CN116040952A

CN116040952A - Glass etching liquid, glass with crystal-shining pattern and production method thereof

Info

Publication number: CN116040952A
Application number: CN202111267088.XA
Authority: CN
Inventors: 袁涛; 罗富华; 马兰; 潘玲; 赵永灏
Original assignee: BYD Co Ltd
Current assignee: BYD Co Ltd
Priority date: 2021-10-28
Filing date: 2021-10-28
Publication date: 2023-05-02

Abstract

The application provides a glass etching liquid, which comprises the following components in percentage by mass: ammonium bifluoride: 30% -45%; carboxylate: 0.5 to 1.5 percent; phosphate: 0.5 to 1.5 percent; hydrochloric acid: 0.5 to 4 percent; nitric acid: 31% -45%; water: 10% -20%; the phosphate comprises one or more of normal phosphate, monohydrogen phosphate and dihydrogen phosphate. The glass etching liquid has stable performance, and when the glass etching liquid is applied to a glass etching process, the production requirement is low, and a brilliant pattern can be formed on the surface of glass through simple steps, so that the attractiveness of the glass is greatly improved. The application also provides glass with a blazed pattern and a production method thereof.

Description

Glass etching liquid, glass with crystal-shining pattern and production method thereof

Technical Field

The application relates to the technical field of glass processing, in particular to glass etching liquid, glass with brilliant patterns and a production method thereof.

Background

Glass has wide application as a cheaper decorative material, however, the glass on the market at present has monotonous appearance, can not meet the personalized demands of people, has weak competitiveness of products, and besides, the etching liquid adopted by the existing glass etching process has complex components and poor stability, so that the etching effect is uneven and the yield of products is low. Therefore, it is necessary to provide a new glass etching liquid to efficiently produce glass having a novel appearance with high quality.

Disclosure of Invention

In view of the above, the application provides a glass etching liquid, which has stable performance, and when the glass etching liquid is applied to a glass etching process, the production requirement is low, and a brilliant pattern can be formed on the surface of glass through simple steps, so that the attractiveness of the glass is greatly improved.

The first aspect of the application provides a glass etching liquid, which comprises the following components in percentage by mass:

ammonium bifluoride: 30% -45%;

carboxylate: 0.5 to 1.5 percent;

phosphate: 0.5 to 1.5 percent;

hydrochloric acid: 0.5 to 4 percent;

nitric acid: 31% -45%;

water: 10% -20%;

the phosphate comprises one or more of normal phosphate, monohydrogen phosphate and dihydrogen phosphate.

In the etching solution, ammonium bifluoride can erode the surface of glass under an acidic condition, the surface of the glass is softened, and fluorosilicate, which is a reaction product, can form crystals and be deposited on the surface of the glass together with supersaturated precipitated ammonium bifluoride; the carboxylate, phosphate, nitric acid and hydrochloric acid can cooperatively adjust the structure and distribution of crystals, so that crystals are piled up to form a crystal mixture with complete particles and distinct layers, the crystal mixture can form pressing points on the surface of softened glass, the surface of the glass is deformed, a crystal-like stacked structure is formed on the surface of the glass, the crystals in the same stacking direction are gathered to form clusters, namely a flare, and a plurality of flare combinations form a crystal-flare pattern. Under the synergistic effect of the components with the specific mass percentage, the obtained glass etching liquid has stable components, can generate uniformly distributed flare on the surface of the glass, and has high attractive appearance and good visual experience.

Optionally, the mass ratio of the carboxylate to the ammonium bifluoride is 1 (30-90).

Optionally, the mass ratio of the carboxylate to the phosphate is 1 (0.5-2).

Optionally, the carboxylate comprises one or more of zinc acetate, magnesium acetate, potassium acetate, sodium acetate, zinc propionate, magnesium propionate, potassium propionate, sodium lactate, potassium lactate, sodium oxalate, potassium oxalate, sodium acrylate, potassium acrylate, sodium benzoate, potassium benzoate, sodium citrate, and sodium succinate.

Optionally, the phosphoric acid normal salt includes one or more of sodium phosphate, potassium phosphate, calcium phosphate, and aluminum phosphate.

Optionally, the monohydrogen phosphate comprises one or more of sodium monohydrogen phosphate, potassium monohydrogen phosphate, calcium monohydrogen phosphate, and aluminum monohydrogen phosphate.

Optionally, the monobasic phosphate includes one or more of sodium monobasic phosphate, potassium monobasic phosphate, calcium monobasic phosphate, and aluminum monobasic phosphate.

Optionally, the glass etching solution further comprises 1-5% of organic acid by mass percent.

Optionally, the organic acid includes one or more of acetic acid, oxalic acid, tartaric acid, citric acid, sulfamic acid, sorbic acid, and maleic acid.

Optionally, the glass etching liquid further comprises a thickener with the mass percent of 0.5% -5%.

Optionally, the thickener comprises one or more of glycerol, triethanolamine, ethylene glycol, methanol, hexanol, octanol, maltose, sodium polyacrylate, polyethylene glycol, polyvinylpyrrolidone, and polyacrylamide.

Optionally, the glass etching solution comprises the following components in percentage by mass:

ammonium bifluoride: 35% -45%;

carboxylate: 0.5 to 1 percent;

phosphate: 0.5 to 1 percent;

hydrochloric acid: 0.5% -2%;

nitric acid: 35% -45%;

organic acid: 2% -4%;

and (3) a thickening agent: 2% -4%;

water: 10% -15%;

in a second aspect, the present application provides a method of producing glass having a blazed pattern, comprising the steps of:

providing a glass etching solution according to the first aspect;

and placing the glass into the glass etching liquid for etching to obtain the glass with the brilliant patterns.

Optionally, the etching time is 0.75 min-5 min.

Optionally, the etching temperature is 10-30 ℃.

Optionally, the glass is subjected to a soaking treatment in advance, and the soaking treatment comprises: and soaking the glass in an acidic solution for 5-60 s.

Optionally, the glass comprises one or more of aluminosilicate glass, soda lime glass, colored glass, sodium-potassium glass.

The production method of the glass with the blazed patterns is simple in treatment method, short in treatment time and suitable for industrial production.

In a third aspect, the present application provides a glazing having a blazed pattern, the glazing having a blazed pattern produced by the method of producing of the second aspect.

Optionally, the glass surface with the blazed pattern is provided with a plurality of blazes, the blazes are formed by orderly arranging a plurality of crystal-like bodies, and the average grain diameter of the crystal-like bodies is 10-200 μm.

The glass with the brilliant pattern provided by the third aspect of the application is attractive and good in appearance, has the anti-dizziness effect, can enable light to be soft and not to be pricked, brings good visual experience to users, and meets personalized pursuits and fashionable pursuits of the users.

Drawings

FIG. 1 is a micrograph of a glass surface having a blazed pattern according to one embodiment of the present application;

FIG. 2 is a schematic illustration of a glass surface flare distribution with a sparkle pattern;

FIG. 3 is a schematic illustration of a method for preparing a glass etching solution according to an embodiment of the present disclosure;

FIG. 4 is a schematic illustration of a method for preparing a glass etching solution according to an embodiment of the present disclosure;

FIG. 5 is a micrograph of glass with a blazed pattern prepared in example 6;

FIG. 6 is a micrograph of glass with a blazed pattern prepared in example 7;

FIG. 7 is a micrograph of glass with a blazed pattern prepared in example 8;

FIG. 8 is a micrograph of glass with a blazed pattern prepared in example 9;

FIG. 9 is a micrograph of the glass with a blazed pattern prepared in example 10;

FIG. 10 is a micrograph of glass with a blazed pattern prepared in example 11;

FIG. 11 is a micrograph of glass with a blazed pattern prepared in example 12;

FIG. 12 is a micrograph of glass with a blazed pattern prepared in example 13;

FIG. 13 is a micrograph of glass with a blazed pattern prepared in example 14;

FIG. 14 is a micrograph of glass with a blazed pattern prepared in example 15;

FIG. 15 is a micrograph of glass with a blazed pattern prepared in example 16;

FIG. 16 is a micrograph of glass with a blazed pattern prepared in example 17;

FIG. 17 is a micrograph of a glass with a blazed pattern prepared in example 18;

FIG. 18 is a micrograph of glass with a blazed pattern prepared in example 19;

FIG. 19 is a micrograph of a glass with a blazed pattern prepared in example 20;

FIG. 20 is a micrograph of glass with a blazed pattern prepared in example 21;

FIG. 21 is a micrograph of glass with a blazed pattern prepared in example 22;

FIG. 22 is a micrograph of etched glass prepared from comparative example 3;

FIG. 23 is a micrograph of etched glass prepared in comparative example 4.

Detailed Description

The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.

The existing glass etching process is complex, the process conditions are strict, the processing time is long, and the formed etched glass is single in appearance and cannot meet the diversified demands of users. The application provides a glass etching liquid, and the glass can be soaked in the glass etching liquid to form a crystal-shining pattern on the surface of the glass.

For an explanation of a specific structure of the blazed pattern of the present application, please refer to fig. 1 and fig. 2, fig. 1 is a microscopic image of a glass surface with the blazed pattern provided in an embodiment of the present application, and fig. 2 is a schematic diagram of a blaze distribution of the glass surface with the blaze pattern. As can be seen from fig. 1, different areas of the glass surface have different reflectivities for light, and areas with similar reflectivities can be seen as a flare, and as can be seen from the schematic diagram of fig. 2, a total of 7 flares can be seen in the microscopic diagram shown in fig. 1. Further, as can be seen in fig. 1, the flare on the glass surface microscopically presents a stacked structure resembling a bar-shaped crystal, which is an indentation formed on the glass surface by the crystal mixture generated by the reaction of the glass etching liquid and the glass, i.e., the stacked structure is a microstructure of the glass body, and is not a crystal formed by the reaction of the glass etching liquid and the glass. For convenience of description, the structure of the strip-like crystals in the indentation is named as a crystal-like structure, and as can be seen from fig. 1, the crystal-like crystals in the same arrangement direction are gathered to form a flare, and a plurality of flare combinations form a flare pattern, so that glass with the flare pattern can generate unique visual effects through refraction and reflection of light under different angles, and the ornamental value of the glass is greatly improved.

In the embodiment of the application, the glass etching solution comprises the following components in percentage by mass: ammonium bifluoride: 30% -45%, carboxylate: 0.5 to 1.5 percent of phosphate: 0.5 to 1.5 percent of hydrochloric acid: 0.5 to 4 percent of nitric acid: 31% -45%, water: 10% -20%, wherein the phosphate comprises one or more of normal phosphate, monohydrogen phosphate and dihydrogen phosphate.

In the glass etching liquid, ammonium bifluoride reacts with nitric acid to generate hydrofluoric acid, the hydrofluoric acid can erode and soften glass, and fluorosilicate crystals which are reaction products and ammonium bifluoride crystals which are supersaturated and separated out form a porous and lamellar crystal mixture to be adhered to the surface of the glass together; the hydrochloric acid can accelerate the stripping of metal elements in the glass through pitting, so that the crystallization mixture has complete and regular particles, and the corrosion speed of the glass is accelerated; phosphate forms phosphoric acid under the condition of strong acid, and the phosphate and carboxylate act together to enable pitting corrosion to be quickly converted into local corrosion, promote silicon oxygen chains which are corroded and broken and encircle metal elements of glass to form crystals which are orderly arranged and have certain directivity, adhere to the surface of softened glass to enable the surface of the glass to deform, form different flare spots on the surface of the glass, and remove crystals on the surface of the glass through a cleaning process after the etching is finished, so that the glass with the flare patterns is obtained.

In the embodiment of the application, the mass percentage of the ammonium bifluoride in the glass etching liquid is 30% -45%, and the mass percentage of the ammonium bifluoride in the glass etching liquid can be specifically but not limited to 30%, 35%, 38%, 40%, 42% or 45%. If the content of ammonium bifluoride is too high, the stability of the etching solution is poor, and ammonium bifluoride can be greatly precipitated due to supersaturation, so that a large number of unordered crystals are generated on the surface of glass, the uniformity of crystal arrangement is destroyed, sand leakage can be caused more seriously, and the product yield is low. If the content of ammonium bifluoride is too low, the number of crystals formed is small, the etching depth of the glass surface is shallow, and the crystal flare pattern is not obvious.

In the glass etching liquid, on one hand, the hydrochloric acid can create a strong acid environment, promote the separation of metal elements in glass and accelerate the corrosion speed of ammonium bifluoride, and on the other hand, the hydrochloric acid can adjust the concentration of hydrogen ions and control the precipitation speed of crystals, so that crystals with complete particles and similar sizes are obtained. In the embodiment of the application, the mass percentage of the hydrochloric acid is 0.5% -4%. The mass percentage of the hydrochloric acid in the glass etching liquid can be specifically but not limited to 0.5%, 1%, 2%, 3% or 4%. When the mass percentage of the hydrochloric acid is too low, metal elements in the glass are difficult to separate, the content of metal ions in etching liquid is low, the content of formed crystals is low, and the crystal shining patterns are not obvious.

In the present application, nitric acid is used as a solvent to promote the dissolution of ammonium bifluoride and phosphate in glass etching liquid, and nitric acid is used for providing hydrogen ions H ⁺ To create a strong acid environment. In the embodiment of the application, the mass percentage of the nitric acid in the glass etching liquid is 31% -45%, and the mass percentage of the nitric acid in the glass etching liquid can be specifically but not limited to 31%, 35%, 38%, 40%, 42% or 45%.

In the glass etching liquid, carboxylate is organic carboxylate soluble in acid, and on one hand, the carboxylate provides metal ions and accelerates fluosilicate ions (SiF ₆ ^2- ) Promoting the adequate formation of crystals; on the other hand, the carboxylate has certain complexation in strong acid environment, can accelerate the removal of metal elements in glass and stabilize generated fluorineThe silicate enables the fluorosilicate and ammonium bifluoride crystals to grow orderly, the size of the crystals and the coverage area of the crystal mixture are increased, and the size of the glass surface crystals is also increased, so that more obvious flare is formed; in addition, carboxylate can reduce liquid level tension, promote glass etching liquid to fully infiltrate glass, and reduce sand leakage rate. In some embodiments of the present application, the carboxylate salt comprises one or more of zinc acetate, magnesium acetate, potassium acetate, sodium acetate, zinc propionate, magnesium propionate, potassium propionate, sodium lactate, potassium lactate, sodium oxalate, potassium oxalate, sodium acrylate, potassium acrylate, sodium benzoate, potassium benzoate, sodium citrate, and sodium succinate. In some embodiments of the present application, the carboxylate in the glass etching solution is selected from acetate, and the acetate can reduce the surface tension of the solution, enlarge the contact area of the glass after immersion, ensure the sufficient contact between the solution and the glass, and reduce the etching failure. In some embodiments of the application, carboxylate in the glass etching solution is selected from zinc acetate, the zinc acetate not only can promote uniform dispersion of each component, but also can accelerate stripping of metal elements such as Al, ca and the like in glass to form a polymer, so that the glass etching speed is accelerated; zinc acetate has good stabilizing effect on the polymer and can balance the metal ion content in the solution.

In the embodiment of the application, the mass percentage of the carboxylate in the glass etching liquid is 0.5% -1.5%, and the mass percentage of the carboxylate in the glass etching liquid can be specifically but not limited to 0.5%, 0.6%, 0.8%, 1%, 1.25% or 1.5%. When the carboxylate content is too high, the metal ion content in the glass etching liquid is increased, so that the crystal nucleation position is unstable, the arrangement of crystals tends to be disordered, and the formed flare is small in size and poor in uniformity. When the carboxylate content is too low, the crystal size is small, the etching depth is shallow, and the flare size is small, and the aesthetic property of the obtained glass is also reduced. In the application, when the flare size of the surface of the glass is 400-700 mu m, the flare pattern of the glass is more obvious and attractive, and the glass has good visual effect. In some embodiments of the present application, the mass ratio of carboxylate to ammonium bifluoride is 1 (30-90), and the mass ratio of carboxylate to ammonium bifluoride may be, but is not limited to, 1:30, 1:35, 1:37, 1:40, 1:50, 1:70 or 1:90 in particular. The mass ratio of carboxylate to ammonium bifluoride is controlled to form crystals with complete grains and uniform size, so that uniform quasi-crystals are formed on the surface of glass.

In the application, the phosphate can not only provide metal ions and accelerate the deposition of fluorosilicate, but also form phosphoric acid in a strong acid environment, and the phosphoric acid can convert pitting corrosion into local corrosion so as to connect a reaction area into slices. In embodiments of the present application, the phosphate salt includes one or more of a normal phosphate salt, a monohydrogen phosphate salt, and a dihydrogen phosphate salt. In some embodiments of the present application, the normal phosphate salt comprises one or more of sodium phosphate, potassium phosphate, calcium phosphate, and aluminum phosphate, the mono-hydrogen phosphate salt comprises one or more of sodium phosphate monobasic, potassium phosphate monobasic, calcium phosphate monobasic, and aluminum phosphate monobasic, and the mono-hydrogen phosphate salt comprises one or more of sodium phosphate monobasic, potassium phosphate monobasic, calcium phosphate monobasic, and aluminum phosphate monobasic. In some embodiments of the present application, the glass etching solution includes a phosphoric acid normal salt, the phosphoric acid normal salt has a higher metal content than the hydrogen phosphate salt, a regular porous layered crystallization mixture is easier to form, and the phosphoric acid normal salt forms phosphoric acid in a strong acid environment at a high speed. In the embodiment of the application, the mass percentage of the phosphate in the glass etching liquid is 0.5% -1.5%, and the mass percentage of the phosphate in the glass etching liquid can be specifically but not limited to 0.5%, 0.6%, 0.8%, 1%, 1.25% or 1.5%. When the content of phosphate is too high, the acid environment of the solution is affected, the stability of etching solution is reduced, sediment is generated, and the frosting effect is achieved; when the content of phosphate is too low, the flare uniformity of the glass surface is poor, and the aesthetic property is greatly reduced.

In the application, under the strong acid environment, phosphate and carboxylate have the functions of synergistically promoting precipitated ammonium bifluoride and corroded and broken silicon oxygen chains surrounding glass metal elements to form a crystal mixture which is orderly arranged and has certain directivity, the crystal mixture forms orderly distributed quasi-crystals on the surface of softened glass, and the orderly distributed quasi-crystals which face the same are macroscopically presented as flare; the arrangement direction of the quasi-crystals in the flare depends on the distribution and growth direction of the crystals in the crystal mixture, the crystal mixture generated in the glass etching liquid is a lamellar porous structure connected in a lamellar manner, the size of the lamellar region determines the size of the flare, and when the crystals in different lamellar regions are arranged and grow in different directions, the quasi-crystal clusters with different directions are obtained when the crystals are reversely acted on the glass surface, namely, different flare patterns are formed by a plurality of flare patterns on the glass surface. In embodiments of the present application, the mass ratio of carboxylate to phosphate is 1 (0.5-2), and the mass ratio of carboxylate to phosphate may specifically be, but is not limited to, 1:0.5, 1:1, 1:1.5, or 1:2.

In some embodiments of the present application, the glass etching solution further includes 0.1% -5% by mass of an organic acid. The mass percentage of the organic acid in the glass etching liquid can be specifically but not limited to 0.1%, 0.5%, 1%, 3% or 5%. The organic acid can regulate the concentration of hydrogen ions in the glass etching liquid, inhibit the problem of uneven etching caused by over-strong acidity and over-fast local reaction, and promote the uniform dispersion of each component in the etching liquid. Specifically, the negatively charged organic acid radical can be combined with the positively charged solute to form an organic film, so that the aggregation effect between solutes is inhibited, each component in the glass etching liquid can be uniformly dispersed, the glass etching liquid can have longer service life, and the glass etching liquid can be stored for a long time. In some embodiments of the present application, the organic acid comprises one or more of oxalic acid, tartaric acid, citric acid, acetic acid, sulfamic acid, sorbic acid, and maleic acid. The organic acid can effectively promote the uniform dispersion of the components, and no bubbles are generated, so that the crystal and brilliant pattern on the surface of the glass can be uniformly distributed. In some embodiments of the present application, the organic acid used is citric acid, pK of citric acid _a 3.15, the acidity is moderate, the pH value of the solution can be effectively regulated, and the dispersion effect is good.

In some embodiments of the present application, the glass etching solution further includes a thickener, the thickener can adjust the viscosity of the glass etching solution, the mass percentage of the thickener in the glass etching solution is 0.5% -5%, and the mass percentage of the thickener in the glass etching solution can be specifically but not limited to 0.5%, 1%, 3% or 5%. In embodiments of the present application, one or more of glycerol, triethanolamine, ethylene glycol, methanol, hexanol, octanol, maltose, sodium polyacrylate, polyethylene glycol, polyvinylpyrrolidone, and polyacrylamide are included. In some embodiments of the present application, the viscosity adjustment range of the thickener is 2cP to 50cP, the viscosity of the final glass etching solution is 4cP to 100cP, and the viscosity of the glass etching solution may be, but is not limited to, 4cP, 10cP, 20cP, 30cP, 50cP, 80cP or 150cP. In some embodiments of the present application, the viscosity of the glass etching solution is 4cP to 55cP. The viscosity of the glass etching liquid is controlled, so that the diffusion speed of the reaction ions is moderate, and uniform etching is realized.

In the present application, water in the glass etching liquid acts as a diluent and a solvent to promote ionization of hydrogen ions and dissolve carboxylate and phosphate. In the embodiment of the application, the mass percentage of the water in the glass etching liquid is 10% -20%, and the mass percentage of the water in the glass etching liquid can be specifically but not limited to 10%, 13%, 15% or 20%.

The glass etching liquid provided by the application has simple and uniform components, does not contain solid components, has good stability, and can be stored for a long time; when the glass etching agent is applied to a glass etching process, a crystal pattern can be formed on the surface of the glass, so that the aesthetic property of the glass is improved, and the glass has the anti-dizziness function; the glass etching liquid can be reused, and the spent components of the solution can be reused after being filtered and replenished, so that the cost of the glass etching process is reduced, and compared with the existing etching liquid, the glass etching liquid is more environment-friendly.

The application also provides a preparation method of the glass etching liquid, which comprises the following steps: mixing 30-45% of ammonium bifluoride, 0.5-1.5% of carboxylate, 0.5-1.5% of phosphate, 0.5-5% of hydrochloric acid, 30-45% of nitric acid and 10-20% of water to obtain glass etching liquid, wherein the phosphate comprises one or more of normal phosphate, monohydrogen phosphate and dihydrogen phosphate.

In some embodiments of the present application, a method for preparing a glass etching solution is shown in fig. 3, referring to fig. 3, fig. 3 is a method for preparing a glass etching solution according to an embodiment of the present application, and the method is named as a first preparation method, where the first preparation method includes:

Step 100: adding ammonium bifluoride into nitric acid and uniformly stirring to obtain a first mixture;

step 200: adding phosphate and carboxylate to the first mixture to obtain a second mixture;

step 300: and adding water and hydrochloric acid into the second mixture, and uniformly stirring to obtain the glass etching liquid.

In some embodiments of the present application, the glass etching solution further includes an organic acid with a mass percentage of 1% -5% and a thickener with a mass percentage of 0.5% -5%, and the first preparation method of the glass etching solution includes:

step 100: adding nitric acid into citric acid and uniformly stirring to obtain a first mixture;

step 200: adding ammonium bifluoride into the first mixture and uniformly stirring to obtain a second mixture;

step 300: adding a thickener into the second mixture and uniformly stirring to obtain a third mixture;

step 400: adding phosphate and carboxylate into the third mixture and stirring uniformly to obtain a fourth mixture;

step 500: and adding water and hydrochloric acid into the fourth mixture, and uniformly stirring to obtain the glass etching liquid.

In some embodiments of the present application, a method for preparing a glass etching solution is shown in fig. 4, referring to fig. 4, fig. 4 is a method for preparing a glass etching solution according to an embodiment of the present application, and the method is named as a second preparation method, where the second preparation method includes:

Step 100: uniformly mixing ammonium bifluoride, phosphate and carboxylate to obtain a first mixture;

step 200: adding nitric acid into the first mixture and uniformly stirring to obtain a second mixture;

In some embodiments of the present application, the glass etching solution further includes an organic acid with a mass percentage of 1% -5% and a thickener with a mass percentage of 0.5% -5%, and the second preparation method of the glass etching solution includes:

step 100: uniformly mixing citric acid, ammonium bifluoride, phosphate and carboxylate to obtain a first mixture;

step 300: and adding a thickener, water and hydrochloric acid into the second mixture, and uniformly stirring to obtain the glass etching liquid.

In the preparation method, after water and hydrochloric acid are added into the mixture, the mixture can be kept still for a period of time to enable the solute to be fully ionized in the glass etching liquid, so that the glass etching liquid can be used for uniformly etching glass, and the problem of sand leakage is solved. In some embodiments of the present application, the standing time is 3h to 20h, and the standing time may be, but not limited to, 3h, 7h, 10h, 15h, or 20h.

In the application, when the first preparation method is adopted, as the solid salt components are added into the acid liquid step by step, the nitric acid can promote the dissolution of the solid salt, and the organic acid can promote the uniform dispersion of the components, so that the glass etching liquid with uniform components can be obtained, and the method avoids the problem of liquid splashing caused by mixing multiple solutes and adding the solvent, and has higher safety.

The preparation method of the glass etching liquid is simple to operate, is favorable for industrial preparation, can produce the glass etching liquid with stable components, and is favorable for popularization and use of the glass etching liquid.

The application also provides a production method of the glass with the blazed patterns, which comprises the following steps:

and placing the glass into the glass etching liquid for etching to obtain the glass with the brilliant pattern.

In some embodiments of the present application, the glass is cleaned and infiltrated prior to etching, the infiltrating comprising: and (3) soaking the glass in an acidic solution for a period of time, wherein the acidic solution comprises hydrofluoric acid, the mass percentage of the hydrofluoric acid is 1-5%, and the soaking treatment time is 5-60 s. The glass is subjected to infiltration treatment, so that the hydrophilic performance of the glass can be improved, and the etching liquid is favorable for fully infiltrating the surface of the glass, so that the reaction between the glass etching liquid and the glass is promoted, and the glass is uniformly etched. In some embodiments of the present application, etching is performed only on one side surface of glass, that is, only a blazed pattern is formed on one side surface of glass, for forming a single-side blazed pattern, one side surface of glass can be protected first, a protective layer is arranged on the surface which does not need etching, after the etching process is completed, glass with a blazed pattern on one side can be obtained by cleaning, drying and removing the protective layer, and if the blazed pattern is to be formed on both sides of glass, the glass is not required to be protected.

In this embodiment, the etching time is 0.75min to 5min, and the etching time may be, but is not limited to, 0.75min, 1min, 2min, 3min or 5min. The etching time is controlled to ensure that the surface of the glass has clear crystal patterns and the glass has good texture. In the embodiment of the application, the etching temperature is 10-30 ℃, the etching temperature can be particularly but not limited to 10 ℃, 20 ℃, 25 ℃, 28 ℃ or 30 ℃, the etching liquid has low temperature requirement, and glass can be etched at normal temperature, so that the process cost is reduced.

In the embodiment of the application, after etching is completed, the glass with the blazed pattern is soaked in water for 10 s-5 min to remove crystals attached to the surface of the glass, and after soaking is completed, the surface of the glass is cleaned and dried to obtain the glass with the blazed pattern, wherein the time for soaking the glass after etching in water can be specifically but not limited to 10s, 30s, 1min, 2min, 3min or 5min.

The production method of the glass with the brilliant patterns has wide application range, can etch various glasses, and can be aluminum silicon glass, sodium glass, soda lime glass, colored glass and sodium potassium glass. The production method has the advantages of simple conditions, short treatment time, low process cost and good application prospect.

The application also provides the glass with the blazed pattern, which is prepared by the production method of the glass with the blazed pattern. In the embodiment of the application, the glass surface with the blazed pattern is provided with the quasi-crystals, and the quasi-crystals are orderly arranged to form the blaze. In the present embodiment, the average particle diameter of the quasi-crystals is 10 μm to 200 μm, and the average particle diameter of the quasi-crystals may be, but not limited to, 10 μm, 30 μm, 50 μm, 80 μm, 100 μm, 150 μm or 200 μm. In embodiments of the present application, the average diameter of the flare may be, but is not limited to, specifically 100 μm, 200 μm, 300 μm, 500 μm, 600 μm, 700 μm, or 800 μm. In some embodiments of the present application, when the average diameter of the flare is 400 μm to 700 μm and the average diameter of the flare is 400 μm to 700 μm, it indicates that the orientation of the crystal-like clusters is relatively regular and the area of the clusters is relatively large, so that the flare is more obvious on a macroscopic scale, and the visual effect of the crystal-like patterns is more prominent. In some embodiments of the present application, the glass having a blazed pattern has an etch depth of 3 μm to 30 μm, which can be measured by a surface roughness meter.

Embodiments of the present application are further described below in terms of a number of examples.

Example 1

A method for preparing glass with a blazed pattern, comprising:

adding citric acid into nitric acid, stirring uniformly, sequentially adding sodium phosphate, stirring uniformly, zinc acetate dihydrate, ammonium bifluoride, water and hydrochloric acid mixture, glycerol, and standing for 8 hours to obtain glass etching liquid. The glass etching liquid comprises the following components in percentage by mass:

sodium phosphate (Na) ₃ PO ₄ ): 1, zinc acetate dihydrate (C) ₄ H ₁₀ O ₆ Zn): 1, ammonium bifluoride (NH) ₄ HF ₂ ): 37%, water (H) ₂ O): 15% nitric acid (HNO) ₃ ): 39%, citric acid (C) ₆ H ₈ O ₇ ): 3%, glycerol (C) ₃ H ₈ O ₃ )：4％。

Example 2

Adding ammonium bifluoride into nitric acid, stirring uniformly, sequentially adding sodium phosphate, stirring uniformly zinc acetate dihydrate, stirring uniformly a mixture of water and hydrochloric acid, stirring uniformly glycerol, and standing for 8 hours to obtain glass etching liquid. The glass etching liquid comprises the following components in percentage by mass:

sodium phosphate (Na) ₃ PO ₄ ): 1, zinc acetate dihydrate (C) ₄ H ₁₀ O ₆ Zn): 1, ammonium bifluoride (NH) ₄ HF ₂ ): 37%, water (H) ₂ O): 18%, nitric acid (HNO) ₃ ): 39%, glycerol (C) ₃ H ₈ O ₃ )：4％。

Example 3

sodium phosphate (Na) ₃ PO ₄ ): 1, zinc acetate dihydrate (C) ₄ H ₁₀ O ₆ Zn): 0.5% ammonium bifluoride (NH) ₄ HF ₂ ): 37.5%, water (H) ₂ O): 15% nitric acid (HNO) ₃ ): 39%, citric acid (C) ₆ H ₈ O ₇ ): 3%, glycerol (C) ₃ H ₈ O ₃ )：4％。

Example 4

sodium phosphate (Na) ₃ PO ₄ ): 1.25%, ethylene dihydrateZinc acid (C) ₄ H ₁₀ O ₆ Zn): 0.75% ammonium bifluoride (NH) ₄ HF ₂ ): 37%, water (H) ₂ O): 15% nitric acid (HNO) ₃ ): 39%, citric acid (C) ₆ H ₈ O ₇ ): 3%, glycerol (C) ₃ H ₈ O ₃ )：4％。

Example 5

Adding citric acid into nitric acid, stirring uniformly, sequentially adding sodium dihydrogen phosphate, stirring uniformly, sodium acetate trihydrate, ammonium bifluoride, water and hydrochloric acid mixture, maltose, and standing for 8 hours to obtain glass etching liquid. The glass etching liquid comprises the following components in percentage by mass:

Sodium monohydrogen phosphate (Na) ₂ HPO ₄ ): 1, sodium acetate trihydrate (C ₄ H ₁₀ O ₆ Na ₂ ): 1, ammonium bifluoride (NH) ₄ HF ₂ ): 37%, water (H) ₂ O): 18%, nitric acid (HNO) ₃ ): 39%, citric acid (C) ₆ H ₈ O ₇ ): 3%, maltose (C) ₁₂ H ₂₂ O ₁₁ )：1％。

Comparative example 1

sodium phosphate (Na 3PO 4): 1%, sodium dodecyl sulfate (C4H 10O6 Zn): 0.3% ammonium bifluoride (NH 4HF 2): 37%, water (H2O): 15.7%, nitric acid (HNO 3): 39%, citric acid (C6H 8O 7): 3%, glycerol (C3H 8O 3): 4%.

Comparative example 2

zinc acetate dihydrate (C) ₄ H ₁₀ O ₆ Zn): 1, ammonium bifluoride (NH) ₄ HF ₂ ): 37.5%, water (H) ₂ O): 16%, nitric acid (HNO) ₃ ): 39%, citric acid (C) ₆ H ₈ O ₇ ): 3%, glycerol (C) ₃ H ₈ O ₃ )：4％。

Effect examples

To verify the properties and effects of the glass etching solutions of the present application, effect examples are also provided.

1) Three glass plates are provided, wherein the No. 1 glass plate is low-alumina silica glass, and the components comprise: aluminum 1.91%, silicon 17.56%, other metal elements 6.8%; the No. 2 glass plate is colored glass, and the components comprise: 10.51% of aluminum, 19.87% of silicon and 16.43% of other metal elements; the No. 3 glass plate is high alumina silica glass, and the components of the glass plate are as follows: 12.71% of aluminum, 31.07% of silicon and 23% of other metal elements. A plurality of glass plates are respectively placed in glass etching solutions of examples 1-5 and comparative examples 1-2, and specifically, the preparation process of glass with a brilliant pattern comprises the following steps: cleaning the surface of the glass, and performing infiltration treatment, wherein the infiltration treatment comprises the following steps: placing the glass in hydrofluoric acid with the mass percentage of 2% for soaking for 20 seconds, and then cleaning with water to obtain wet glass; and placing the wet glass in glass etching liquid, treating for a period of time at a certain temperature, taking out the glass, cleaning the glass, and drying to obtain the glass with the brilliant pattern. Taking example 6 as an example, the preparation process of the glass with the blazed pattern in example 6 is as follows:

And (3) taking a No. 1 glass plate, cleaning and soaking the surface of the glass, placing the glass into the glass etching liquid prepared in the embodiment 1, wherein the etching temperature is 20 ℃, the etching time is 2min, washing the soaked glass with clear water after the etching is finished, and drying the washed glass to obtain the product.

Glass with a blazed pattern was prepared under different conditions, examples 6 to 22 were glasses with a blazed pattern prepared using the glass etching solutions of examples 1 to 5, and comparative examples 3 to 4 were etched glasses prepared using the etching solutions of comparative examples 1 to 2, and the preparation conditions of the etched glasses of examples 6 to 22 and comparative examples 3 to 4 were as shown in table 1.

TABLE 1 preparation conditions Table for etched glasses of examples 6-22 and comparative examples 3-4

2) The surfaces of the glasses with the blazed patterns of examples 6 to 22 and the glasses of comparative examples 3 to 4 were etched using a microscope and naked eyes, and the average particle diameter and average diameter of the blaze of the crystals-like crystals of the surfaces of the glasses of examples 6 to 22 were recorded, see fig. 5 to 23, wherein fig. 5 is a micrograph of the glass with the blazed patterns prepared in example 6, fig. 6 is a micrograph of the glass with the blazed patterns prepared in example 7, fig. 7 is a micrograph of the glass with the blazed patterns prepared in example 8, fig. 8 is a micrograph of the glass with the blazed patterns prepared in example 9, fig. 9 is a micrograph of the glass with the blazed patterns prepared in example 10, fig. 10 is a micrograph of the glass with the blazed patterns prepared in example 11, fig. 11 is a micrograph of the glass with the blazed patterns prepared in example 12, fig. 12 is a micrograph of the glass with a blaze pattern prepared in example 13, fig. 13 is a micrograph of the glass with a blaze pattern prepared in example 14, fig. 14 is a micrograph of the glass with a blaze pattern prepared in example 15, fig. 15 is a micrograph of the glass with a blaze pattern prepared in example 16, fig. 16 is a micrograph of the glass with a blaze pattern prepared in example 17, fig. 17 is a micrograph of the glass with a blaze pattern prepared in example 18, fig. 18 is a micrograph of the glass with a blaze pattern prepared in example 19, fig. 19 is a micrograph of the glass with a blaze pattern prepared in example 20, fig. 20 is a micrograph of the glass having a blazed pattern prepared in example 21, fig. 21 is a micrograph of the glass having a blazed pattern prepared in example 22, fig. 22 is a micrograph of the etched glass prepared in comparative example 3, and fig. 23 is a micrograph of the etched glass prepared in comparative example 4.

Referring to fig. 5, fig. 5 is a micrograph of the glass with a blazed pattern prepared in example 6, wherein the grain size of the crystals in fig. 5 is the length of the long side of the crystals, the grain sizes of the crystals measured are 93.77 μm, 28.63 μm, 40.84 μm, 62.47 μm, 50.10 μm, 64.22 μm, 84.71 μm, 117.89 μm and 26.96 μm, respectively, and the average grain size of the crystals in example 6 is 63.29 μm, and the average diameter of the blaze is 550.38. See table 2 for test results of the glass with blazed patterns of examples 6-22.

Table 2 structural parameter tables of glasses with blazed patterns of examples 6 to 22

Referring to fig. 5 and 6, fig. 5 is a microscopic view of the glass with the blazed pattern prepared in example 6, and fig. 6 is a microscopic view of the glass with the blazed pattern prepared in example 7. As can be seen from examples 6 and 7, the etching temperature affects the sizes of the flare and the quasi-crystal, and the sizes of the quasi-crystal and the flare are smaller under the low temperature condition because the low temperature environment suppresses the ion exchange and the grain growth speed, so the sizes of the quasi-crystal and the flare are smaller.

As can be seen from fig. 9 to 11, that is, the microscopic diagrams of the glass having the blaze pattern of example 10 to example 12, when the glass etching liquid of example 2 containing no organic acid is used, the etching unevenness problem is locally present on the glass surface, the size of part of the blaze is reduced, and the average size of the whole blaze is reduced, which means that the uniformity of etching and the average size of the blaze can be improved by adding the organic acid to the etching liquid.

As can be seen from fig. 12 to fig. 18, that is, the microscopic diagrams of the glasses with the blaze patterns of examples 13 to 19, when the glass etching solutions of examples 3 and 4 are adopted, the blaze sizes of the surfaces of the glasses are larger, and the blaze patterns are more remarkable, which indicates that a proper amount of carboxylate is added, the concentration of metal ions in the solution is reasonably controlled, and the rapid generation of crystalline substances is facilitated, so that the lamellar region is enlarged, and the blaze with a larger size is formed.

As can be seen from fig. 16, i.e., the micrograph of the glass having the blazed pattern of example 17, the extension of the etching time is advantageous for increasing the grain size of the quasi-crystals, but the size of the blaze is reduced because the extension of the etching time allows the grains to sufficiently grow, and the blaze is reduced because a large number of the lamellar regions to grow overlap by the long-time etching, and the crystal orientation of the edge region changes, so the size of the blaze is reduced.

As can be seen from the microscopic images of fig. 19 to 21, i.e., examples 20 to 22, showing the glass having the blazed pattern, the glass etching liquid of example 5 uses different kinds of phosphates and carboxylates, and the obtained etched glass has a reduced surface crystal-like and blaze size, but is still within the range of good visual effect.

As can be seen from fig. 22, which is a micrograph of the etched glass prepared in comparative example 3, the glass etching solution of comparative example 1 does not contain carboxylate, and thus cannot generate a complete flare pattern.

As can be seen from the micrograph of the etched glass prepared in fig. 23, comparative example 4, the absence of the carboxylate has a smaller effect on the crystal-like size and a larger effect on the flare size, because the fluorosilicate grains adhering to the glass surface are mainly generated by the metal elements peeled off by the glass itself, while the fluorosilicate grains participating in the outer grains composing the flaky region are mainly generated by the metal ions of the solution itself, in addition to the precipitated ammonium bifluoride.

3) The glasses with the blazed patterns of examples 6-22 and the etched glasses of comparative examples 3-4 were visually observed to see whether there were unetched areas, and the areas where neither the glasses with the blazed patterns of the examples of the present application had leaked sand were observed, whereas the surface sand leakage rates of the etched glasses of comparative examples 3 and 4 were 5% -6%.

4) The glasses with the blazed patterns of examples 6 to 22 and the etched glasses of comparative examples 3 and 4 were visually observed to see whether there was a region of uneven pattern, and the glasses with the blazed patterns of the examples of the present application were observed to have no region of uneven etching as a whole, whereas the etched glasses of comparative examples 4 and 5 had an uneven etching rate of 5% to 7%.

5) The glass with a blazed pattern of examples 6-22 and the etched glass of comparative examples 3-4 were tested for haze, transmittance, and roughness using a color spectrum haze meter CS-720, and roughness using a surface roughness meter. The test results refer to table 3, wherein the roughness characterization includes: r is R _a : an arithmetic mean; r is R _z : average peak-to-valley depth; r is R _t : the sum of the highest value of the profile peak and the lowest value of the profile valley;

TABLE 3 apparent parameters tables for glass having blazed patterns of examples 6-22 and etched glasses of comparative examples 3-4

As can be seen from Table 3, the glass with the blazed patterns has the advantages of large haze value, lower transmittance, better dizziness preventing effect, lower roughness value and fine hand feeling. The glass etching liquid has larger difference in roughness and etching depth for glasses with different components, and the etching result is related to the glass components in addition to the etching liquid. The normal etching roughness of the first low-alumina silicate glass is generally more than 0.6 mu m, and the depth is generally more than 3.5 mu m; the normal etching roughness of the colored glass II is generally more than 0.15 mu m, and the depth is generally more than 1.5 mu m; the normal etching roughness of the third high alumina silicate glass is generally more than 0.4 mu m, and the depth is generally more than 2.5 mu m.

The foregoing is a preferred embodiment of the present application and is not to be construed as limiting the scope of the present application. It should be noted that modifications and adaptations to the principles of the present application may occur to one skilled in the art and are intended to be comprehended within the scope of the present application.

Claims

1. The glass etching liquid is characterized by comprising the following components in percentage by mass:

ammonium bifluoride: 30% -45%;

carboxylate: 0.5 to 1.5 percent;

phosphate: 0.5 to 1.5 percent;

hydrochloric acid: 0.5 to 4 percent;

nitric acid: 31% -45%;

water: 10% -20%;

2. The glass etching liquid according to claim 1, wherein a mass ratio of the carboxylate to the ammonium bifluoride is 1 (30 to 90).

3. The glass etching liquid according to claim 1 or 2, wherein the mass ratio of the carboxylate to the phosphate is 1 (0.5 to 2).

4. The glass etching solution of any of claims 1-3, wherein the carboxylate salt comprises one or more of zinc acetate, magnesium acetate, potassium acetate, sodium acetate, zinc propionate, magnesium propionate, potassium propionate, sodium lactate, potassium lactate, sodium oxalate, potassium oxalate, sodium acrylate, potassium acrylate, sodium benzoate, potassium benzoate, sodium citrate, and sodium succinate.

5. The glass etching solution according to any one of claims 1 to 4, wherein the phosphoric acid normal salt comprises one or more of sodium phosphate, potassium phosphate, calcium phosphate, and aluminum phosphate; the monohydrogen phosphate comprises one or more of sodium monohydrogen phosphate, potassium monohydrogen phosphate, calcium monohydrogen phosphate and aluminum monohydrogen phosphate; the dihydrogen phosphate salt comprises one or more of sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate and aluminum dihydrogen phosphate.

6. The glass etching solution according to any one of claims 1 to 5, further comprising 1 to 5 mass percent of an organic acid comprising one or more of acetic acid, oxalic acid, tartaric acid, citric acid, sulfamic acid, sorbic acid, and maleic acid.

7. The glass etching solution according to any one of claims 1 to 6, further comprising 0.5 to 5% by mass of a thickener comprising one or more of glycerol, triethanolamine, ethylene glycol, methanol, hexanol, octanol, maltose, sodium polyacrylate, polyethylene glycol, polyvinylpyrrolidone, and polyacrylamide.

8. A method for producing glass with a blazed pattern, comprising the steps of:

providing a glass etching solution according to any one of claims 1 to 7;

9. The method of claim 8, wherein the etching time is 0.75min to 5min; the etching temperature is 10-30 ℃.

10. Glass with a blazed pattern, characterized in that the glass with a blazed pattern is produced by the production method according to claim 8 or 9.