NL2027688B1

NL2027688B1 - Corrosion-resistant glass and preparation method thereof

Info

Publication number: NL2027688B1
Application number: NL2027688A
Authority: NL
Inventors: Wang Kunlun; Sun Hui; Zhama Tuofu; Xin Yanqing
Original assignee: Univ Shandong
Priority date: 2020-03-20
Filing date: 2021-03-03
Publication date: 2022-05-09
Also published as: NL2027688A; CN111377618A; CN111377618B

Abstract

The present disclosure pertains to the ﬁlm-coating technical ﬁeld, in particular to corrosion-resistant glass and a preparation method thereof. The corrosion-resistant glass provided by the present disclosure comprises a glass substrate and a corrosion- resistant ﬁlm layer conﬁgured on the surface of the glass substrate; the glass substrate comprises glass and a functional ﬁlm layer conﬁgured on the surface of the glass, the corrosion-resistant ﬁlm layer has a thickness of 10 to 2000 nm, the corrosion-resistant ﬁlm layer is an alloy comprising at least two elements selected from titanium, aluminum, chromium and nickel. By using the above metal elements as combined, it is possible to achieve the effect of maintaining the optical characteristics of the glass substrate and enhancing the corrosion resistance of the glass substrate without affecting the effect of the functional ﬁlm layer on the surface of the glass when the corrosion- resistant ﬁlm layer is thin.

Description

_1- CORROSION-RESISTANT GLASS AND PREPARATION METHOD

THEREOF

TECHNICAL FIELD The present disclosure pertains to the film-coating technical field, in particular to corrosion-resistant glass and a preparation method thereof.

BACKGROUD Currently, film materials are new materials that have very promising application prospects and are closely related to production activities. With the development of modern scientific technology and film technology as well as the improvement of living standards, there are new demands on the various performance indicators of film materials. Producers hope to make them have good properties to adapt to various application conditions.

In traditional decorative glass coating processes, the coated film materials can meet specific functional requirements, such as color decoration, optical properties, etc, but these functional film layers per se are often not resistant to acid and alkali corrosion, which makes the films vulnerable to damage and affects their product life. In current processes of preparing functional films on glass surfaces, the metal or alloy layer is a very important compositional part and plays a key role in glass coating products. For example, in interference optical films, the metal layer, as an indispensable reflective layer, 1s wrapped on the outermost layer of the optical film system, and plays a role in the interference color formation. Even for a glass substrate material which per se has a color, coating its outer surface with a metal or alloy layer of different thicknesses can also functions as mirror decoration or protection of internal functional film layers. However, for most products on the market, the metal or alloy of the outermost layer does not have corrosion resistance characteristics, thereby resulting in poor product stability and affecting the use effect.

SUMMARY It is an object of the present disclosure to provide a corrosion-resistant glass and a preparation method thereof. The corrosion-resistant glass provided by the present disclosure can improve the corrosion resistance without affecting the functions of the

2. original functional films on the surface of the glass, and without affecting the overall color and decorative effect, and is suitable for popularization and use.

In order to achieve the above inventive object, the present disclosure provides the following technical solutions:

The present disclosure provides a corrosion-resistant glass, comprising a glass substrate and a corrosion-resistant film layer configured on the surface of the glass substrate; the glass substrate comprises glass and a functional film layer configured on the surface of the glass; the corrosion-resistant film layer has a thickness of 10 to 2000 nm; the corrosion-resistant film layer is an alloy comprising at least two elements selected from titanium, aluminum, chromium and nickel.

Preferably, when the corrosion-resistant film layer 1s a titanium-aluminum-chromium- nickel alloy, the molar ratio of the titanium, aluminum, chromium and nickel elements is (6.0 t0 7.5) : (1.2 t0 2) : (0.8 to 1.5): (0.1 to 0.8). Preferably, when the corrosion-resistant film layer is a titanium-aluminum alloy, the molar ratio of the titanium and aluminum elements is (4 to 7) : (3 to 6). Preferably, when the corrosion-resistant film layer is a titanium-chromium alloy, the molar ratio of the titanium and chromium elements is (6 to 8) : (2 to 4). Preferably, the glass substrate is a transparent glass or a colored glass.

The present disclosure also provides a method for preparing the corrosion-resistant glass as described in the above technical solutions, comprising the following step: Coating the surface of the glass substrate with a corrosion-resistant film layer by magnetron sputtering to obtain the corrosion-resistant glass; the sputtering target is an alloy comprising at least two elements selected from titanium, aluminum, chromium and nickel.

Preferably, the sputtering power of the sputtering target is 10 to 600 W.

Preferably, the gas pressure of the magnetron sputtering is 0.1 to 1 Pa.

Preferably, the magnetron sputtering is performed in an argon atmosphere, and the flow rate of the argon is 40 to 300 sccm.

The present disclosure provides a corrosion-resistant glass, comprising a glass substrate and a corrosion-resistant film layer configured on the surface of the glass substrate; the glass substrate comprises glass and a functional film layer configured on the surface of the glass; the corrosion-resistant film layer has a thickness of 10 to 2000 nm; the corrosion-resistant film layer is an alloy comprising at least two elements selected from

-3- titanium, aluminum, chromium and nickel. In the present disclosure, titanium has excellent resistance to strong acid corrosion; aluminum has a strong passivation property; chromium has a passivation effect, and the passivation film thereof has good corrosion resistance; nickel has excellent resistance to alkali corrosion, and is extremely stable in sea water and salt solutions. By using the above metal elements as combined, it is possible to achieve the effect of maintaining the optical transmittance of the glass substrate and enhancing the corrosion resistance of the glass substrate when the corrosion-resistant film layer is thin.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an effect picture of the glass substrate of Comparative Example 1 after undergoing the Chinese national standard salt spray test for 72 hours; FIG. 2 is an effect picture of the corrosion-resistant glass prepared in Example 1 of the present disclosure after undergoing the Chinese national standard salt spray test for 72 hours.

DETAILED DESCRIPTION The present disclosure provides a corrosion-resistant glass, comprising a glass substrate and a corrosion-resistant film layer configured on the surface of the glass substrate; the corrosion-resistant film layer has a thickness of 10 to 2000 nm; the corrosion-resistant film layer is an alloy comprising at least two elements selected from titanium, aluminum, chromium and nickel.

The corrosion-resistant glass provided by the present disclosure comprises a glass substrate. In the present disclosure, the glass substrate comprises glass and a functional film layer configured on the surface of the glass. In the present disclosure, the specific components and preparation methods of the functional film layer are particularly limited, as long as the components and preparation methods are well known to those skilled in the art; specific examples include optical films or decorative films. In the present disclosure, the glass substrate is preferably a transparent glass.

The corrosion-resistant glass provided by the present disclosure comprises a corrosion- resistant film layer configured on the surface of the glass substrate. In the present disclosure, the corrosion-resistant film layer has a thickness of 10 to 2000 nm, preferably 15 to 100 nm, more preferably 20 to 200 nm, and most preferably 50 nm.

-4- The present disclosure limits the thickness of the corrosion-resistant film layer to the above range, which can improve the corrosion resistance of the functional film layer without affecting the effects of the various components of the functional film layer on the glass surface, and without affecting the original overall color and decorative effect of the glass substrate. In the present disclosure, the corrosion-resistant film layer is an alloy comprising at least two elements selected from 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 present disclosure, when the corrosion-resistant film layer is a titanium- aluminum-chromium-nickel alloy, the molar ratio of the titanium, aluminum, chromium and nickel elements is preferably (6.0 to 7.5) : (1.2 to 2.0) : (0.8 to 1.5) : (0.1 t0 0.8), 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 and aluminum elements is preferably (4 to 7) : (3 to 6), more preferably 1 : 1; when the corrosion-resistant film layer is a titanium-chromium alloy, the molar ratio of the titanium and chromium elements is preferably (6 to 8) : (2 to 4), more preferably 7 : 3; when the corrosion-resistant film layer is a titanium-nickel alloy, the molar ratio of the titanium and nickel elements is preferably (9.5 to 9.9) : (0.1 to 0.5), more preferably 9.8 : 0.2; when the corrosion- resistant film layer is an aluminum-chromium alloy, the molar ratio of the aluminum and chromium elements is preferably (3 to 7) : (3 to 7), more preferably 6.5 : 3.5; when the corrosion-resistant film layer is an aluminum-nickel alloy, the molar ratio of the aluminum and nickel elements is preferably (9.5 to 9.9) : (0.1 to 0.5), more preferably

9.7 : 0.3; when the corrosion-resistant film layer is a chromium-nickel alloy, the molar ratio of the chromium and nickel elements is preferably (9.5 to 9.9) : (0.1 to 0.5), more preferably 9.8 : 0.2. The present disclosure provides a method for preparing the corrosion-resistant glass as described in the above technical solutions, comprising the following step: coating the surface of the glass substrate with a corrosion-resistant film layer by magnetron sputtering to obtain the corrosion-resistant glass; the sputtering target is an alloy comprising at least two elements selected from titanium, aluminum, chromium and

-5- nickel.

In the present disclosure, the glass substrate is preferably subjected to a cleaning treatment, and then sputtered with the corrosion-resistant film layer.

In the present disclosure, the specific methods of the cleaning treatment are not particularly limited, and the cleaning methods well known to those skilled in the art can be used to remove impurities on the surface of the glass substrate.

In the present disclosure, the magnetron sputtering equipment is not particularly limited, as long as the magnetron sputtering apparatus is well known to those skilled in the art.

In the examples of the present disclosure, the model of the magnetron sputtering apparatus is preferably TSU-650; the power source used for the magnetron sputtering is preferably a radio frequency power source.

In the present disclosure, the sputtering target is an alloy comprising at least two elements selected from titanium, aluminum, chromium and nickel, and the specific composition 1s the same as the composition of the corrosion-resistant film layer, which will not be repeated herein.

In the present disclosure, the magnetron sputtering power of the sputtering target is preferably 10 to 600 W, more preferably 50 to 300 W, and most preferably 90 W; the gas pressure of the magnetron sputtering 1s preferably 0.1 to 1 Pa, more preferably 0.4 to 0.7 Pa, and most 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 to 300 sccm, more preferably 100 to 200 sccm; in the present disclosure, the coating time of the magnetron sputtering is not particularly limited, as long as it yields a thickness of the corrosion-resistant film layer as described in the above technical solutions.

The technical solutions of the present disclosure will be clearly and completely described below in conjunction with the examples of the present disclosure.

Obviously, the described examples are only a part of the examples of the present disclosure, rather than all the examples.

Based on the examples of the present disclosure, all other examples obtainable by those of ordinary skill in the art without doing inventive work are within the protection scope of the present disclosure.

Example 1 A titanium-aluminum-chromium-nickel alloy is used as the target material, wherein the molar ratio of titanium, aluminum, chromium and nickel elements is 7 : 1.5: 1: 0.5; the power of the magnetron sputtering is controlled at 90 W; the sputtering gas pressure

-6- is 0.7 Pa; the flow rate of the argon is 40 sccm; the sputtering temperature is room temperature; the coating is performed by sputtering on a red glass for 2 min to obtain a corrosion-resistant film layer with a thickness of 200 nm; the red glass comprises a transparent glass and a functional film layer configured on the surface of the transparent glass, which is made of a mixture of nickel oxide and chromium oxide in a ratio of 1:1. Example 2 A titanium-aluminum alloy is used as the target material, wherein the molar ratio of titanium and aluminum elements is 1 : 1; the power of the magnetron sputtering is controlled at 90 W; the sputtering gas pressure is 0.5 Pa; the flow rate of the argon is 40 sccm; the sputtering temperature is room temperature; the coating is performed by sputtering on a red glass for 1 min to obtain a corrosion-resistant film layer with a thickness of 50 nm.

Example 3 A titanium-chromium alloy is used as the target material, wherein the molar ratio of titanium and chromium elements is 7 : 3; the power of the magnetron sputtering is controlled at 90 W; the sputtering gas pressure is 0.4 Pa; the flow rate of the argon is 40 sccm; the sputtering temperature is room temperature; the coating is performed by sputtering on a red glass for 0.5 min to obtain a corrosion-resistant film layer with a thickness of 20 nm.

Comparative Example 1 The red glass used in Example 1 is taken as Comparative Example 1. Test Example 1 According to the method of GB6459-86 acetic acid salt spray test, the red glass of Comparative Example 1 and the corrosion-resistant glass prepared in Example | are tested in the salt spray test for 72 h.

The results are as shown in FIGs. 1 to 2, wherein FIG. 1 is an effect picture of the red glass of Comparative Example | after undergoing the national standard salt spray test for 72 hours; FIG. 2 is an effect picture of the corrosion-resistant glass prepared in Example 1 of the present disclosure after undergoing the national standard salt spray test for 72 hours.

It can be seen from FIGs. 1 to 2 that after undergoing the national standard salt spray test for 72 hours, Comparative Example 1 which does not use the corrosion-resistant film shows a severe corrosion on the surface, and has a shedding area greater than 10%; besides, the thickness of the original red film layer has been seriously affected; as a

-7- result, color unevenness occurs, and the film is significantly damaged.

After undergoing the national standard salt spray test for 72 hours, Example 1 which uses the corrosion- resistant film layer shows no signs of corrosion on the surface, and the color of the film layer is the same as the original one.

After subjecting the corrosion-resistant glasses prepared in Examples 2 to 3 to a salt spray test, the obtained results are similar to those in FIG. 2. This shows that the corrosion-resistant glass provided by the present disclosure has excellent corrosion resistance and does not affect the original decorative effect of the glass substrate.

The above examples are only the preferred examples of the present disclosure.

It should be pointed out that for those of ordinary skill in the art, without departing from the principles of the present disclosure, the alloy materials and components can be changed, especially, the situations where only the coating process is changed shall be regarded as within the protection scope of the present disclosure.

Claims

-8- Conclusions l. Corrosion-resistant glass comprising a glass substrate and a corrosion-resistant fleece layer configured on the surface of the glass substrate; wherein the glass substrate comprises glass and a functional fleece layer configured on the surface of the glass; wherein the corrosion resistant fleece layer has a thickness of 10 - 2000 nm, wherein the corrosion resistant fleece layer is an alloy comprising at least two elements selected from titanium, aluminum, chromium and nickel.

The corrosion-resistant glass of claim 1, wherein, when the corrosion-resistant fleece layer is a titanium-aluminum-chromium-nickel alloy, the molar ratio of the titanium, aluminum, chromium and nickel elements is (6.0 - 7.5): (1 .2-2):(0.8-1.5): (0.1 - 0.8).

The corrosion-resistant glass of claim 1, wherein when the corrosion-resistant fleece layer is a titanium-aluminum alloy, the molar ratio of the titanium and aluminum elements is (4 - 7) : (3 - 6).

The corrosion-resistant glass according to claim 1, wherein when the corrosion-resistant fleece layer is a titanium-chromium alloy, the molar ratio of the titanium and chromium elements is (6 - 8) : (2 - 4).

The corrosion-resistant glass of claim 1, wherein the glass substrate is a transparent glass or a colored glass.

The method of preparing the corrosion-resistant glass according to any one of claims 1 to 5, comprising the step of: coating the surface of the glass substrate with a corrosion-resistant fleece layer by means of magnetron sputtering to obtain the corrosion-resistant glass; wherein the sputtering target is an alloy comprising at least two elements selected from titanium, aluminum, chromium and nickel.

The preparation method according to claim 6, wherein the sputtering power of the

-9- sputtering target is 10 — 600 W.

The production method according to claim 6, wherein the gas pressure of the magnetron sputtering is 0.1-1 Pa.

The production method according to claim 6 or 8, wherein the magnetron sputtering is performed in an argon atmosphere, and the flow rate of the argon is 40-300 sccm.