A novel titanium-based solar control coated glass and a method for manufacturing the same

Abstract

The application provides a novel titanium-based sunlight control coated glass and a preparation method thereof. The preparation method comprises the following steps: preparing a first titanium dioxide film layer, a second silicon dioxide film layer and a third mutually doped titanium dioxide / titanium nitride film layer on the upper surface of the glass in a tin bath by using a chemical vapor deposition method. The titanium dioxide film layer is used as a metal bridge for increasing the bonding capacity of the silicon dioxide film layer and the glass, and forms a double-layer antireflection layer together with the silicon dioxide film layer, so as to reduce the overall reflectivity and reflection interference color of the film layer. The mutually doped titanium dioxide / titanium nitride film layer is used for selectively absorbing visible light and solar energy, so as to reduce the transmittance of the visible light and the solar energy.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of solar control coated glass, and particularly relates to a novel titanium-based solar control coated glass and a preparation method thereof. BACKGROUND

[0002] The solar control coated glass has excellent functions of reducing visible light and solar energy transmittance, and is widely used in the building industry. The main production methods of the solar control coated glass include a magnetron sputtering method and an online chemical vapor deposition method. The solar control coated glass produced by the magnetron sputtering method needs a multi-layer film system structure design, and the structure and control are difficult, and the film layer mainly contains a metal film layer, and generally needs to be synthesized into hollow glass. The solar control coated glass produced by the online chemical vapor deposition method is mainly silicon-based solar control coated glass, the color of the film layer is the body color of the silicon material, and is gray-brown, and can be coated on different color glass substrates. After investigation, no related technology of preparing a titanium nitride film in a tin bath by using a chemical vapor deposition method is found. SUMMARY

[0003] The present application aims to solve the technical problems of the prior art and provides a novel titanium-based solar control coated glass and a preparation method thereof.

[0004] To solve the above technical problems, the content of the present application includes the following:

[0005] A preparation method of a novel titanium-based solar control coated glass includes preparing a first layer of titanium dioxide film, a second layer of silicon dioxide film and a third layer of mutually doped titanium dioxide / titanium nitride film on the upper surface of the glass in the tin bath by using a chemical vapor deposition method; the titanium dioxide film is used as a metal bridge for increasing the bonding ability of the silicon dioxide film and the glass, and forms a double-layer antireflection layer together with the silicon dioxide film to reduce the overall reflectivity and reflection interference color of the film layer; the mutually doped titanium dioxide / titanium nitride film is used for selectively absorbing visible light and solar energy to reduce the transmittance of visible light and solar energy.

[0006] Further, the method specifically includes the following steps:

[0007] S1: preparing the first layer of titanium dioxide film: evaporating a titanium source precursor in an evaporator to obtain precursor vapor, and the evaporation temperature is 110-150℃; introducing the precursor vapor into a first reactor in the tin bath by using nitrogen as a carrying gas, and the dosage of the titanium source precursor is 1-5kg / h, the dosage of nitrogen is 18-42m 3 / h, and the material vapor is reacted on the upper surface of the glass at a temperature of 660-670℃ to prepare the first layer of titanium dioxide film with a thickness of 15-40nm, and the refractive index of the film layer is 1.8-2.1;

[0008] S2: preparing a second layer of silicon dioxide film: introducing a mixed gas material composed of silane, ethylene, oxygen and nitrogen into the second reactor, the ratio of silane-oxygen-ethylene being 1:2-5:4-8, the amount of silane being 0.1-1 m 3 / h, the amount of oxygen being 0.4-4 m 3 / h, the amount of ethylene being 0.6-6 m 3 / h, the amount of nitrogen being 18-42 m 3 / h; when the glass temperature is 650-660℃, the mixed gas material reacts on the first layer of titanium dioxide film to prepare a second layer of silicon dioxide film with a thickness of 15-40 nm and a refractive index of 1.43-1.45;

[0009] S3: preparing a third layer of mutually doped titanium dioxide / titanium nitride film: evaporating the titanium source precursor in an evaporator to obtain titanium source precursor vapor, the evaporation temperature being 110-150℃; mixing ammonia and the titanium source precursor vapor to obtain process gas, and introducing the process gas into the third reactor in the tin tank using nitrogen as carrying gas, the amount of titanium source precursor being 2-10 kg / h, the amount of ammonia being 1-10 m 3 / h, the amount of nitrogen being 18-42 m 3 / h; when the glass temperature is 640-650℃, the material gas reacts on the second layer of silicon dioxide film to prepare a third layer of mutually doped titanium oxide / titanium nitride film with a thickness of 20-100 nm.

[0010] Further, in the step S1, the evaporation temperature of the titanium source precursor is 120-140℃; the amount of titanium source precursor is 1.5-4 kg / h, and the amount of nitrogen is 24-36 m 3 / h; the thickness of the titanium dioxide film is 20-30 nm, and the refractive index of the film is 1.9-1.95.

[0011] Further, in the step S2, the preferred ratio of silane-oxygen-ethylene is 1:3.5-4.5:5.5-6.5; the amount of silane is 0.15-0.72 m 3 / h, the amount of oxygen is 0.6-3 m 3 / h, the amount of ethylene is 1-4.5 m 3 / h, the amount of nitrogen is 24-36 m 3 / h; the thickness of the silicon dioxide film is 20-30 nm.

[0012] Further, in the step S3, the evaporation temperature is 120-140℃; the amount of titanium source precursor is 2.5-8 kg / h, the amount of ammonia is 1.5-8 m 3 / h, the amount of nitrogen is 24-36 m 3The thickness of the mutually doped titanium oxide / titanium nitride film layer is 30-80nm.

[0013] Further, in the steps S1 and S3, the titanium source precursor is ethyl titanate, propyl titanate, butyl titanate and isomers thereof.

[0014] A novel titanium-based sunlight control coated glass is prepared by the above-mentioned novel titanium-based sunlight control coated glass preparation method.

[0015] The beneficial effects of the present application are:

[0016] The present application utilizes chemical vapor deposition to prepare a first layer of titanium dioxide film on the upper surface of the glass in the tin bath as a metal bridge to increase the adhesion of the film layer to the glass; utilizes chemical vapor deposition to prepare a second layer of silicon dioxide film on the first layer of tin dioxide film, and the silicon dioxide film and the titanium dioxide film form a double-layer antireflection layer to reduce the overall reflectivity and reflection interference color of the film layer; utilizes chemical vapor deposition to prepare a third layer of mutually doped titanium oxide / titanium nitride film on the second layer of silicon dioxide film, which has selective absorption effect on visible light and solar energy and can effectively reduce the transmittance of visible light and solar energy. DETAILED DESCRIPTION

[0017] To facilitate the understanding of the present application, the present application will be further described in detail below in conjunction with specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations on the present application.

[0018] The present application provides a novel titanium-based sunlight control coated glass preparation method, which comprises utilizing chemical vapor deposition to sequentially prepare a first layer of titanium dioxide film, a second layer of silicon dioxide film and a third layer of mutually doped titanium oxide / titanium nitride film on the upper surface of the glass in the tin bath; the titanium dioxide film is used as a metal bridge to increase the adhesion of the silicon dioxide film to the glass, and together with the silicon dioxide film forms a double-layer antireflection layer to reduce the overall reflectivity and reflection interference color of the film layer; the mutually doped titanium oxide / titanium nitride film is used for selectively absorbing visible light and solar energy to reduce the transmittance of visible light and solar energy.

[0019] The novel titanium-based sunlight control coated glass preparation method of the present application specifically comprises the following steps:

[0020] S1: preparing a first layer of titanium dioxide film: evaporating a titanium source precursor in an evaporator to obtain a precursor vapor, the evaporation temperature is 110-150℃; utilizing nitrogen as a carrying gas to introduce the precursor vapor into a first reactor in the tin bath, the amount of the titanium source precursor is 1-5kg / h, the amount of nitrogen is 18-42m 3 / h, the material vapor reacts on the upper surface of the glass at a temperature of 660-670℃ to prepare a first layer of titanium dioxide film with a thickness of 15-40nm and a refractive index of 1.8-2.1;

[0021] S2: preparing a second layer of silicon dioxide film: introducing a mixed gas material composed of silane, ethylene, oxygen and nitrogen in different proportions into the second reactor, the ratio of silane-oxygen-ethylene being 1:2-5:4-8, the amount of silane being 0.1-1m 3 / h, the amount of oxygen being 0.4-4m 3 / h, the amount of ethylene being 0.6-6m 3 / h, the amount of nitrogen being 18-42m 3 / h; at a glass temperature of 650-660℃, the mixed gas material reacts on the first layer of titanium dioxide film to prepare a second layer of silicon dioxide film with a thickness of 15-40nm and a refractive index of 1.43-1.45;

[0022] S3: preparing a third layer of mutually doped titanium dioxide / titanium nitride film: evaporating the titanium source precursor in an evaporator to obtain titanium source precursor vapor, the evaporation temperature being 110-150℃; mixing ammonia gas with the titanium source precursor vapor to obtain process gas, and introducing the process gas into the third reactor in the tin tank using nitrogen gas as carrying gas, the amount of titanium source precursor being 2-10kg / h, the amount of ammonia gas being 1-10m 3 / h, the amount of nitrogen being 18-42m 3 / h; at a glass temperature of 640-650℃, the material gas reacts on the second layer of silicon dioxide film to prepare a third layer of mutually doped titanium oxide / titanium nitride film with a thickness of 20-100nm.

[0023] The new titanium-based sunlight control coated glass is prepared by the method.

[0024] The overall transmittance of the coated glass is 20-50%, and different colors from light blue to golden yellow are presented according to the thickness of the mutually doped titanium dioxide / titanium nitride film.

[0025] In the above step S1, the evaporation temperature of the titanium source precursor is preferably 120-140℃; the amount of titanium source precursor is preferably 1.5-4kg / h, and the amount of nitrogen is preferably 24-36m 3 / h; the thickness of the titanium dioxide film is preferably 20-30nm, and the refractive index of the film is preferably 1.9-1.95.

[0026] In the above step S2, the preferred ratio of silane-oxygen-ethylene is 1:3.5-4.5:5.5-6.5; the amount of silane is preferably 0.15-0.72m 3 / h, the amount of oxygen is preferably 0.6-3 m 3 / h, the amount of ethylene is preferably 1-4.5 m 3 / h, the amount of nitrogen is preferably 24-36 m 3 / h; the thickness of the silicon dioxide film layer is preferably 20-30 nm.

[0027] In the above step S3, the evaporation temperature is preferably 120-140℃; the amount of titanium source precursor is preferably 2.5-8 kg / h, and the amount of ammonia is preferably 1.5-8 m 3 / h, the amount of nitrogen is preferably 24-36 m 3 / h; the thickness of the mutually doped titanium oxide / titanium nitride film layer is preferably 30-80 nm.

[0028] In the above steps S1 and S3, the titanium source precursor is ethyl titanate, propyl titanate, butyl titanate and its isomers. Example

[0029] Common float glass, substrate thickness 6 mm, plate speed 470 m / h.

[0030] (1) Preparation of the first layer of titanium dioxide film

[0031] The titanium source precursor is butyl titanate, the amount is 1.5 kg / h, and the amount of nitrogen is 24 m 3 / h, the evaporation temperature of the evaporator is 125℃, the material vapor is introduced into the first reactor, the glass substrate temperature is 660℃, the tin dioxide film is generated by reaction on the hot glass plate, the film thickness is 25 nm, and the refractive index is 2.

[0032] (2) Preparation of the second layer of silicon dioxide film

[0033] The amount of silane is 0.24 m 3 / h, the amount of oxygen is 0.96 m 3 / h, the amount of ethylene is 1.44 m 3 / h, the amount of nitrogen is 24 m 3 / h; the material mixed gas is introduced into the second reactor, the glass substrate temperature is 650℃, the silicon dioxide film layer is generated by reaction on the titanium dioxide film layer, the film thickness is 25 nm, and the refractive index is 1.45.

[0034] (3) Preparation of the third layer of mutually doped titanium dioxide / titanium nitride film

[0035] The titanium source precursor is butyl titanate, the amount is 5 kg / h, and the amount of nitrogen is 24 m 3 / h, the evaporation temperature of the evaporator is 125℃, and the amount of ammonia is 4 m 3 / h, process gas is introduced into the third reactor, the glass substrate temperature is 640 DEG C, and a mutual doped titanium dioxide / titanium nitride film layer is prepared on the silicon dioxide film layer, and the film layer thickness is 50 nm.

[0036] The three film layers prepared on the glass surface in sequence by the chemical vapor deposition method form a solar control coated glass, and the visible light transmittance is 45%.

[0037] Although the embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a novel titanium-based solar control coated glass, characterized in that, The method includes sequentially preparing a first titanium dioxide film, a second silicon dioxide film, and a third mutually doped titanium dioxide / titanium nitride film on the upper surface of glass using chemical vapor deposition inside a tin bath. The titanium dioxide film serves as a metal bridge to increase the adhesion between the silicon dioxide film and the glass, and together with the silicon dioxide film, forms a double-layer antireflection layer to reduce the overall reflectivity and reflected interference colors of the film. The mutually doped titanium dioxide / titanium nitride film selectively absorbs visible light and solar energy to reduce the transmittance of visible light and solar energy. The preparation method specifically includes the following steps: S1: Preparation of the first titanium dioxide film layer: The titanium source precursor is evaporated in an evaporator to obtain precursor vapor at an evaporation temperature of 110-150℃; the precursor vapor is introduced into the first reactor in the tin bath using nitrogen as a carrier gas, with a titanium source precursor dosage of 1-5 kg / h and a nitrogen dosage of 18-42 mg / h. 3 / h, material vapor reacts on the upper surface of glass at a temperature of 660-670℃ to prepare a first titanium dioxide film with a thickness of 15-40nm and a refractive index of 1.8-2.

1. S2: Preparation of the second silica film layer: A mixed gaseous material composed of silane, ethylene, oxygen, and nitrogen in different proportions is introduced into the second reactor. The silane-oxygen-ethylene ratio is 1:2-5:4-8, and the amount of silane used is 0.1-1 mg / L. 3 / h, oxygen consumption is 0.4-4m³ / h. 3 / h, the ethylene dosage is 0.6-6m³. 3 / h, nitrogen consumption is 18-42m³. 3 / h; At a glass temperature of 650-660℃, the mixed gas material reacts on the first titanium dioxide film to prepare a second silicon dioxide film with a thickness of 15-40nm and a refractive index of 1.43-1.

45. S3: Preparation of the third layer of interdoped titanium dioxide / titanium nitride film: The titanium source precursor is evaporated in an evaporator to obtain titanium source precursor vapor at an evaporation temperature of 110-150℃; ammonia gas is mixed with the titanium source precursor vapor to obtain process gas, and nitrogen gas is used as the carrier gas to introduce the process gas into the third reactor in the tin bath. The titanium source precursor dosage is 2-10 kg / h, and the ammonia gas dosage is 1-10 mg / h. 3 / h, nitrogen consumption is 18-42m³. 3 / h; At a glass temperature of 640-650℃, the material gas reacts on the second silicon dioxide film to prepare a third layer of mutually doped titanium oxide / titanium nitride film with a thickness of 20-100nm.

2. The preparation method according to claim 1, characterized in that, In step S1, the evaporation temperature of the titanium source precursor is 120-140℃; the amount of titanium source precursor used is 1.5-4 kg / h; and the amount of nitrogen used is 24-36 m³ / h. 3 / h; the thickness of the titanium dioxide film is 20-30nm, and the refractive index of the film is 1.9-1.

95.

3. The preparation method according to claim 1, characterized in that, In step S2, the ratio of silane-oxygen-ethylene is 1:3.5-4.5:5.5-6.5; the amount of silane used is 0.15-0.72 mg / L. 3 / h, oxygen consumption is 0.6-3m³ / h. 3 / h, the ethylene dosage is 1-4.5m³. 3 / h, nitrogen consumption is 24-36m³. 3 / h; the thickness of the silicon dioxide film is 20-30nm.

4. The preparation method according to claim 1, characterized in that, In step S3, the evaporation temperature is 120-140℃; the amount of titanium source precursor used is 2.5-8 kg / h; and the amount of ammonia used is 1.5-8 m³ / h. 3 / h, nitrogen consumption is 24-36m³. 3 / h; the thickness of the mutually doped titanium oxide / titanium nitride film is 30-80nm.

5. The preparation method according to claim 1, characterized in that, In steps S1 and S3, the titanium source precursor is ethyl titanate, propyl titanate, butyl titanate, or their isomers.

6. A novel titanium-based solar control coated glass, characterized in that, It is prepared by the preparation method according to any one of claims 1-5.