CN104310798B - Preparation method of thermotropic reflective infrared coated glass - Google Patents

Abstract

The invention discloses a preparation method of thermotropic reflective infrared coated glass. The method comprises the following steps: plating a silicon dioxide isolating layer on a high boron silicon glass substrate by adopting a magnetron sputtering method; plating a metal vanadium film layer on the isolating layer by adopting the magnetron sputtering method; using vanadium metal or tungsten doped vanadium metal as a target; plating a silicon dioxide on an infrared reflective layer by adopting the magnetron sputtering method as an antireflection layer to obtain the coated glass; and carrying out thermal treatment in an atmospheric environment and at a spatial temperature of 600-750 DEG C, wherein the metal vanadium film layer is oxidized to form the infrared reflective layer and meanwhile, the coated glass is tempered. The method is simple in preparation process, mature and free from pollution in the preparation process. The thermal treatment of the film layer of the obtained coated glass and the coated glass tempering are accomplished at one time, so that infrared rays can be reflected, visible light reflection is reduced, and the thermal shock resistance of the glass is improved.

Description

A kind of preparation method of thermoreflective infrared coating glass

technical field

The invention belongs to the technical field of composite material preparation, and in particular relates to a preparation method of heat-induced reflective infrared coated glass.

Contents of the invention

In areas such as home appliances, household appliances, kitchen ovens and ovens, locomotive and ship window glass, and buildings that require short-term or long-term ambient temperatures exceeding 200°C to 500°C, ordinary glass transmits and absorbs the solar spectrum, including visible light and near, Mid-infrared rays have adverse effects on some specific occasions where glass is used. Absorption of infrared rays causes glass temperature rise, expansion and bursting, and even glass softening and loss of strength; transmission of infrared rays causes heat to flow from high temperature areas to low temperature areas, resulting in energy loss. For example: the window glass of an oven generally needs to withstand 300°C to 500°C, and ordinary float glass or ordinary float tempered glass cannot withstand thermal shock in this temperature range for a long time. Although low-expansion borosilicate glass can withstand this temperature shock, it cannot effectively prevent heat transfer and cause energy loss.

In order to overcome the disadvantages of energy loss caused by heat transfer of glass, glass burst caused by glass expansion, and glass softening and loss of strength caused by temperature rise, a glass that reflects infrared rays, low expansion, and high glass softening temperature is needed. This kind of glass can be realized by coating thermoreflective infrared on high borosilicate glass.

Thermally reflected infrared is to adjust whether to reflect infrared according to the ambient temperature of the glass or the temperature of the glass.

Vanadium dioxide is a metal oxide with phase transition properties. Its phase transition temperature is 68°C. The structural changes before and after the phase transition lead to a reversible transition from transmission to reflection of infrared light. However, this switch to reflecting infrared light also reduces visible light transmission. According to the theory of thin film optics, the way to reduce the reflected light of glass is to coat the glass surface with a dielectric film with a lower refractive index than glass.

At present, the methods for coating thin films on glass mainly include sputtering, evaporation, and wet chemical methods. Among them, the mature magnetron sputtering method has the advantages of good uniformity of the film, easy control of the thickness of the film, and The characteristics of good glass bonding and no pollution have been widely used in the field of producing coated glass.

Contents of the invention

The invention provides a method for preparing thermally induced reflective infrared coated glass, which can reflect infrared rays as the temperature rises, thereby preventing heat transfer and delaying the temperature rise of the glass. It can be used in fields such as ovens, architectural glass, heat-resistant window glass for locomotives and ships.

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

A method for preparing thermoreflective infrared coated glass, comprising the following steps:

1) A silicon dioxide isolation layer is plated on a high borosilicate glass substrate by magnetron sputtering;

2) A metal vanadium film layer is plated on the isolation layer by magnetron sputtering; vanadium metal or tungsten-doped vanadium metal is used as the target;

3) adopt magnetron sputtering method to coat silicon dioxide film on the infrared reflection layer and obtain coated glass as the anti-reflection layer;

4) Heat treatment in the air environment and at a space temperature of 600-750° C., the metal vanadium film layer is oxidized to form an infrared reflection layer, and the coated glass is tempered at the same time.

According to the above solution, the silicon dioxide isolation layer is 10-15 nm in size.

According to the above scheme, the thickness of the infrared reflection layer is 20-60nm.

According to the above solution, the thickness of the silicon dioxide anti-reflection layer is 70-125 nm.

According to the above scheme, the doping amount of the tungsten-doped vanadium metal is 0-3.5wt%.

According to the above solution, the thermally reflective infrared coated glass is used for heat-resistant window glass.

The present invention adopts the magnetron sputtering method at normal temperature to plate a multilayer film on high borosilicate glass, utilizes the phase change of the vanadium dioxide film to reflect infrared rays, and the low refractive index film layer matching the refractive index of the vanadium dioxide film reduces the Visible light reflectance/increased visible light transmittance. The expansion coefficient of high borosilicate glass is small, which can withstand the thermal shock of 300 ℃ ~ 500 ℃, reducing the chance of glass bursting; when the ambient temperature reaches a certain temperature, the coated glass reflects infrared rays to prolong the temperature rise time of the glass and delay the time for the glass to reach the softening point , so that the glass has mechanical strength; the phase change coating reduces heat transfer and prevents energy loss or entry; the anti-reflection coating makes the glass window clearer. The coated glass achieves the purpose of heat treatment of the film layer and increasing the strength of the glass at the same time through tempering. Form a dual-function coated glass with thermal reflection infrared and visible light anti-reflection, which has a uniform film layer, is firmly bonded to the glass, and has hardness, wear resistance and thermal shock resistance that meet practical requirements. It can be used for temperature-resistant and heat-insulating window glass, such as oven glass, building heat-resistant partition glass, locomotives and ships, etc. where glass is used.

The beneficial effects of the present invention are:

The preparation process is simple and the method is mature;

The preparation process is pollution-free;

The heat treatment of the film layer of the obtained coated glass and the tempering of the coated glass are completed at one time, which can reflect infrared rays, reduce the reflection of visible light, and improve the thermal shock resistance of the glass.

detailed description

The following examples further illustrate the technical solutions of the present invention, but are not intended to limit the protection scope of the present invention.

The preparation method of thermal reflective infrared coated glass of the present invention, the preparation process is as follows:

1) A silicon dioxide isolation layer is plated on a high borosilicate glass substrate by magnetron sputtering;

2) A metal vanadium film layer is plated on the isolation layer by magnetron sputtering; vanadium metal or tungsten-doped vanadium metal is used as the target;

3) adopt magnetron sputtering method to coat silicon dioxide film on the infrared reflection layer and obtain coated glass as the anti-reflection layer;

4) Heat treatment in the air environment and at a space temperature of 600-750° C., the metal vanadium film layer is oxidized to form an infrared reflection layer, and the coated glass is tempered at the same time.

Optimally, the silicon dioxide isolation layer has a thickness of 10-15 nm.

Optimally, the thickness of the infrared reflection layer is 20-60 nm.

Optimally, the thickness of the silicon dioxide anti-reflection layer is 70-125 nm.

Optimally, the doping amount of tungsten-doped vanadium metal is 0-3.5wt%.

Optimally, the thermoreflective infrared coated glass is used for heat-resistant window glass. For example: oven glass, building heat-resistant partition glass, locomotives and ships, etc.

Optimally, the pretreatment of the high borosilicate glass substrate to be coated: the high borosilicate glass substrate to be coated is cleaned and dried with deionized water to obtain clean glass; the clean glass is placed in a vacuum box for sputter coating, Under normal pressure nitrogen, the glass surface is treated with plasma formed by 1100-1300V voltage; then the air pressure of the vacuum box is pumped to 3.5-8.5*10 ^-4 Pa.

Example 1

1. Plating isolation layer: In the vacuum box, the flow ratio of oxygen and argon is 5%, the sputtering pressure is 2.5*10 ^-1 Pa, using pure silicon, or silicon aluminum, or silicon boron as the target material, the deposited silicon oxide The film thickness is 10nm.

2. Plating infrared reflective layer: In the vacuum box, argon is used as the working gas, the sputtering pressure is 2.5*10 ^-1 Pa, vanadium metal is used as the target material, and the metal vanadium film is deposited on the glass coated with the isolation layer, and the deposited The film thickness is 20nm.

3. Coating anti-reflection layer: In the vacuum box, the flow ratio of oxygen and argon is 5%, and the sputtering pressure is 2.5*10 ^-1 Pa. Reactive sputtering deposits a high refractive index film/silicon dioxide film composite film layer, and the thickness of the film layer 70nm.

4. The obtained coated glass is heat-treated/tempered at an ambient temperature of 600-750°C, and the metal vanadium film layer is oxidized to vanadium dioxide by heat treatment, and the coated glass is tempered.

In the spectral wavelength range of 380nm to 1100nm, the transmittance of the coated glass is 45%; when the ambient temperature of the glass reaches 70°C, the infrared reflectivity of 2500nm wavelength is 45%; the hardness of the film layer is 5.5H ~ 6.5H; the coated glass can withstand 1000 times 300 ℃～500℃ thermal radiation for 3.5 hours thermal shock.

Example 2

1. Plating isolation layer: In the vacuum box, the flow ratio of oxygen and argon is 10%, the sputtering pressure is 3.5*10 ^-1 Pa, using pure silicon, or silicon aluminum, or silicon boron as the target material, the deposited silicon oxide The film thickness is 15nm.

2. Plating infrared reflective layer: In the vacuum box, argon is used as the working gas, the sputtering pressure is 3.5*10 ^-1 Pa, and tungsten-doped vanadium metal is used as the target material (tungsten doping amount: 0.5% by weight), The thickness of the deposited film layer is 20nm.

3. Plating anti-reflection layer: In the vacuum box, the flow ratio of oxygen and argon is 5%, the sputtering pressure is 2.5*10 ^-1P a reactive sputtering to deposit high refractive index film/silicon dioxide film composite film layer, the thickness of the film layer 70nm.

4. The obtained coated glass is tempered at an ambient temperature of 600-750°C, the tungsten-doped vanadium film is oxidized to vanadium dioxide by heat treatment, and the coated glass is tempered.

In the spectral wavelength range of 380nm to 1100nm, the transmittance of the coated glass is 45%; when the ambient temperature of the glass reaches 57°C, the infrared reflectivity of 2500nm wavelength is 50%; the hardness of the film layer is 5.5H ~ 6.5H; the coated glass can withstand 1000 times at 300°C ~500°C thermal radiation for 3.5 hours thermal shock.

Example 3

1. Plating isolation layer: In the vacuum box, the flow ratio of oxygen and argon is 10%, the sputtering pressure is 3.0*10 ^-1 Pa, using pure silicon, or silicon aluminum, or silicon boron as the target material, the deposited silicon oxide The film thickness is 15nm.

2. Plating infrared reflective layer: In the vacuum box, argon is used as the working gas, the sputtering pressure is 3.0*10 ^-1 Pa, and tungsten-doped vanadium metal is used as the target material (tungsten doping amount: 1.5% by weight), The thickness of the deposited film layer is 40nm.

3. Plating anti-reflection layer: In the vacuum box, the flow ratio of oxygen and argon is 10%, and the sputtering pressure is 3.0*10 ^-1 Pa. Reactive sputtering deposits a high refractive index film/silicon dioxide film composite film layer, and the thickness of the film layer 90nm.

4. The obtained coated glass is tempered at an ambient temperature of 600-750°C, the tungsten-doped vanadium film is oxidized to vanadium dioxide by heat treatment, and the coated glass is tempered.

In the spectral wavelength range from 380nm to 1100nm, the transmittance of the coated glass is 50%; when the ambient temperature of the glass starts from 43°C, the reflectivity of the coated glass to infrared rays with a wavelength of 2500nm is 50%; the hardness of the film layer is 6.0H; the coated glass can withstand 1000 times 300℃～500℃ thermal radiation for 3.5 hours thermal shock.

Example 4

1. Plating isolation layer: In the vacuum box, the flow ratio of oxygen and argon is 15%, the sputtering pressure is 3.5*10 ^-1 Pa, using pure silicon, or silicon aluminum, or silicon boron as the target material, the deposited silicon oxide The film thickness is 15nm.

2. Plating infrared reflective layer: In the vacuum box, argon is used as the working gas, the sputtering pressure is 3.0*10 ^-1 Pa, and tungsten-doped vanadium metal is used as the target (tungsten doping amount: 2.5% by weight), The deposited film thickness is 60nm.

3. Plating anti-reflection layer: In the vacuum box, the flow ratio of oxygen and argon is 15%, and the sputtering pressure is 3.5*10 ^-1 Pa. Reactive sputtering deposits a high refractive index film/silicon dioxide film composite film layer, and the thickness of the film layer 125nm.

4. The obtained coated glass is tempered at an ambient temperature of 600-750°C, the tungsten-doped vanadium film is oxidized to vanadium dioxide by heat treatment, and the coated glass is tempered.

In the spectral wavelength range from 380nm to 1100nm, the transmittance of the coated glass is 60%; when the ambient temperature of the glass starts from 42°C, the reflectivity of the coated glass to infrared rays with a wavelength of 2500nm is 55%; the hardness of the film layer is 6.5H; the coated glass can withstand 1000 times 300℃～500℃ thermal radiation for 3.5 hours thermal shock.

Example 5

1. Plating isolation layer: In the vacuum box, the flow ratio of oxygen and argon is 25%, the sputtering pressure is 3.5*10 ^-1 Pa, using pure silicon, or silicon aluminum, or silicon boron as the target material, the deposited silicon oxide The film thickness is 13nm.

2. Plating infrared reflective layer: In the vacuum box, the flow ratio of oxygen and argon is 1%, the sputtering pressure is 3.5*10 ^-1 Pa, using vanadium metal as the target material, and depositing an oxygen-deficient vanadium oxide film with a thickness of 60nm .

3. Coating anti-reflection layer: In the vacuum box, the flow ratio of oxygen and argon is 25%, and the sputtering pressure is 3.5*10 ^-1 Pa. Reactive sputtering deposits a high refractive index/silicon dioxide composite film with a film thickness of 100nm.

4. The obtained coated glass is tempered at an ambient temperature of 600-750°C, the vanadium film layer is oxidized to vanadium dioxide by heat treatment, and the coated glass is tempered.

In the spectral wavelength range of 380nm to 1100nm, the transmittance of the coated glass is 65%; when the ambient temperature of the glass starts from 62°C, the reflectivity of the coated glass to infrared rays with a wavelength of 2500nm is 55%; the hardness of the coating layer is 5.5-6.5H; the coated glass is 1000 3.5 hours of thermal radiation at 350°C to 500°C for one time, and 1000 thermal shocks at 300°C to 500°C for 3.5 hours of thermal radiation on the coated glass.

Example 6

1. Plating isolation layer: In the vacuum box, the flow ratio of oxygen and argon is 20%, the sputtering pressure is 3.5*10 ^-1 Pa, using pure silicon, or silicon aluminum, or silicon boron as the target material, the deposited silicon oxide The film thickness is 50nm.

2. Plating infrared reflective layer: In the vacuum box, the flow ratio of oxygen and argon is 1%, argon is used as the working gas, the sputtering pressure is 4.0*10 ^-1 Pa, and tungsten-doped vanadium metal is used as the target material (tungsten-doped Impurities: 3.5% by weight), deposit an oxygen-deficient vanadium oxide film with a thickness of 60nm.

3. Plating anti-reflection layer: In the vacuum box, the flow ratio of oxygen and argon is 25%, and the sputtering pressure is 3.5*10 ^-1 Pa. Reactive sputtering deposits a high refractive index/silicon dioxide composite film with a film thickness of 125nm.

4. The obtained coated glass is tempered at an ambient temperature of 600-750°C, the tungsten-doped vanadium film is oxidized to vanadium dioxide by heat treatment, and the coated glass is tempered.

In the spectral wavelength range from 380nm to 1100nm, the transmittance of the coated glass is 55%; when the ambient temperature of the glass starts from 32°C, the reflectivity of the coated glass to infrared rays with a wavelength of 2500nm is 65%; the hardness of the coating layer is 6.5H; the coated glass has been subjected to 1000 times 350℃～500℃ heat radiation for 3.5 hours, and the coated glass is subjected to 1000 times of 300℃～500℃ heat radiation for 3.5 hours thermal shock.

Example 7

1. Plating isolation layer: In the vacuum box, the flow ratio of oxygen and argon is 20%, the sputtering pressure is 3.0*10 ^-1 Pa, using pure silicon, or silicon aluminum, or silicon boron as the target material, the deposited silicon oxide The film thickness is 15nm.

2. Plating infrared reflective layer: In the vacuum box, argon is used as the working gas, the sputtering pressure is 4.0*10 ^-1 Pa, and tungsten-doped vanadium metal is used as the target (tungsten doping amount: 3.5% by weight), The thickness of the deposited film layer is 50nm.

3. Plating anti-reflection layer: In the vacuum box, the flow ratio of oxygen and argon is 20%, the sputtering pressure is 3.0*10 ^-1 Pa, and the high refractive index/silicon dioxide composite film is deposited by reactive sputtering, and the film thickness is 120nm.

4. The obtained coated glass is tempered at an ambient temperature of 600-750°C, the tungsten-doped vanadium film is oxidized to vanadium dioxide by heat treatment, and the coated glass is tempered.

In the spectral wavelength range from 380nm to 1100nm, the transmittance of the coated glass is 65%; when the ambient temperature of the glass starts from 35°C, the reflectivity of the coated glass to infrared rays with a wavelength of 2500nm is 60%; the hardness of the film layer is 6.5H; the coated glass has been subjected to 1000 times 350℃～500℃ heat radiation for 3.5 hours, and the coated glass is subjected to 1000 times of 300℃～500℃ heat radiation for 3.5 hours thermal shock.

Claims (3)

1. a preparation method of heat-induced reflective infrared coated glass, is characterized in that comprising the following steps: 1) A silicon dioxide isolation layer is plated on a high borosilicate glass substrate by magnetron sputtering; 2) A metal vanadium film layer is plated on the isolation layer by magnetron sputtering; vanadium metal or tungsten-doped vanadium metal is used as the target; 3) adopt magnetron sputtering method to coat silicon dioxide film on the infrared reflection layer and obtain coated glass as the anti-reflection layer; 4) Heat treatment in the atmospheric environment and at a space temperature of 600-750°C, the metal vanadium film layer is oxidized to form an infrared reflection layer, and the coated glass is tempered at the same time; Wherein, the silicon dioxide isolation layer is 10-15 nm; the thickness of the infrared reflection layer is 20-60 nm; and the thickness of the anti-reflection layer is 70-125 nm. 2. The method for preparing thermoreflective infrared coated glass according to claim 1, characterized in that the doping amount of said tungsten-doped vanadium metal is 0-3.5wt%. 3. The preparation method of thermoreflective infrared coated glass as claimed in claim 1, characterized in that said thermoreflective infrared coated glass is used for heat-resistant window glass.