CN111377618A - Corrosion-resistant glass and preparation method thereof - Google Patents
Corrosion-resistant glass and preparation method thereof Download PDFInfo
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- CN111377618A CN111377618A CN202010200627.7A CN202010200627A CN111377618A CN 111377618 A CN111377618 A CN 111377618A CN 202010200627 A CN202010200627 A CN 202010200627A CN 111377618 A CN111377618 A CN 111377618A
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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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3607—Coatings of the type glass/inorganic compound/metal
-
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/23—Mixtures
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/25—Metals
- C03C2217/27—Mixtures of metals, alloys
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention relates to the technical field of coating, in particular to corrosion-resistant glass and a preparation method thereof. The invention provides corrosion-resistant glass, which comprises a glass substrate and a corrosion-resistant film layer arranged on the surface of the glass substrate; the glass substrate comprises glass and a functional film layer arranged on the surface of the glass; the thickness of the corrosion-resistant film layer is 10-2000 nm; the corrosion-resistant film layer is an alloy including at least two elements of titanium, aluminum, chromium and nickel. By combining the metal elements, the optical characteristics of the glass substrate can be maintained and the corrosion resistance of the glass substrate can be enhanced under the condition that the corrosion-resistant film layer is thin and on the premise that the function of the functional film layer on the surface of the glass is not influenced.
Description
Technical Field
The invention relates to the technical field of coating, in particular to corrosion-resistant glass and a preparation method thereof.
Background
The film material is a novel material with application prospect at present, is closely related to the production activities of people, and with the development of modern science and technology and film technology and the improvement of the living standard of people, new requirements are provided for various performance indexes of the film material, and producers hope to enable the film material to have good performance suitable for various application conditions.
In the traditional coating process for decorative glass, although the coated film material can meet specific functional requirements such as color decoration, optical properties and the like, the functional film layers are not resistant to acid-base corrosion, so that the film is easy to damage and the service life of the product is influenced. In the current process for preparing a functional film on the surface of glass, a metal or alloy layer is a very important component and plays a key role in glass coating products. For example, in an interference optical film, a metal layer is wrapped as an indispensable reflective layer in the outermost layer of an optical film system, and plays a role in interference coloring. Even if the glass substrate material has color, the metal or alloy layer with different thicknesses plated on the outer surface can play the role of mirror decoration effect or internal functional film layer protection. However, most of the outermost layer metals or alloys in the current market do not have corrosion resistance, so that the stability of the product is poor, and the using effect is affected.
Disclosure of Invention
The invention aims to provide corrosion-resistant glass and a preparation method thereof. The corrosion-resistant glass provided by the invention can improve the corrosion resistance, does not influence the function of the original glass surface functional film layer, does not influence the integral color and decorative effect, and is suitable for popularization and use.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides corrosion-resistant glass, which comprises a glass substrate and a corrosion-resistant film layer arranged on the surface of the glass substrate; the glass substrate comprises glass and a functional film layer arranged on the surface of the glass; the thickness of the corrosion-resistant film layer is 10-2000 nm; the corrosion-resistant film layer is an alloy including at least two elements of titanium, aluminum, chromium and nickel.
Preferably, when the corrosion-resistant film layer is a titanium-aluminum-chromium-nickel alloy, the molar ratio of the titanium, the aluminum, the chromium and the nickel elements is (60-75): (12-20): (8-15): (0.1-0.8).
Preferably, when the corrosion-resistant film layer is a titanium-aluminum alloy, the molar ratio of the titanium to the aluminum elements is (4-7): (3-6).
Preferably, when the corrosion-resistant film layer is a titanium-chromium alloy, the molar ratio of the titanium to the chromium is (6-8): 2-4.
Preferably, the glass substrate is transparent glass or colored glass.
The invention also provides a preparation method of the corrosion-resistant glass in the technical scheme, which comprises the following steps:
plating a corrosion-resistant film layer on the surface of a glass substrate by adopting magnetron sputtering to obtain corrosion-resistant glass; the sputtering target is an alloy including at least two elements of titanium, aluminum, chromium, and nickel.
Preferably, the sputtering power of the sputtering target is 10-600W.
Preferably, the pressure of the magnetron sputtering is 0.1-1 Pa.
Preferably, the magnetron sputtering is carried out in an argon atmosphere, and the flow rate of the argon is 40-300 sccm.
The invention provides corrosion-resistant glass, which is characterized by comprising a glass substrate and a corrosion-resistant film layer arranged on the surface of the glass substrate; the glass substrate comprises glass and a functional film layer arranged on the surface of the glass; the thickness of the corrosion-resistant film layer is 10-2000 nm; the corrosion-resistant film layer is an alloy including at least two elements of titanium, aluminum, chromium and nickel. In the invention, titanium has excellent strong acid corrosion resistance, aluminum has strong passivation property, chromium has passivation effect, the passivation film has good corrosion resistance, nickel has excellent alkali corrosion resistance, and nickel is extremely stable in seawater and salt solution. By combining the metal elements, the effects of maintaining the optical transmittance of the glass substrate and enhancing the corrosion resistance of the glass substrate can be achieved under the condition that the corrosion-resistant film layer is thin.
Drawings
FIG. 1 is a diagram showing the effect of a glass substrate of comparative example 1 after a 72-hour national standard salt spray experiment;
FIG. 2 is a diagram showing the effect of the corrosion-resistant glass prepared in example 1 of the present invention after a 72-hour national standard salt spray experiment.
Detailed Description
The invention provides corrosion-resistant glass, which comprises a glass substrate and a corrosion-resistant film layer arranged on the surface of the glass substrate; the glass substrate comprises glass and a functional film layer arranged on the surface of the glass; the thickness of the corrosion-resistant film layer is 10-2000 nm; the corrosion-resistant film layer is an alloy including at least two elements of titanium, aluminum, chromium and nickel.
The corrosion resistant glass provided by the invention comprises a glass substrate. In the invention, the glass substrate comprises glass and a functional film layer arranged on the surface of the glass. The present invention is not particularly limited to specific components and preparation methods of the functional film layer, and components and preparation methods known to those skilled in the art, such as optical films or decorative films, can be used. In the present invention, the glass substrate is preferably transparent glass.
The corrosion-resistant glass provided by the invention comprises a corrosion-resistant film layer arranged on the surface of the glass substrate. In the invention, the thickness of the corrosion-resistant film layer is 10-2000 nm, preferably 15-100 nm, more preferably 20-200 nm, and even more preferably 50 nm. The thickness of the corrosion-resistant film layer is limited to be within the range, so that the corrosion resistance of the functional film layer can be improved on the premise of not influencing the functions of all components of the functional film layer on the surface of the glass, and the integral color and decorative effect of the original glass substrate are not influenced.
In the present invention, the corrosion-resistant film layer is an alloy including at least two elements of titanium, aluminum, chromium, and nickel. Specifically, the corrosion-resistant film layer is a titanium-aluminum-chromium-nickel alloy, a titanium-aluminum alloy, a titanium-chromium alloy, a titanium-nickel alloy, an aluminum-chromium alloy, an aluminum-nickel alloy or a chromium-nickel alloy.
In the invention, when the corrosion-resistant film layer is a titanium-aluminum-chromium-nickel alloy, the molar ratio of the titanium, the aluminum, the chromium and the nickel elements is preferably (6.0-7.5): 1.2-2.0): 0.8-1.5): 0.1-0.8, and more preferably 7:1.5:1: 0.5; when the corrosion-resistant film layer is a titanium-aluminum alloy, the molar ratio of the titanium to the aluminum is preferably (4-7): 3-6, and more preferably 1: 1; when the corrosion-resistant film layer is made of titanium-chromium alloy, the molar ratio of the titanium to the chromium is preferably (6-8): 2-4, and more preferably 7: 3; when the corrosion-resistant film layer is made of titanium-nickel alloy, the molar ratio of the titanium to the nickel is preferably (9.5-9.9): (0.1-0.5), and more preferably 9.8: 0.2; when the corrosion-resistant film layer is made of aluminum-chromium alloy, the molar ratio of aluminum to chromium is preferably (3-7): 3-7, and more preferably 6.5: 3.5; when the corrosion-resistant film layer is made of an aluminum-nickel alloy, the molar ratio of the aluminum to the nickel is preferably (9.5-9.9): (0.1-0.5), and more preferably 9.7: 0.3; when the corrosion-resistant film layer is made of chromium-nickel alloy, the molar ratio of the chromium to the nickel is preferably (9.5-9.9): (0.1-0.5), and more preferably 9.8: 0.2.
The invention provides a preparation method of the corrosion-resistant glass in the technical scheme, which comprises the following steps: plating a corrosion-resistant film layer on the surface of a glass substrate by adopting magnetron sputtering to obtain corrosion-resistant glass; the sputtering target is an alloy including at least two elements of titanium, aluminum, chromium, and nickel.
In the present invention, the glass substrate is preferably cleaned and then sputtered with a corrosion-resistant film. The specific method of the cleaning treatment is not particularly limited in the present invention, and impurities on the surface of the glass substrate may be removed by a cleaning method known to those skilled in the art.
The magnetron sputtering apparatus of the present invention is not particularly limited, and a magnetron sputtering apparatus known to those skilled in the art may be used. In the embodiment of the invention, the equipment model of the magnetron sputtering is preferably TSU-650; the power supply used for magnetron sputtering is preferably a radio frequency power supply.
In the present invention, the sputtering target is an alloy including at least two elements of titanium, aluminum, chromium and nickel, and the specific composition is consistent with that of the corrosion-resistant film layer, which is not described herein again.
In the invention, the magnetron sputtering power of the sputtering target is preferably 10-600W, more preferably 50-300W, and further preferably 90W; the air pressure of the magnetron sputtering is preferably 0.1-1 Pa, more preferably 0.4-0.7 Pa, and further preferably 0.5 Pa; the magnetron sputtering is preferably carried out in an argon atmosphere, and the flow rate of the argon is preferably 40-300 sccm, more preferably 100-200 sccm; the coating time of the magnetron sputtering is not specially limited, so that the thickness of the corrosion-resistant film layer according with the technical scheme is obtained.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the 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.
Example 1
Taking a titanium-aluminum-chromium-nickel alloy as a target material, wherein the molar ratio of titanium to aluminum to chromium to nickel is 7:1.5:1: 0.5; controlling the magnetron sputtering power to be 90W, the sputtering pressure to be 0.7Pa, the argon flow to be 40sccm, and the sputtering temperature to be room temperature, and performing sputtering coating on the surface of red glass for 2min to obtain a corrosion-resistant film layer with the thickness of 200nm, wherein the red glass is transparent glass, and nickel oxide and chromium oxide are arranged on the surface of the transparent glass according to the ratio of 1:1 mixed functional film layer.
Example 2
Taking a titanium-aluminum alloy as a target material, wherein the molar ratio of titanium to aluminum-nickel elements is 1: 1; controlling the magnetron sputtering power to be 90W, the sputtering pressure to be 0.5Pa, the argon flow to be 40sccm, and the sputtering temperature to be room temperature, and carrying out sputtering coating on the red glass surface for 1min to obtain the corrosion-resistant film layer with the thickness of 50 nm.
Example 3
Taking a titanium-chromium alloy as a target material, wherein the molar ratio of titanium to chromium is 7: 3; controlling the magnetron sputtering power to be 90W, the sputtering pressure to be 0.4Pa, the argon flow to be 40sccm, and the sputtering temperature to be room temperature, and carrying out sputtering coating on the surface of the red glass for 0.5min to obtain the corrosion-resistant film layer with the thickness of 20 nm.
Comparative example 1
The red glass used in example 1 was used as comparative example 1.
Test example 1
According to the method of GB6459-86 acetate salt spray test, the red glass of the comparative example 1 and the corrosion resistant glass prepared in the example 1 are tested for 72 hours in the salt spray test, and the obtained results are shown in the figures 1-2; wherein, FIG. 1 is an effect diagram of red glass of comparative example 1 after 72 hours of national standard salt spray experiment; FIG. 2 is a diagram showing the effect of the corrosion-resistant glass prepared in example 1 of the present invention after a 72-hour national standard salt spray experiment.
As can be seen from the graphs of FIGS. 1-2, after the comparative example 1 without using the corrosion-resistant film layer is tested in the national standard salt spray test for 72 hours, the surface corrosion is serious, the falling area is more than 10 percent, and the thickness of the original red film layer is seriously influenced, so that the phenomenon of uneven color is generated, and the film is seriously damaged; example 1, using a corrosion resistant film, showed no signs of corrosion after 72 hours in the salt spray test, and the film color was consistent with the original. The results of the salt spray tests performed on the corrosion resistant glasses prepared in examples 2-3 are similar to those shown in FIG. 2. The corrosion-resistant glass provided by the invention has excellent corrosion resistance, and the original decorative effect of the glass substrate is not influenced.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that it is within the scope of the present invention for a person of ordinary skill in the art to change the alloy material and composition, especially only to change the coating process, without departing from the principle of the present invention.
Claims (9)
1. The corrosion-resistant glass is characterized by comprising a glass substrate and a corrosion-resistant film layer arranged on the surface of the glass substrate; the glass substrate comprises glass and a functional film layer arranged on the surface of the glass; the thickness of the corrosion-resistant film layer is 10-2000 nm; the corrosion-resistant film layer is an alloy including at least two elements of titanium, aluminum, chromium and nickel.
2. The corrosion-resistant glass of claim 1, wherein when the corrosion-resistant film is a titanium aluminum chromium nickel alloy, the molar ratio of the titanium, aluminum, chromium, and nickel elements is (60-75): (12-20): (8-15): (0.1-0.8).
3. The corrosion-resistant glass of claim 1, wherein when the corrosion-resistant film layer is a titanium-aluminum alloy, the molar ratio of the titanium to the aluminum elements is (4-7) to (3-6).
4. The corrosion-resistant glass of claim 1, wherein when the corrosion-resistant film layer is a titanium-chromium alloy, the molar ratio of the titanium to the chromium is (6-8) to (2-4).
5. The corrosion resistant glass of claim 1, wherein the glass substrate is clear glass or tinted glass.
6. A method of making a corrosion resistant glass as claimed in any one of claims 1 to 5, comprising the steps of:
plating a corrosion-resistant film layer on the surface of a glass substrate by adopting magnetron sputtering to obtain corrosion-resistant glass; the sputtering target is an alloy including at least two elements of titanium, aluminum, chromium, and nickel.
7. The method according to claim 6, wherein the sputtering power of the sputtering target is 10-600W.
8. The method according to claim 6, wherein the magnetron sputtering is carried out under a pressure of 0.1 to 1 Pa.
9. The method according to claim 6 or 8, wherein the magnetron sputtering is performed in an argon atmosphere, and a flow rate of the argon gas is 40 to 300 sccm.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010200627.7A CN111377618B (en) | 2020-03-20 | 2020-03-20 | Corrosion-resistant glass and preparation method thereof |
| NL2027688A NL2027688B1 (en) | 2020-03-20 | 2021-03-03 | Corrosion-resistant glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010200627.7A CN111377618B (en) | 2020-03-20 | 2020-03-20 | Corrosion-resistant glass and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN111377618A true CN111377618A (en) | 2020-07-07 |
| CN111377618B CN111377618B (en) | 2022-04-26 |
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| CN202010200627.7A Active CN111377618B (en) | 2020-03-20 | 2020-03-20 | Corrosion-resistant glass and preparation method thereof |
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| NL (1) | NL2027688B1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1518838A1 (en) * | 2003-09-24 | 2005-03-30 | Nippon Electric Glass Co., Ltd. | Glass article |
| WO2006120387A2 (en) * | 2005-05-11 | 2006-11-16 | Sheffield Hallam University | Sol-gel derived coating |
| CN201132817Y (en) * | 2007-08-31 | 2008-10-15 | 湖州金泰镀业有限公司 | Golden yellow coated glass or ceramic |
| CN201554075U (en) * | 2009-06-18 | 2010-08-18 | 刘凤祥 | Glass wash basin |
| CN103003211A (en) * | 2010-06-30 | 2013-03-27 | 尤罗科拉公司 | Cooking device |
| CN105431392A (en) * | 2013-03-12 | 2016-03-23 | 分子间公司 | Electrically insulating material for thermal sprayed coatings |
-
2020
- 2020-03-20 CN CN202010200627.7A patent/CN111377618B/en active Active
-
2021
- 2021-03-03 NL NL2027688A patent/NL2027688B1/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1518838A1 (en) * | 2003-09-24 | 2005-03-30 | Nippon Electric Glass Co., Ltd. | Glass article |
| WO2006120387A2 (en) * | 2005-05-11 | 2006-11-16 | Sheffield Hallam University | Sol-gel derived coating |
| CN201132817Y (en) * | 2007-08-31 | 2008-10-15 | 湖州金泰镀业有限公司 | Golden yellow coated glass or ceramic |
| CN201554075U (en) * | 2009-06-18 | 2010-08-18 | 刘凤祥 | Glass wash basin |
| CN103003211A (en) * | 2010-06-30 | 2013-03-27 | 尤罗科拉公司 | Cooking device |
| CN105431392A (en) * | 2013-03-12 | 2016-03-23 | 分子间公司 | Electrically insulating material for thermal sprayed coatings |
Non-Patent Citations (2)
| Title |
|---|
| 王连伟等: "《蒸镀铬钛合金装饰膜的研究》", 《腐蚀与防护》 * |
| 陈希等: "《钛铝合金溅射镀膜靶材的研究进展》", 《湖南有色金属》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| NL2027688B1 (en) | 2022-05-09 |
| NL2027688A (en) | 2021-05-18 |
| CN111377618B (en) | 2022-04-26 |
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