CN116040951A

CN116040951A - Glass etching liquid and preparation method thereof, striped glass and production method thereof

Info

Publication number: CN116040951A
Application number: CN202111267082.2A
Authority: CN
Inventors: 袁涛; 罗富华; 马兰
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
Anticipated expiration: 2041-10-28
Also published as: CN116040951B

Abstract

The application provides a glass etching liquid, which comprises the following components in percentage by mass: ammonium bifluoride: 20% -30%; metal fluoride: 2% -5%; hydrogen phosphate: 2% -5%; nitric acid: 15% -30%; sulfuric acid: 12% -25%; organic acid: 5% -10%; water: 15% -20%. The glass etching liquid has uniform components and good stability, and etching stripes can be formed on the surface of the glass through simple steps when the glass etching liquid is applied to a glass etching process, so that the glass has uniform, comprehensive and attractive stripe appearance effect. The application also provides a preparation method of the glass etching liquid, stripe glass and a production method thereof.

Description

Glass etching liquid and preparation method thereof, striped glass and production method thereof

Technical Field

The application relates to the technical field of glass processing, in particular to glass etching liquid and a preparation method thereof, and striped glass 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 requirements of people, and has weak competitiveness. And the conventional glass etching method is difficult to process special patterns, so that the commercialization process of special pattern glass is limited. Therefore, there is a need to provide a new appearance glass product and a method for making the same to meet the different needs of people for glass products.

Disclosure of Invention

In view of the above, the present application provides a glass etching solution, which has uniform components and good stability, and when applied to a glass etching process, can form etching stripes on the surface of glass through simple steps, so that the glass has uniform, comprehensive and beautiful stripe appearance effect.

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

ammonium bifluoride: 20% -30%;

metal fluoride: 2% -5%;

hydrogen phosphate: 2% -5%;

nitric acid: 15% -30%;

sulfuric acid: 12% -25%;

organic acid: 5% -10%;

water: 15% -20%.

In the etching solution, ammonium bifluoride and metal fluoride can erode the surface of glass under an acidic condition, the surface of the glass is softened, and fluorosilicate which is a reaction product of the ammonium bifluoride and the ammonium bifluoride can form precipitation and be deposited on the surface of the glass together with supersaturated ammonium bifluoride precipitation to form a micro-sink; the structure of the precipitate can be adjusted cooperatively by the hydrogen phosphate, the metal fluoride, the sulfuric acid, the nitric acid and the organic acid, so that the micro-sink formed by the precipitate is macroscopically in a striped pattern. Under the synergistic effect of the components with the specific mass percentage, the obtained glass etching liquid has uniform components, is not easy to generate coagulation, has good stability and can generate uniform stripe patterns on the surface of glass.

Optionally, the glass etching solution further comprises phosphoric acid, and the mass percentage of the phosphoric acid is less than or equal to 10%.

Optionally, the glass etching liquid further comprises a thickener, wherein the mass percentage of the thickener is 1% -2%.

Optionally, the metal fluoride includes one or more of potassium fluoride, sodium fluoride, and aluminum fluoride.

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

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

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

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

ammonium bifluoride: 20% -30%;

metal fluoride: 2% -3%;

hydrogen phosphate: 2% -4%;

nitric acid: 20% -29%;

sulfuric acid: 18% -20%;

phosphoric acid: 7% -10%;

organic acid: 7% -10%;

and (3) a thickening agent: 1 to 2 percent of

Water: 17% -20%.

Optionally, the molar concentration of the fluoride ions in the glass etching liquid is 8mol/L-20mol/L.

Optionally, the molar concentration of hydrogen ions in the glass etching liquid is 18mol/L-33mol/L.

Optionally, the viscosity of the glass etching liquid is 40-150 cP.

In a second aspect, the present application provides a method for preparing a glass etching solution, including the following steps:

uniformly mixing the following raw materials in percentage by mass to obtain a glass etching solution:

ammonium bifluoride: 20% -30%;

metal fluoride: 2% -5%;

hydrogen phosphate: 2% -5%;

nitric acid: 15% -30%;

sulfuric acid: 12% -25%;

organic acid: 5% -10%;

water: 15% -20%.

Optionally, the preparation method comprises the following steps: and uniformly mixing the ammonium bifluoride, the metal fluoride, the hydrogen phosphate and the organic acid, adding the nitric acid into the mixture, uniformly stirring the mixture, adding the water into the mixture, uniformly stirring the mixture, and then adding the sulfuric acid into the mixture to obtain the glass etching liquid.

Optionally, the raw materials further comprise phosphoric acid with the mass percent of less than or equal to 10%, and the preparation method comprises the following steps: and uniformly mixing the ammonium bifluoride, the metal fluoride, the hydrogen phosphate and the organic acid, adding the nitric acid into the mixture, uniformly stirring the mixture, adding the phosphoric acid into the mixture, uniformly stirring the mixture, adding the water into the mixture, uniformly stirring the mixture, and adding the sulfuric acid into the mixture to obtain the glass etching solution.

Optionally, the raw materials further comprise 1-2% of thickener by mass percent, and the preparation method comprises the following steps: and uniformly mixing the ammonium bifluoride, the metal fluoride, the hydrogen phosphate and the organic acid, adding the nitric acid into the mixture, uniformly stirring the mixture, adding the phosphoric acid into the mixture, uniformly stirring the mixture, adding the water and the thickener into the mixture, uniformly stirring the mixture, and adding the sulfuric acid into the mixture to obtain the glass etching liquid.

Optionally, the preparation method comprises the following steps: sequentially adding the organic acid, the ammonium bifluoride, the hydrogen phosphate and the metal fluoride into the nitric acid, uniformly mixing, adding the water, uniformly stirring, and then adding the sulfuric acid to obtain the glass etching liquid.

Optionally, the raw materials further comprise phosphoric acid with the mass percent of less than or equal to 10%, and the preparation method comprises the following steps: mixing the nitric acid with the phosphoric acid, sequentially adding the organic acid, the ammonium bifluoride, the hydrogen phosphate and the metal fluoride into the mixture, uniformly mixing the mixture, adding the water, uniformly stirring the mixture, and then adding the sulfuric acid to obtain the glass etching liquid.

Optionally, the raw materials further comprise 1-2% of thickener by mass percent, and the preparation method comprises the following steps: mixing the nitric acid with the phosphoric acid, sequentially adding the organic acid, the ammonium bifluoride, the hydrogen phosphate and the metal fluoride into the mixture, uniformly mixing the mixture, adding the water and the thickener, uniformly stirring the mixture, and then adding the sulfuric acid to obtain the glass etching liquid.

Optionally, the temperature of the mixing is 0 ℃ to 30 ℃.

Optionally, the preparation method further comprises: and (3) uniformly mixing the raw materials, and standing for 1-6 hours to obtain the glass etching liquid.

The preparation method of the glass etching liquid provided by the second aspect of the application is simple in steps, suitable for large-scale industrial production, and the glass etching liquid with uniform components and good stability can be obtained by adopting the preparation method.

In a third aspect, the present application provides a method for producing a striped glass, 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 striped glass.

Optionally, the etching time is 0.5 min-6 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 5s-3min.

Optionally, the glass comprises aluminosilicate glass.

The production method of the striped glass provided by the third aspect of the application is wide in application range, simple in treatment method, short in treatment time and suitable for industrial production.

In a fourth aspect, the present application provides a striped glass produced by the production method of the third aspect.

Optionally, the striped glass surface has a plurality of etched stripes, and the etched stripes have a width of 10 μm to 50 μm.

Optionally, the distance between adjacent etching stripes is 50 μm-800 μm.

Optionally, a micro-sink is arranged between the adjacent etching stripes, and the depth of the micro-sink is 0.01-10 mu m; the width of the micro-sink is 0.01-5 μm.

The striped glass surface provided by the fourth aspect of the application has uniform striped patterns, so that the glass has special visual effect, and can provide good visual impression for users.

Drawings

FIG. 1 is a schematic illustration of a method for preparing a glass etching solution according to an embodiment of the present disclosure;

FIG. 2 is a schematic illustration of a method for preparing a glass etching solution according to another embodiment of the present disclosure;

FIG. 3 is a micrograph of striped glass prepared in example 8;

FIG. 4 is a pattern diagram of striped glass prepared in example 8;

FIG. 5 is a pattern diagram of striped glass prepared in example 13;

FIG. 6 is a pattern diagram of striped glass prepared in example 15;

FIG. 7 is a pattern diagram of the etched glass prepared in comparative example 4;

FIG. 8 is a pattern diagram of the etched glass prepared in comparative example 5.

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, wherein stripe patterns can be formed on the surface of glass by soaking glass in the glass etching liquid, the method is simple in process, the prepared stripe glass is attractive and attractive, the effect of preventing dizziness is achieved, light rays can be soft and not pricked, good visual experience is brought to users, and personalized pursuits and fashionable pursuits of users are met.

In the embodiment of the application, the glass etching solution comprises the following components in percentage by mass:

ammonium bifluoride: 20% -30%;

metal fluoride: 2% -5%;

hydrogen phosphate: 2% -5%;

nitric acid: 15% -30%;

sulfuric acid: 12% -25%;

organic acid: 5% -10%;

water: 15% -20%.

In the application, sulfuric acid, nitric acid and organic acid can provide hydrogen ions, ammonium bifluoride and metal fluoride can erode the surface of glass in a strong acid environment to soften the glass, silicon in the glass can form fluosilicate radical ions with the fluoride ions, the fluosilicate radical can combine with the metal ions in etching liquid to form flocculent crystal precipitation, and as the concentration of the acid is reduced, ammonium bifluoride can be precipitated and attached to the surface of the glass due to supersaturation; the glass surface is precipitated on the surface of the softened glass to form micro-gaps, and the distribution of the micro-gaps can be regulated through the synergistic effect of the components in the etching solution, so that the surface of the glass presents a stripe pattern;

in the embodiment of the application, the mass percentage of the ammonium bifluoride in the glass etching liquid is 20% -30%, and the mass percentage of the ammonium bifluoride in the glass etching liquid can be specifically but not limited to 20%, 23%, 25%, 27% or 30%. The solubility of ammonium bifluoride in different systems is ordered as: nitric acid > water > sulfuric acid, in the etching process, the acidity of the glass etching liquid is reduced, the solubility of ammonium bifluoride is reduced, and then the ammonium bifluoride is separated out due to supersaturation, so that micro-ravines are formed on the surface of the glass, and the separation process is accompanied with the glass etching reaction, so that the formed micro-ravines are regular. If the content of ammonium bifluoride is too high, the stability of the etching solution is poor, and ammonium bifluoride can be greatly precipitated, so that a large number of irregular micro-sink is generated on the surface of glass, the uniformity of the stripe pattern can be damaged by the irregular micro-sink, and the etching stripe pattern can not be formed seriously. If the content of ammonium bifluoride is too low, less precipitate is generated, the depth of glass surface micro-sink is shallow, and the stripe pattern is not clear.

In this application, metal fluoride not only provides the metal ion in order to promote the formation fluorosilicate deposit, and metal fluoride still can form hydrofluoric acid in strong acid environment to soften glass surface and make the deposit on glass surface have loose structure, and then control the distribution of micro-sink, in addition, metal fluoride can also reduce and separate out the adhesion of crystallization deposit to glass, so that wash and get rid of crystallization deposit. In an embodiment of the present application, the metal fluoride is an acid-soluble metal fluoride salt, and further, the metal fluoride includes one or more of potassium fluoride, sodium fluoride, and aluminum fluoride. In the embodiment of the application, the mass percentage of the metal fluoride in the glass etching liquid is 2% -5%, and the mass percentage of the metal fluoride in the glass etching liquid can be specifically but not limited to 2%, 3%, 4% or 5%. If the content of the metal fluoride is too high, the etched fringe pattern cannot be formed.

In the application, except providing metal ions, the hydrogen phosphate can promote fluosilicic acid radical deposition to form precipitation, and the concentration of the hydrogen ions can be regulated by the hydrogen phosphate, so that the etching speed of the glass surface is controlled, the phenomenon of pits formed by excessively rapid etching of local areas of the glass surface is relieved, and the stripe patterns are uniform. In addition, hydrogen phosphate is a weak acid which ionizes or combines with hydrogen ions to form H ₃ PO ₄ 、H ₂ PO ₄ ^1- 、HPO ₄ ^2- Or PO (PO) ₄ ^3- Form exists, so that the crystal is dispersed and inserted in the crystal sediment, the density of the crystal sediment is reduced, and the crystal on the surface of the glass is causedAnd the etching depth is controlled to ensure that a clear stripe pattern is formed. In the embodiment, the hydrogen phosphate is metal hydrogen phosphate which is soluble in acid, the hydrogen phosphate comprises monobasic phosphate and monobasic phosphate, and further, the hydrogen phosphate comprises monobasic potassium phosphate, dibasic potassium phosphate, monobasic sodium phosphate, dibasic sodium phosphate, monobasic aluminum phosphate, monobasic calcium phosphate and dibasic calcium phosphate. In some embodiments of the present application, the hydrogen phosphate is dihydrogen phosphate, which is capable of providing hydrogen phosphate and phosphate ions, and forming phosphoric acid in a strong acid environment, and a small amount of phosphoric acid can promote pitting to be converted into local etching, so as to promote formation of regular etching stripes. In the embodiment of the application, the mass percentage of the hydrogen phosphate in the glass etching liquid is 2% -5%, and the mass percentage of the hydrogen phosphate in the glass etching liquid can be specifically but not limited to 2%, 3%, 4% or 5%.

In the present application, nitric acid is used as a solvent to promote the dissolution of ammonium bifluoride, metal fluoride and hydrogen phosphate in a glass etching solution, 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 15% -30%, and the mass percentage of the nitric acid in the glass etching liquid can be specifically but not limited to 15%, 17%, 19%, 20%, 25% or 30%.

In the embodiment of the application, the mass percentage of sulfuric acid in the glass etching liquid is 12% -25%, and the mass percentage of nitric acid in the glass etching liquid can be specifically but not limited to 12%, 15%, 20% or 25%. The etching solution is added with a proper amount of sulfuric acid to increase the roughness of the glass surface, enlarge the etching reaction area, promote pitting to be converted into surface etching so as to form striped micro-sink, if the content of the sulfuric acid is too high, uneven pits are formed on the glass surface, the uniformity of the striped pattern is destroyed, if the content of the sulfuric acid is too low, obvious pitting is formed on the glass surface, and the glass has frosting effect and cannot form the striped pattern.

In the embodiment of the application, the organic acid can also promote the uniform dispersion of each component in the etching liquid besides adjusting the hydrogen ion concentration in the glass 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 can be stored for a long time, and besides, the dispersing agent can promote uniform dispersion of crystal precipitation and ensure that the crystal precipitation has uniform density. In embodiments of the present application, the organic acid includes 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 does not generate bubbles, thereby ensuring that a uniform stripe pattern is obtained. In the embodiment of the application, the mass percentage of the organic acid in the glass etching liquid is 5% -10%, and the mass percentage of the organic acid in the glass etching liquid can be specifically but not limited to 5%, 7%, 9% or 10%. The content of the organic acid is controlled, so that the glass etching liquid has good stability and proper acidity.

In some embodiments of the present application, the glass etching solution further comprises phosphoric acid. The phosphoric acid has stronger coordination capability, is favorable for promoting the dissolution of metal salt, and can also regulate the etching reaction speed and promote the formation of uniform stripe patterns. In some embodiments of the present application, the mass percentage of phosphoric acid is less than or equal to 10%, and the mass percentage of phosphoric acid may be specifically but not limited to 0.5%, 1%, 3%, 5%, 8%, or 10%.

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 1% -2%, and the mass percentage of the thickener in the glass etching solution can be, but is not limited to, 1%, 1.2%, 1.5% or 2%. In embodiments of the present application, the thickener comprises one or more of glycerol, triethanolamine, ethylene glycol, methanol, hexanol, octanol, polyethylene glycol, polyvinylpyrrolidone, and polyacrylamide. In some embodiments of the present application, the viscosity of the thickener is adjusted to a range of 5cP to 20cP, and the viscosity of the final glass etching solution is 40cP to 150cP, and the viscosity of the glass etching solution may be, but is not limited to, 40cP, 50cP, 80cP, 100cP, 120cP or 150cP. 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 application, the water in the glass etching liquid is used as a diluent and a solvent to promote ionization of hydrogen ions and dissolve organic acid and a thickener. In the embodiment of the application, the mass percentage of the water in the glass etching liquid is 15% -20%, and the mass percentage of the water in the glass etching liquid can be specifically but not limited to 15%, 17%, 19% or 20%.

In the glass etching liquid, the molar concentration of fluorine ions is 8mol/L-20mol/L, and the molar concentration of hydrogen ions is 18mol/L-33mol/L. In some embodiments of the present application, the molar concentration of fluoride ion is 8mol/L to 10mol/L and the molar concentration of hydrogen ion is 18mol/L to 20mol/L. In some embodiments of the application, the molar ratio of the fluorine ions to the hydrogen ions is 1 (1.25-2), the control of the molar ratio of the fluorine ions to the hydrogen ions in a certain range can ensure the formation of clear stripe patterns, and the control of the molar ratio of the fluorine ions to the hydrogen ions can inhibit the formation of frosting effects, so that the glass surface has uniform etching stripes.

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, etching stripes can be formed on the surface of the glass, 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 solution can be reused after being filtered and the consumed components are 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: the glass etching liquid is prepared by mixing 20-30% by mass of ammonium bifluoride, 2-5% by mass of metal fluoride, 2-5% by mass of hydrogen phosphate, 15-30% by mass of nitric acid, 12-25% by mass of sulfuric acid, 5-10% by mass of organic acid and 15-20% by mass of water.

In some embodiments of the present application, a method for preparing a glass etching solution is shown in fig. 1, referring to fig. 1, fig. 1 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: uniformly mixing ammonium bifluoride, metal fluoride, hydrogen phosphate and organic acid to obtain a first mixture;

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

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

step 400: and adding sulfuric acid into the third mixture and stirring uniformly to obtain the glass etching liquid.

In some embodiments of the present application, the glass etching solution further includes phosphoric acid with a mass percentage less than or equal to 10% and a thickener with a mass percentage of 1% -2%, and the first preparation method of the glass etching solution includes:

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

step 400: adding water and a thickening agent into the third mixture and uniformly stirring to obtain a fourth mixture;

step 500: and adding sulfuric acid into the fourth mixture and stirring uniformly 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. 2, referring to fig. 2, fig. 2 is a method for preparing a glass etching solution according to another embodiment of the present application, and the method is named as a second preparation method, where the second preparation method includes:

step 100: providing nitric acid, and sequentially adding an organic acid, ammonium bifluoride, hydrogen phosphate and metal fluoride into the nitric acid to obtain a first mixture;

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

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

In some embodiments of the present application, the glass etching solution further includes phosphoric acid with a mass percentage less than or equal to 10% and a thickener with a mass percentage of 1% -2%, and the second preparation method of the glass etching solution includes:

step 100: mixing nitric acid and phosphoric acid and uniformly stirring to obtain a first mixture;

step 200: sequentially adding organic acid, ammonium bifluoride, hydrogen phosphate and metal fluoride into the first mixture to obtain a second mixture;

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

In the preparation method, after sulfuric acid is added into the mixture, the mixture can be kept still for a period of time to fully release heat of the sulfuric acid, and the solute is 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 the application, when the second preparation method is adopted, as the solid salt components are added into the acid liquor 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 uniform and stable components, and is favorable for popularization and use of the glass etching liquid.

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

and (3) placing the glass in glass etching liquid for etching to obtain the striped glass.

In this embodiment, the etching time is 0.5min to 6min, and the etching time may be, but is not limited to, 0.5min, 1min, 2min, 4min or 6min. In some embodiments of the application, etching time is 0.5 min-2 min, and the glass etching liquid can form clear etching stripes on the surface of glass under a short treatment time, and if the treatment time is too long, excessive etching can be caused, so that the texture of the glass is reduced. In the present embodiment, the etching temperature is 10 to 30 ℃, and the etching temperature may be, but not limited to, 10 ℃, 15 ℃,20 ℃, or 30 ℃. The etching liquid has low temperature requirement, and can etch glass at normal temperature, thereby reducing the process cost.

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 acid solution for a period of time, wherein the acid solution comprises an aqueous solution of hydrofluoric acid, the mass percentage of the hydrofluoric acid is 2% -5%, and the soaking time is 5s-3min. The hydrophilic performance of the glass can be improved by carrying out the infiltration treatment on the glass, and the etching liquid is favorable for fully infiltrating the surface of the glass, so that the softening of 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, etching stripes are formed only on one side surface of glass, in order to form a single-side stripe 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, the glass is cleaned, dried and the protective layer is removed, so that glass with a single-side stripe pattern can be obtained, and if stripe patterns are formed on both sides of the glass, the glass is not required to be protected.

The stripe glass production method provided by the application is wide in application range, various glasses can be etched, the types of the glasses can be high-alumina silica glass and low-alumina silica glass, and the glasses can be float glass or glass prepared by a drawing method. And different stripe patterns can be obtained by adjusting process parameters, for example, the definition of the patterns can be adjusted by adjusting the processing time, and besides, the process has the advantages of simpler preparation conditions, short processing time, low process cost and good application prospect.

The application also provides the striped glass, which is prepared by the production method of the striped glass. In the embodiment of the present application, the stripe pitch of the stripe glass surface is 50 μm to 800 μm, and the stripe width of the stripe glass surface is 10 μm to 50 μm. The stripe pitch refers to the distance between two adjacent etched stripes. The measuring method of the stripe spacing and the stripe width comprises the following steps: the microscope is enlarged to 100-200 times, the lens is deflected vertically by a certain angle to make the stripes clear, the deflection angle is 5-30 degrees, one linear protrusion is regarded as one stripe, the width of the protrusion is the width of the stripe, and the distance between the highest points of adjacent protrusions is the stripe distance. The stripe pitch may be, in particular but not limited to, 50 μm, 100 μm, 200 μm, 300 μm, 500 μm or 600 μm. In some embodiments of the present application, the stripe pitch is 300 μm to 500 μm. The striped glass with the interval range has good anti-dizziness effect and visual impression. In the embodiment of the present application, the surface of the striped glass has a micro-sink with a depth of 0.01 μm to 10 μm and a width of 0.01 μm to 5 μm. The depth of the micro-sink may be, but not limited to, 0.01 μm, 0.1 μm, 0.5 μm, 1 μm, 3 μm, 5 μm or 10 μm, and the width of the micro-sink may be, but not limited to, 0.01 μm, 0.1 μm, 0.5 μm, 1 μm, 3 μm or 5 μm. Controlling the depth and width of the micro-sink can ensure that the stripe pattern on the surface of the glass has higher definition and the glass has better hand feeling. The measuring method of the micro-sink depth and the micro-sink width comprises the following steps: cutting glass in a direction perpendicular to stripes to obtain glass slices by adopting a method similar to a metallographic manufacturing method, vertically placing the glass cuts, wrapping the glass slices by using epoxy resin containing a curing agent, polishing the glass cuts after curing to remove edge spikes and cutting marks formed by the glass during cutting, and observing the shape of the glass cuts under a microscope to obtain the depth and width of a micro-sink, wherein the polishing conditions are as follows: coarse polishing-400-mesh sand paper, polishing at 300 rpm for 5min, fine polishing-polishing cotton and cerium oxide polishing solution, and polishing at 400 rpm for 3min.

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

Example 1

A preparation method of glass etching liquid comprises the following steps:

adding phosphoric acid into nitric acid at 25 ℃ and stirring uniformly, sequentially adding oxalic acid, ammonium bifluoride, monopotassium phosphate and potassium fluoride under stirring, sequentially adding water and glycerol after stirring uniformly, stirring again, finally adding sulfuric acid and stirring uniformly, and standing for 4 hours to obtain the glass etching liquid. The glass etching liquid comprises the following components in percentage by mass: monopotassium phosphate (KH) ₂ PO ₄ ): 5%, potassium fluoride (KF): 5%, nitric acid (HNO) ₃ ) 20%, sulfuric acid (H) ₂ SO ₄ ): 20%, phosphoric acid (H) ₃ PO ₄ ): 8%, water (H) ₂ O): 15%, oxalic acid (C) ₂ H ₂ O ₄ ): 5%, ammonium bifluoride (NH) ₄ HF ₂ ): 20% glycerol (C) ₃ H ₈ O ₃ )：2％。

Example 2

A preparation method of glass etching liquid comprises the following steps:

mixing oxalic acid, ammonium bifluoride, potassium dihydrogen phosphate and potassium fluoride uniformly at 25 ℃, adding nitric acid, stirring uniformly, adding phosphoric acid, stirring uniformly, adding water and glycerol, stirring, adding sulfuric acid, stirring uniformly, and standing for 4 hours to obtain the glass etching liquid. The glass etching liquid comprises the following components in percentage by mass: monopotassium phosphate (KH) ₂ PO ₄ ): 2%, potassium fluoride (KF): 2%, nitric acid (HNO) ₃ ): 20%, phosphoric acid (H) ₃ PO ₄ ): 7%, sulfuric acid (H) ₂ SO ₄ ): 19%, water (H) ₂ O): 18%, oxalic acid (C) ₂ H ₂ O ₄ ): 7%, ammonium bifluoride (NH) ₄ HF ₂ ): 23%, glycerol (C) ₃ H ₈ O ₃ )：2％。

Example 3

Ammonium bifluoride and phosphoric acid at 25 DEG CAdding potassium dihydrogen, potassium fluoride and oxalic acid into nitric acid respectively, stirring, adding water and glycerol, stirring, adding sulfuric acid, stirring, and standing for 4 hr to obtain glass etching solution. The glass etching liquid comprises the following components in percentage by mass: monopotassium phosphate (KH) ₂ PO ₄ ): 5%, potassium fluoride (KF): 5%, nitric acid (HNO) ₃ ): 22%, sulfuric acid (H) ₂ SO ₄ ): 22%, water (H) ₂ O): 17%, oxalic acid (C) ₂ H ₂ O ₄ ): 5%, ammonium bifluoride (NH) ₄ HF ₂ ): 22%, glycerol (C) ₃ H ₈ O ₃ )：2％。

Example 4

Adding phosphoric acid into nitric acid at 25 ℃ and stirring uniformly, then adding ammonium bifluoride, monopotassium phosphate, potassium fluoride and oxalic acid into the mixed solution and stirring uniformly, then adding water and glycerol and stirring uniformly, finally adding sulfuric acid and stirring uniformly, and standing for 4 hours to obtain the glass etching solution. The glass etching liquid comprises the following components in percentage by mass: phosphoric acid (H) ₃ PO ₄ ): 12%; monopotassium phosphate (KH) ₂ PO ₄ ): 3%, potassium fluoride (KF): 3%, nitric acid (HNO) ₃ ): 21%, sulfuric acid (H) ₂ SO ₄ ): 17%, water (H) ₂ O): 17%, oxalic acid (C) ₂ H ₂ O ₄ ): 6%, ammonium bifluoride (NH) ₄ HF ₂ ): 20% glycerol (C) ₃ H ₈ O ₃ )：1％。

Example 5

A preparation method of glass etching liquid comprises the following steps:

and uniformly mixing ammonium bifluoride, magnesium dihydrogen phosphate and potassium fluoride sodium fluoride at 25 ℃, adding nitric acid, uniformly stirring, adding phosphoric acid, uniformly stirring, adding water, acetic acid and maltose, uniformly stirring, finally adding sulfuric acid, uniformly stirring, and standing for 4 hours to obtain the glass etching liquid. The glass etching liquid comprises the following components in percentage by mass: ammonium bifluoride: 20% of a base; magnesium dihydrogen phosphate (Mg (H) ₂ PO ₄ ) ₂ ): 3%; sodium fluoride (NaF): 3%; nitric acid (HNO) ₃ ): 24%; phosphoric acid (H) ₃ PO ₄ ): 7%; water (H) ₂ O): 17%; acetic acid (CH) ₃ COOH): 7%; maltose (C) ₁₂ H ₂₂ O ₁₁ ): 1%; sulfuric acid (H) ₂ SO ₄ )：18％；。

Example 6

And respectively adding ammonium bifluoride, potassium dihydrogen phosphate, potassium fluoride and oxalic acid into nitric acid at 25 ℃ and stirring uniformly, adding water and stirring, finally adding sulfuric acid and stirring uniformly, and standing for 4 hours to obtain the glass etching liquid. The glass etching liquid comprises the following components in percentage by mass: monopotassium phosphate (KH) ₂ PO ₄ ): 5%, potassium fluoride (KF): 5%, nitric acid (HNO) ₃ ): 22%, sulfuric acid (H) ₂ SO ₄ ): 22%, water (H) ₂ O): 19%, oxalic acid (C) ₂ H ₂ O ₄ ): 5%, ammonium bifluoride (NH) ₄ HF ₂ )：22％。

Comparative example 1

And respectively adding ammonium bifluoride, potassium fluoride and oxalic acid into nitric acid at 25 ℃ and uniformly stirring, then adding water, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and acacia and uniformly stirring, finally adding sulfuric acid and uniformly stirring, and standing for 4 hours to obtain the glass etching liquid. The glass etching liquid comprises the following components in percentage by mass: potassium fluoride (KF): 17%, nitric acid (HNO) ₃ ): 14%, sulfuric acid (H) ₂ SO ₄ ): 11%, water (H) ₂ O): 27%, ammonium bifluoride (NH) ₄ HF ₂ ): 27%, sodium dodecyl sulfate (K12): sodium Dodecyl Benzene Sulfonate (SDBS): 2.8%, acacia (E414): 0.2%.

Comparative example 2

And respectively adding ammonium bifluoride, potassium fluoride and oxalic acid into nitric acid at 25 ℃ and stirring uniformly, adding water and glycerol and stirring uniformly, finally adding sulfuric acid and stirring uniformly, and standing for 4 hours to obtain the glass etching liquid. The glass etching liquid comprises the following components in percentage by mass: potassium fluoride (KF): 5%, nitric acid (HNO) ₃ ): 22%, sulfuric acid (H) ₂ SO ₄ ): 22%, water (H) ₂ O): 17%, oxalic acid (C) ₂ H ₂ O ₄ ): 5%, ammonium bifluoride (NH) ₄ HF ₂ ): 22%, glycerol (C) ₃ H ₈ O ₃ )：2％。

Comparative example 3

Adding phosphoric acid into nitric acid at 25 ℃ and stirring uniformly, sequentially adding oxalic acid, ammonium bifluoride, monopotassium phosphate, potassium fluoride and sodium fluosilicate under stirring, sequentially adding water and glycerol after stirring uniformly, finally adding sulfuric acid, and standing for 4 hours to obtain the glass etching liquid. The glass etching liquid comprises the following components in percentage by mass: monopotassium phosphate (KH) ₂ PO ₄ ): 5%, potassium fluoride (KF): 5%, sodium fluorosilicate (Na) ₂ SiF ₆ ): 0.8%, nitric acid (HNO) ₃ ): 20%, sulfuric acid (H) ₂ SO ₄ ): 20%, phosphoric acid (H) ₃ PO ₄ ): 8%, water (H) ₂ O): 14.2%, oxalic acid (C) ₂ H ₂ O ₄ ): 5%, ammonium bifluoride (NH) ₄ HF ₂ ): 20% glycerol (C) ₃ H ₈ O ₃ )：2％。

Effect examples

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

1) Measurement of the concentration c of Hydrogen ions in the glass etching solutions of examples 1 to 6 ₁ And concentration of fluoride ion c ₂ And the glass etching solutions of examples 1 to 6 were measured, and the parameters of the glass etching solutions of examples 1 to 6 are shown in Table 1.

TABLE 1 parameter Table for glass etchants of examples 1-6

Experimental group	H ⁺ (c ₁ /mol·L ^-1 )	F ^- (c ₂ /mol·L ^-1 )	Viscosity (cp)
				Example 1	19.14	10.58	98.45
Example 2	20.24	17.22	86.14
				Example 3	19.64	14.69	104.73
Example 4	19.46	11.84	87.1
				Example 5	17.75	11.23	91.7
Example 6	20.13	14.56	81.85

2) Providing 3 glass plates, wherein the glass No. 1 and the glass No. 2 are drawn and formed plate glass, the glass plates are high-alumina silicon glass, the mass percentage of aluminum in the glass No. 1 is 14.21%, and the mass percentage of silicon is 38.35%; 11.22 mass percent of aluminum and 39.6 mass percent of silicon in the No. 2 glass; the No. 3 glass plate is a float formed glass plate and is low-aluminum silicon glass, wherein the mass percentage of aluminum in the No. 3 glass is 1.913%, and the mass percentage of silicon is 17.56%.

The preparation process of the striped glass comprises the following steps: coating a protective layer on any surface of the glass, cleaning a non-shielding surface of the glass, and performing infiltration treatment, wherein the infiltration treatment comprises: soaking glass in hydrofluoric acid with the mass percentage of 2% for 10s; and (3) placing the wet glass in glass etching liquid for a period of time, taking out the glass, and cleaning and drying the glass to obtain the striped glass. Taking example 7 as an example, the preparation process of the striped glass in example 7 is as follows:

and (3) arranging a protective layer on one side surface of the No. 1 glass, cleaning and soaking the unprotected side surface of the glass, and placing the No. 1 glass into the glass etching liquid prepared in the embodiment 1, wherein the etching temperature is 20 ℃ and the etching time is 1min.

Striped glasses were prepared using different glasses and preparation conditions, examples 7 to 15 were striped glasses prepared using the glass etching solutions of examples 1 to 6, respectively, and comparative examples 4 to 6 were etched glasses prepared using the etching solutions of comparative examples 1 to 3, respectively, and the preparation conditions of the striped glasses of examples 7 to 15 and the etched glasses of comparative examples 4 to 6 were shown in Table 2.

TABLE 2 preparation conditions Table for example 7-15 striped glass and comparative example 4-6 etched glass

Experimental group	Glass numbering	Etching liquid	Time (min)
				Example 7	No. 1	Example 1	1
Example 8	No. 1	Example 2	1
				Example 9	No. 1	Example 3	1
Example 10	No. 1	Example 4	1
				Example 11	No. 1	Example 5	1
Example 12	No. 1	Example 6	1
				Example 13	No. 1	Example 2	4
Example 14	No. 2	Example 2	1
				Example 15	No. 3	Example 2	1
Comparative example 4	No. 1	Comparative example 1	3
				Comparative example 5	No. 1	Comparative example 2	3
Comparative example 6	No. 1	Comparative example 3	3

3) The patterns on the surfaces of the striped glasses of examples 7 to 15 were observed with a microscope and naked eyes, and the stripe pitches of the striped glasses of examples 7 to 15 were recorded, and the stripe pitches were measured by observing with a microscope, taking stripe measurements at different positions on the glass surfaces and taking an average value. Referring to fig. 3, fig. 3 is a micrograph of the striped glass prepared in example 8, the stripe pitch in fig. 3 is the distance between adjacent protrusions, and the measured stripe pitches are 514.08 μm, 372.96 μm, 513.7 μm, 336.71 μm and 199.33 μm, respectively, and the average value is taken to obtain the stripe pitch 387 μm in example 8. The striped glass test results of examples 7-15 are shown in Table 3.

TABLE 3 fringe spacing Meter for striped glasses of examples 7-15

Experimental group	Fringe spacing (mum)
		Example 7	263
Example 8	387
		Example 9	171
Example 10	611
		Example 11	418
Example 12	536
		Example 13	423
Example 14	400
		Example 15	340

Referring to fig. 4, fig. 4 is a pattern diagram of the striped glass prepared in example 8, wherein the pattern diagram of the striped glass refers to the visual effect of the striped glass on the macroscopic scale, i.e. the appearance of the glass observed by naked eyes. As can be seen from fig. 4, the glass surface has clear etched streaks. Referring to fig. 5, fig. 5 is a pattern diagram of striped glass prepared in example 13, in which example 13 is etched for a longer time, and as can be seen from fig. 5, the surface of the glass still has clear stripes when the etching time is longer, which indicates that the etching solution of the present application has low requirement on time, and the reaction time is not required to be strictly controlled, so that the preparation process can be simplified, and the production cost can be reduced. Referring to fig. 6, fig. 6 is a pattern diagram of striped glass prepared in example 15, the glass used in example 15 is low-alumina silica glass, and as can be seen from fig. 6, the etching solution of the present application has good etching effect on different types of glass, and can form etching striped patterns on the surface of the glass.

Referring to fig. 7 and 8, fig. 7 is a pattern diagram of the etched glass prepared in comparative example 4, and fig. 8 is a pattern diagram of the etched glass prepared in comparative example 5, and it can be seen from fig. 7 and 8 that the etching solutions of comparative example 1 and comparative example 2 do not form etching stripes, and the glass surface only exhibits an uneven rough structure. The glass etching solution of comparative example 3 contained fluorosilicate, which had poor stability, produced precipitation in a static state and exhibited cloudiness, and after the glass etching solution of comparative example 3 was left for one week, glass etching was performed to find that the glass etching solution had failed. The etching solutions of examples 1 to 6 of the present application were not precipitated after standing for one week, and the glass obtained when etching the glass still had clear etching stripes.

4) The striped glass of examples 7-15 and the etched glass of comparative examples 4 and 5 were visually inspected for unetched areas, and the striped glass of examples of the present application was observed to have no sand leakage areas, whereas the sand leakage rates of the etched glass surfaces of comparative examples 4 and 5 were 1% -2%.

5) The striped glass of examples 7 to 15 and the etched glass of comparative examples 4 and 5 were visually observed for the presence or absence of areas of uneven patterns, and the striped glass of examples of the present application was observed to have no areas of uneven etching as a whole, whereas the etched glass of comparative examples 4 and 5 had an uneven etching rate of 1% to 5%.

6) The striped glasses of examples 7-15 and the etched glasses of comparative examples 4 and 5 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 4, 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; the transverse direction is perpendicular to the stripe direction, and the longitudinal direction is parallel to the stripe direction.

TABLE 4 apparent parameters of the striped glasses of examples 7-15 and the etched glasses of comparative examples 4-6

As can be seen from Table 4, the striped glass prepared by the embodiment of the application has the advantages of good light transmittance, low roughness value, good appearance effect and hand feeling, and greatly reduced subsequent processing time.

The etched glass of comparative example 4 has high haze, low transmittance of glass, and poor touch, and the appearance effect is affected, and the roughness value of glass is too large. Etched glass of comparative example 5 and transverse R _z Examples of similar values are compared, R of examples _a Are all larger than comparative example 5, indicating that comparative example 5 has an insufficient average depth and width of etching, and a longitudinal direction R _a Of all values, the examples are smaller than the transverse direction R _z Value of comparative example is greater than transverse R _z Value, and R _t A value less than R _z Values, which indicate that comparative example 5 is only randomCorrosion is caused.

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: 20% -30%;

metal fluoride: 2% -5%;

hydrogen phosphate: 2% -5%;

nitric acid: 15% -30%;

sulfuric acid: 12% -25%;

organic acid: 5% -10%;

water: 15% -20%.

2. The glass etching solution according to claim 1, further comprising phosphoric acid, wherein the mass percentage of the phosphoric acid is less than or equal to 10%.

3. The glass etching solution according to claim 1 or 2, wherein the metal fluoride comprises one or more of potassium fluoride, sodium fluoride, and aluminum fluoride.

4. The glass etching solution according to any one of claims 1 to 3, wherein the hydrogen phosphate salt comprises one or more of potassium dihydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, aluminum dihydrogen phosphate, calcium dihydrogen phosphate, and calcium hydrogen phosphate.

5. The glass etching solution of any of claims 1-4, wherein the organic acid comprises one or more of oxalic acid, tartaric acid, citric acid, acetic acid, sulfamic acid, sorbic acid, and maleic acid.

6. The glass etching liquid according to any one of claims 1 to 5, further comprising a thickener, wherein the thickener is 1 to 2% by mass.

7. The glass etching solution according to claim 6, wherein the thickener comprises one or more of glycerol, triethanolamine, ethylene glycol, methanol, hexanol, octanol, polyethylene glycol, polyvinylpyrrolidone, and polyacrylamide.

8. The glass etching liquid according to claim 1, wherein the glass etching liquid comprises the following components in percentage by mass:

ammonium bifluoride: 20% -30%;

metal fluoride: 2% -3%;

hydrogen phosphate: 2% -4%;

nitric acid: 20% -29%;

sulfuric acid: 18% -20%;

phosphoric acid: 7% -10%;

organic acid: 7% -10%;

and (3) a thickening agent: 1% -2%;

water: 17% -20%.

9. The glass etching solution according to any one of claims 1 to 8, wherein the viscosity of the glass etching solution is 40cP to 150cP.

10. The preparation method of the glass etching liquid is characterized by comprising the following steps:

ammonium bifluoride: 20% -30%;

metal fluoride: 2% -5%;

hydrogen phosphate: 2% -5%;

nitric acid: 15% -30%;

sulfuric acid: 12% -25%;

organic acid: 5% -10%;

water: 15% -20%.

11. A method for producing striped glass, comprising the steps of:

providing a glass etching solution according to any one of claims 1 to 9;

and placing the glass in the glass etching liquid for etching to obtain the striped glass.

12. The method of claim 11, wherein the etching time is 0.5min to 6min; the etching temperature is 10-30 ℃.

13. A striped glass is characterized in that the surface of the striped glass is provided with a plurality of etched stripes, and the width of each etched stripe is 10 mu m-50 mu m.

14. The striped glass according to claim 13, wherein the etched stripes are adjacent to each other at a distance of 50 μm to 800 μm.