane with the dropping speed of 0.05ml/s is added dropwise, the mixture is mixed at the low temperature of below 15 ℃, ammonium phosphate aqueous solution with the pH value of 4.5-6.0 is used for titration under stirring, the dropping speed is 0.05ml/s, the using amount is 5 parts, the gel is completely gelled, the aging is carried out for 6-12 hours at the normal temperature, the water in the gel is replaced by excessive absolute ethyl alcohol, the gel is submerged by the ethyl alcohol solution, and the replacing time is 12-24 hours. Supercritical drying is adopted to obtain modified titanium dioxide aerogel particles, and the particles are ground until the particle size is 300 nanometers.

2. 100 parts of ethyl silicate solution with the mass content of 40 percent: 10 parts of methyltrimethoxysilane 4%, uniformly mixing at normal temperature, and slowly adding 5 parts by mass of titanium dioxide aerogel powder into the mixed solution under stirring. After uniform mixing, titrating 5 parts of ammonium phosphate aqueous solution with the pH value of 4.5-6.0 under stirring, completely gelling, aging for 6-12 hours at normal temperature, and replacing water in the gel with excess ethanol for 12-24 hours. And (3) performing supercritical drying to obtain modified composite aerogel target prefabricated particles, and grinding the prefabricated particles to the particle size of 500 nanometers to obtain the magnetron sputtering target.

3. The method comprises the following steps of using common glass as a substrate, cleaning the substrate by using a cleaning agent, and washing 3 times by using deionized water. Drying in a clean room. Sputtering the target material in a bin with the vacuum degree of 0.01-10 Pa for 5-10 minutes by using the radio frequency of 1-2.5 KV. Installing the substrate in a sputtering chamber, and adjusting the parameters of magnetron sputtering equipment: the vacuum degree is 500Pa, the radio frequency is 1.9KV, the sputtering argon gas pressure is 0.5Pa, the substrate temperature is preheated to 70 ℃, and the sputtering is carried out for 40 minutes, thus obtaining the film thickness of 10 microns.

4. Film thickness characteristics:

coefficient of thermal conductivity: 0.006 w/(mk); ultraviolet blocking ratio: 99.9 percent; infrared blocking ratio: 99.1 percent; visible light blocking ratio: 20 percent; film adhesion: 5B; membrane hydrophobic angle: not less than 120; pencil hardness: 2H; cold-hot cycle aging resistance: no change after more than 3000 hours.

Example 4

This example differs from example 1 in that SiO was changed₂：TiO₂The other steps are the same, i.e. 10: 1.

Film thickness characteristics: coefficient of thermal conductivity: 0.004 w/(mk); ultraviolet blocking ratio: 98.0 percent; infrared blocking ratio: 95 percent; visible light blocking ratio: 7 percent; film adhesion: 5B; membrane hydrophobic angle: 120 degrees; pencil hardness: h; cold-hot cycle aging resistance: no change after more than 3000 hours.

Example 5

This example differs from example 1 in that the magnetron sputtering target was obtained by grinding to a particle size of 2000 nm in step 1 and grinding the preform to a particle size of 2300nm in step 2.

Film thickness characteristics: coefficient of thermal conductivity: 0.01 w/(mk); ultraviolet blocking ratio: 99.9 percent; infrared blocking ratio: 99.0 percent; visible light blocking ratio: 40 percent; film adhesion: 5B; membrane hydrophobic angle: 120 degrees; pencil hardness: 3H; cold-hot cycle aging resistance: no change after more than 3000 hours.

Example 6

The difference between this example and example 1 is that step 3 changes the parameters of the magnetron sputtering equipment: the vacuum degree is 500Pa, the radio frequency is 1.5KV, the sputtering argon gas pressure is 0.5Pa, the substrate temperature is preheated to 70 ℃, and the sputtering is carried out for 40 minutes, thus obtaining the film thickness of 10 microns.

Coefficient of thermal conductivity: 0.006 w/(mk); ultraviolet blocking ratio: 99.9 percent; infrared blocking ratio: 99.1 percent; visible light blocking ratio: 20 percent; film adhesion: 3B; membrane hydrophobic angle: not less than 120; pencil hardness: 2H; cold-hot cycle aging resistance: no change after more than 3000 hours.

Comparative example 1

Adding 10 parts of conventional titanium dioxide powder into 100 parts of silicon dioxide precursor, uniformly mixing, dropwise adding 5 parts of methyltrimethoxysilane ammonium for catalysis to obtain silicon dioxide-coated titanium dioxide hydrogel, coating the hydrogel on the surface of clean glass, replacing water with ethanol, and naturally drying to obtain the coating film of 10 um.

Testing the performance of the coating film:

coefficient of thermal conductivity: 0.1 w/(mk); ultraviolet blocking ratio: 99.9 percent; infrared blocking ratio: 50 percent; visible light blocking ratio: 80 percent; film adhesion: 1B; membrane hydrophobic angle: not less than 120; pencil hardness: 6B; cold-hot cycle aging resistance: powdering for 1 hour.

Comparative example 2

Adding 10 parts of conventional titanium dioxide powder into 100 parts of silicon dioxide precursor, uniformly mixing, dropwise adding 5 parts of methyltrimethoxysilane ammonium for catalysis to obtain silicon dioxide-coated titanium dioxide hydrogel, coating the hydrogel on the surface of clean glass, replacing water with ethanol, and performing supercritical drying to obtain a coating film of 10 um.

Testing the performance of the coating film:

coefficient of thermal conductivity: 0.03 w/(mk); ultraviolet blocking ratio: 99.9 percent; infrared blocking ratio: 50 percent; visible light blocking ratio: 70 percent; film adhesion: 1B; membrane hydrophobic angle: not less than 120; pencil hardness: 6B; cold-hot cycle aging resistance: powdering for 1 hour.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.