CN112876093B - Method for preparing silicon dioxide-titanium dioxide composite aerogel target material and rigid film by magnetron sputtering method - Google Patents
Method for preparing silicon dioxide-titanium dioxide composite aerogel target material and rigid film by magnetron sputtering method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
- C03C17/2456—Coating containing TiO2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
Abstract
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 ammonium phosphate aqueous solution, completely gelling, aging, replacing, drying and grinding to obtain the composite aerogel target material with the particle size of 300-2300 nm. The method changes 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.
Description
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 the window glass of automobiles is adhered with the heat insulation film, the heat insulation film reduces the damage of ultraviolet rays to human bodies and ornaments in the 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 cost of the automobiles.
Chinese patents (CN 201720052999.3, CN201920913523.3, CN201920097348.5, CN202010646618.0 and the like) all disclose aerogel heat-insulating films, mainly comprising SiO 2 The aerogel layer is compounded with other layer structures, and the heat insulation film has brittleness, is only used as an interlayer, is easy to fall powder, has thick thickness, and has poor light transmission, 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 SiO 2 Coated TiO 2 The 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 objects of the present invention is to provide a SiO 2 -TiO 2 Composite gasThe preparation method of the gel 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 SiO 2 -TiO 2 And (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 mode 2 -TiO 2 The 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:
in a first aspect, the present invention provides a SiO 2 -TiO 2 The preparation method of the composite aerogel target material comprises the following steps:
(a) Obtaining the nano TiO 2 Aerogel 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 the nano TiO with the particle size of 200-2200 nm 2 An aerogel core material;
(b) Preparation of SiO 2 -TiO 2 Composite aerogel target material: mixing a silicon source solution and a second modifier solution, and adding the nano TiO obtained in the step (a) 2 Uniformly mixing the aerogel core material, dripping ammonium phosphate aqueous solution with the pH value of 4.5-6.0,after complete gelation, aging, replacement treatment, drying and grinding are carried out to obtain SiO with the grain diameter of 300-2300 nm 2 Aerogel coated nano TiO 2 SiO of aerogel core material 2 -TiO 2 Compounding 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 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 first modifier solution is 1-10%;
preferably, the mass ratio of the titanium source solution to the first modifier solution is 100:1 to 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 6-12h;
preferably, the solvent used for replacement is an alcohol solvent, the replacement temperature is 10-60 ℃, and the replacement time is 12-24h;
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 TiO 2 The addition amount of the aerogel core material is 0.1-10%.
Preferably, the addition amount of the ammonium phosphate aqueous solution is 1 to 5%.
Further, the aging temperature is 10-30 ℃, and the aging time is 6-12h;
preferably, the solvent used for replacement is an alcohol solvent, the replacement temperature is 10-60 ℃, and the replacement time is 12-24h;
preferably, the drying is supercritical drying.
In a second aspect, the present invention provides a SiO 2 -TiO 2 Composite aerogel target materialPrepared by the preparation method;
the SiO 2 -TiO 2 The composite aerogel target material comprises nano TiO 2 Aerogel core and outer SiO layer 2 Aerogels, siO 2 Aerogel coated nano TiO 2 An aerogel core material; the SiO 2 -TiO 2 The grain diameter of the composite aerogel target material is 300-2300 nm, and the nano TiO 2 The grain diameter 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 sputtering 2 -TiO 2 And (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 invention 2 -TiO 2 The 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: 0.001-0.01 w/(mk);
ultraviolet blocking ratio: 90 to 99.5 percent;
infrared blocking ratio: 80 to 95 percent;
visible light blocking ratio: 10 to 30 percent;
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 embodiments or the prior art descriptions 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 invention 2 -TiO 2 A 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 invention 2 -TiO 2 A 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 SiO 2 -TiO 2 Preparation method of composite aerogel target materialThe method comprises the following steps:
(a) Obtaining the nano TiO 2 Aerogel 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 the nano TiO with the particle size of 200-2200 nm 2 An aerogel core material;
(b) Preparation of SiO 2 -TiO 2 Compounding an aerogel target material: mixing the silicon source solution and the second modifier solution, and adding the nano TiO in the step (a) 2 Uniformly mixing an aerogel core material, then dropwise adding ammonium phosphate aqueous solution with the pH value of 4.5-6.0, completely gelling, then aging, replacing, drying and grinding to obtain SiO with the particle size of 300-2300 nm 2 Aerogel coated nano TiO 2 SiO of aerogel core material 2 -TiO 2 Compounding 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 titanium source solution has a mass concentration of 20 to 100%, such as 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 first modifier solution has a mass concentration of 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, such as 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 purpose of adding an aqueous solution of ammonium phosphate at a pH of 4.5 to 6.0 (e.g., pH =4.5, 5.0, 5.5, 6.0) is to act as a catalyst to provide ammonium hydrolysis ions, and a pH that is too low will not result in gelation, and a pH that is too high will not result in a very good titania aerogel structure.
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, grinding to a particle size of 200-2200 (e.g., 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 silicon source solution has a mass concentration of 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%, such as 1%, 2%, 3%, 4%, 5%.
In a preferred embodiment, the second modifier solution is a 4% by mass methyltrimethoxysilane-ethanol solution.
Preferably, the silicon source solution and the second modifier solution are mixed in a mass ratio of 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 TiO 2 The 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%, 9%;
the purpose of adding an aqueous solution of ammonium phosphate at a pH of 4.5 to 6.0 (e.g., pH =4.5, 5.0, 5.5, 6.0) is to hydrolyze the ammonium phosphate to release phosphate ions and ammonium ions, hydrolyze the organosilicon to release silicate ions, and cause a double hydrolysis reaction between the ammonium ions and silicate ions, thereby causing silica gel, and causing two-dimensional network bonding of part of phosphate and silicate 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 temperature of aging is 10 to 30 ℃ (e.g., 15 ℃, 25 ℃) and the time of aging is 6 to 12 hours (e.g., 6, 7, 8, 9, 10, 11, 12 hours);
preferably, the solvent used for the replacement is an alcohol solvent, the temperature of the replacement is 10 to 60 ℃ (e.g., 25 ℃, 30 ℃, 40 ℃, 50 ℃), and the time of the replacement is 12 to 24h (e.g., 12, 14, 16, 18, 20, 22, 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 SiO 2 -TiO 2 The composite aerogel target material prepared by the preparation method comprises nano TiO 2 Aerogel core and outer SiO layer 2 Aerogels, siO 2 Aerogel coated nano TiO 2 An aerogel core material; nano TiO 2 2 The grain diameter of the aerogel core material is 200-2200 nm; siO 2 2 -TiO 2 The 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 invention 2 -TiO 2 The 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 SiO 2 ：TiO 2 The distance between the titanium dioxide core and the core is controlled within 1 to 3 times of the visible light wavelength range (the visible light wavelength range is 400 to 760) by controlling the gel time, concentration, grinding and other conditions according to the principle of light diffraction, so the particle diameter controlled by the method is controlled within 200 to 2200 nanometers, and the visible light part can be controlledAnd passes through the film layer from over diffraction, thereby improving transparency and blocking infrared rays and ultraviolet rays.
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 silica precursor, the silica precursor enters the titanium dioxide voids, a network penetrating is formed during gelation, similar to threading a bead with a wire, and the thickness of the film layer outside the titanium dioxide is controlled by the concentration of the silica 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 sputtering 2 -TiO 2 And (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 preheating temperature of the substrate 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 preheating temperature of the substrate 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 prepared by the above method for preparing 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 ray blocking rate is 80-95%; the visible light barrier 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：SiO 2 Precursor coated TiO 2 Aerogel: 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: under the stirring state, dropping organosilane 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: pretreatment of magnetron sputtering of target materials: 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 gas 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, thus obtaining the film thickness of 1-10 microns.
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: the paint film hardness is measured by GB/T6739-2006 color paint and varnish pencil method.
And (3) cold-hot cycle aging resistance, namely testing method standards of cold-hot cycle of the color paint and varnish paint film of CNCIA-HG/T0004-2012.
Example 1
1. 100 parts of butyl titanate solution with the mass content of 30 percent is put into a tank body, 3 parts of methyl trioxasilane is added dropwise, the dropping speed is 0.05ml/s, 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 dosage is 5 parts, the gel is completely gelled, the gel is aged for 6-12 hours at 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 replacement 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, mixing uniformly at normal temperature, and slowly adding 5 parts by mass of titanium dioxide aerogel powder into the mixed solution under stirring. After mixing evenly, 5 parts of ammonium phosphate aqueous solution with the pH value of 4.5-6.0 is used for titration under stirring, complete gelation is carried out, aging is carried out for 6-12 hours at normal temperature, excessive ethanol replaces water in the gel, and the replacement time is 12-24 hours. And (3) obtaining prefabricated particles of the modified composite aerogel target material by adopting supercritical drying, and grinding the prefabricated products to the particle size of 500 nanometers to obtain the magnetron sputtering target material.
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 SiO 2 -TiO 2 A 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, 3 parts of methyl trioxasilane is added dropwise, the dropping speed is 0.05ml/s, 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 dosage is 5 parts, the gel is completely gelled, the gel is aged for 6-12 hours at 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 replacement 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, mixing uniformly at normal temperature, and slowly adding 10 parts by mass of titanium dioxide aerogel powder into the mixed solution under stirring. After being mixed evenly, 5 parts of ammonium phosphate aqueous solution with the pH value of 4.5-6.0 is titrated under stirring to completely gel, the gel is aged for 6-12 hours at normal temperature, excessive ethanol replaces water in the gel, and the replacement time is 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, 3 parts of methyl trioxasilane is added dropwise, the dropping speed is 0.05ml/s, 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 dosage is 5 parts, the gel is completely gelled, the gel is aged for 6-12 hours at 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 replacement 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, mixing uniformly at normal temperature, and slowly adding 5 parts by mass of titanium dioxide aerogel powder into the mixed solution under stirring. After being mixed evenly, 5 parts of ammonium phosphate aqueous solution with the pH value of 4.5-6.0 is titrated under stirring to completely gel, the gel is aged for 6-12 hours at normal temperature, excessive ethanol replaces water in the gel, and the replacement time is 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 substrate is cleaned by using a cleaning agent and washed by deionized water for 3 times by using common glass as the substrate. 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 changed 2 ：TiO 2 The ratio of (1), i.e. 10.
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 rate: 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 10um.
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 10um.
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 these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. SiO (silicon dioxide) 2 -TiO 2 The preparation method of the composite aerogel target material is characterized by comprising the following steps:
(a) Obtaining the nano TiO 2 Aerogel 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 nano TiO with the particle size of 200-2200 nm 2 An aerogel core material;
the drying in the step (a) is supercritical drying;
(b) Preparation of SiO 2 -TiO 2 Composite aerogel target material: mixing a silicon source solution and a second modifier solution, and adding the nano TiO obtained in the step (a) 2 Uniformly mixing an aerogel core material, 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 SiO with the particle size of 300 to 2300nm 2 Aerogel coated nano TiO 2 SiO of aerogel core material 2 -TiO 2 Compounding an aerogel target material;
the drying in the step (b) is supercritical drying;
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;
the mass concentration of the titanium source solution is 20 to 100 percent;
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;
the mass concentration of the first modifier solution is 1-10%;
the mixing mass ratio of the titanium source solution to the first modifier solution is 10:0.1 to 5;
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;
the aging temperature is 10-30 ℃, and the aging time is 6-12h;
the solvent used for replacement is an alcohol solvent, the temperature of replacement is 10 to 60 ℃, and the time of replacement is 12 to 24 hours.
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;
the mass concentration of the silicon source solution is 20 to 50 percent;
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;
the mass concentration of the second modifier solution is 2-10%;
the mixing mass ratio of the silicon source solution to the second modifier solution is 10:0.1 to 5;
and the temperature for mixing the silicon source solution and the second modifier solution is normal temperature.
5. The method according to any one of claims 1 to 4, wherein in the step (b), the nano TiO is used 2 The adding amount of the aerogel core material is 0.1 to 10 percent of the mass of the silicon source;
the addition amount of the ammonium phosphate aqueous solution is 1~5%.
6. The process according to any one of claims 1 to 4, wherein in step (b), the temperature of aging is 10 to 30 ℃ and the time of aging is 6 to 12 hours;
the solvent used for replacement is an alcohol solvent, the temperature of replacement is 10 to 60 ℃, and the time of replacement is 12 to 24 hours.
7. SiO (silicon dioxide) 2 -TiO 2 Composite aerogel targetA material produced by the production method according to any one of claims 1 to 6;
the SiO 2 -TiO 2 The composite aerogel target material comprises nano TiO 2 Aerogel core and outer layer of SiO 2 Aerogels, siO 2 Aerogel coated nano TiO 2 An aerogel core material; the SiO 2 -TiO 2 The particle size of the composite aerogel target material is 300 to 2300nm, and the nano TiO 2 The grain diameter of the aerogel core material is 200 to 2200nm.
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 sputtering 2 -TiO 2 And (3) compounding the aerogel target material.
9. The method of claim 8, wherein the magnetron sputtering parameters include:
the vacuum degree is 200 to 800Pa, the radio frequency is 1.4 to 2.4KV, the sputtering argon pressure is 0.3 to 0.8Pa, the substrate preheating temperature is 60 to 80 ℃, and the sputtering time is 15 to 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 to 10 mu m;
the thermal conductivity coefficient of the thermal insulation film is 0.001 to 0.01 w/(mk); the ultraviolet blocking rate is 90 to 99.5 percent; the infrared blocking rate is 80 to 95 percent; the visible light blocking rate is 10 to 30 percent; film adhesion 5B; the membrane hydrophobic angle is 90 to 150 degrees; the pencil hardness is 2H; the cold-heat cycle aging resistance is not less than 3000 hours without change.
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