CN113666644A

CN113666644A - Glass frosting liquid, prepared frosted glass and preparation method

Info

Publication number: CN113666644A
Application number: CN202110980421.5A
Authority: CN
Inventors: 韩伟军; 杨宇翔; 刘稳文; 黄忠祥; 汤哲辉; 黄艳
Original assignee: Xiangshi Photoelectric Technology Kunshan Co ltd
Current assignee: Xiangshi Photoelectric Technology Kunshan Co ltd
Priority date: 2021-08-25
Filing date: 2021-08-25
Publication date: 2021-11-19

Abstract

The invention discloses a glass frosting solution, prepared frosted glass and a preparation method, wherein the glass frosting solution comprises a frosting powder and a solvent, the total amount of the frosting powder is 100% by mass percent, and the glass frosting solution comprises the following raw materials: 1.0-5.0% of oxalic acid dihydrate, 2.0-8.0% of sulfamic acid, 0-2.0% of white granulated sugar, 0-3.0% of cane sugar, 11.0-14.0% of barium sulfate, 5.0-11.0% of barium fluoride, 0.02-0.5% of calcium fluoride, 0.1-2.5% of sodium fluoride, 0.05-4.0% of potassium fluoride dihydrate, 0-3.0% of potassium chloride, 1.5-6.0% of aluminum fluosilicate, 0.5-1.5% of sodium dodecyl sulfonate, 0.1-9% of ammonium fluoride, 0.5-3.0% of magnesium fluosilicate and the balance of ammonium bifluoride.

Description

Glass frosting liquid, prepared frosted glass and preparation method

Technical Field

The invention relates to the technical field of frosted glass preparation, in particular to a glass frosting liquid, prepared frosted glass and a preparation method.

Background

Glass is broadly defined as an amorphous solid with a completely long-range disorder of structure and glass transition characteristics, and narrowly defined as an inorganic substance obtained by cooling a melt without precipitating crystals. Glass is therefore an amorphous inorganic non-metallic material, and is also a material similar to a material having both a solid outer structure and a liquid inner structure.

Since glass has various excellent properties such as high mechanical strength, excellent optical properties, uniform texture, difficult aging, smooth surface, etc., glass is widely used in daily life of people, such as glass cups, glass doors, glasses, etc. One particular use of glass is in decorative finishing. The surface of the glass is modified to a certain extent, so that the glass can be applied to various fields such as decoration, illumination, buildings, furniture, home decoration, packaging glass, advertisements, artistic projects and the like, and the decoration of the glass can be carried out in the forming process or after the production is finished. The decoration method of the formed glass comprises the technologies of spraying, hand painting, direct and indirect silk screen printing, bedding and the like. Extinction is a process for modifying the surface of glass in order to provide it with uniform light scattering properties. This phenomenon is achieved by creating microscopic unevennesses in the glass surface, by which the glass loses its smoothness and gloss, becomes no longer transparent, but is still capable of transmitting light.

Although glass has many excellent properties, it causes serious light pollution to our living environment due to high reflectivity of the glass surface and imperfect process of glass products. The glass curtain wall enters the Chinese market in the last century, belongs to a wall decoration process, and is suitable for all people in large cities, but the glass curtain wall with special performance is the main source of the problem of light pollution, can cause harm to users, can cause discomfort to human bodies, can hurt eyes, and is quite dangerous due to the fact that the eyesight is blocked, dizziness is caused to the head, even insomnia and vomiting are caused, and the problem of light pollution can also cause very adverse effects to traffic accidents, and the driver can cause the eyesight to be blocked due to the light pollution, and the head can generate the dizziness, so that the situation is quite dangerous, and the problem of light pollution caused by glass is solved, and the problem becomes a hotspot concerned in scientific research of current materials.

With the wide use of glass, the living standard and artistic appreciation ability of people are slowly changed by the glass, but glass products such as glass curtain walls and glazed brick walls cause serious light pollution problems, so that the glass not only causes great physical harm to people, but also has bad influence on ecological environment and ecological diversity. The high reflectivity of the glass can be reduced after the glass is frosted, the anti-glare function is achieved, the light pollution problem can be prevented from the source, and therefore the glass frosting process plays a vital role in solving the light pollution problem. Therefore, the problem of light pollution is not easy to solve, and the prior art of glass frosting process is not perfect, so that the improvement of the glass frosting process is imperative.

Disclosure of Invention

The invention aims to provide a glass frosting solution to solve the problem of light pollution caused by glass.

The invention also aims to provide a method for preparing frosted glass by adopting the glass frosting liquid.

In order to achieve the purpose, the invention provides the following scheme:

the invention provides a glass frosting solution which comprises a frosting powder and a solvent, wherein the total content of the frosting powder is 100% by mass percent, and the glass frosting solution comprises the following raw materials: 1.0 to 5.0 percent of oxalic acid dihydrate, 2.0 to 8.0 percent of sulfamic acid, 0 to 2.0 percent of white granulated sugar, 0 to 3.0 percent of cane sugar, 11.0 to 14.0 percent of barium sulfate, 5.0 to 11.0 percent of barium fluoride, 0.02 to 0.5 percent of calcium fluoride, 0.1 to 2.5 percent of sodium fluoride, 0.05 to 4.0 percent of potassium fluoride dihydrate, 0 to 3.0 percent of potassium chloride, 1.5 to 6.0 percent of aluminum fluosilicate, 0.5 to 1.5 percent of sodium dodecyl sulfonate, 0.1 to 9 percent of ammonium fluoride, 0.5 to 3.0 percent of magnesium fluosilicate and the balance of ammonium bifluoride.

Further, the glass frosting solution comprises frosting powder and a solvent, wherein the total content of the frosting powder is 100% by mass, and the glass frosting solution comprises the following raw materials: 1.2 to 4.9 percent of oxalic acid dihydrate, 2.0 to 8.0 percent of sulfamic acid, 0 to 1.95 percent of white granulated sugar, 0 to 2.92 percent of cane sugar, 11.72 to 13.63 percent of barium sulfate, 5.65 to 9.98 percent of barium fluoride, 0.05 to 0.4 percent of calcium fluoride, 0.1 to 2.5 percent of sodium fluoride, 0.05 to 3.7 percent of potassium fluoride dihydrate, 0 to 2.5 percent of potassium chloride, 1.6 to 5.57 percent of aluminum fluosilicate, 0.5 to 1.2 percent of sodium dodecyl sulfonate, 0.1 to 8.4 percent of ammonium fluoride, 0.5 to 2.8 percent of magnesium fluosilicate and the balance of ammonium bifluoride.

Further, the frosting powder comprises AG frosting powder and B frosting powder, wherein:

the AG frosting powder is 100% in total by mass percent and comprises the following raw materials: 56-58% of ammonium bifluoride, 0-0.2% of ammonium fluoride, 2-5% of oxalic acid dihydrate, 4-8% of sulfamic acid, 0-2% of white granulated sugar, 0-3% of cane sugar, 11-14% of barium sulfate, 5-6% of barium fluoride, 0.3-0.5% of calcium fluoride, 0.1% of sodium fluoride, 2.0-4.0% of potassium fluoride dihydrate, 2.0-3.0% of potassium chloride, 3.0-6.0% of aluminum fluosilicate, 0.5-1.0% of sodium dodecyl sulfate and 0-3.0% of magnesium fluosilicate.

The frosting powder B is calculated according to the mass percent, the total is 100 percent, and comprises the following raw materials: 1-2% of oxalic acid dihydrate, 2-4% of sulfamic acid, 8.0-9.0% of ammonium fluoride, 11.5-14% of barium sulfate, 9-11% of barium fluoride, 0.02-0.1% of calcium fluoride, 1-2.5% of sodium fluoride, 0.03-0.2% of potassium fluoride dihydrate, 1-3% of aluminum fluosilicate, 0.4-1.5% of sodium dodecyl sulfate and 58-62% of ammonium bifluoride. Preferably, the frosting powder B is 100% in total according to the mass percentage and comprises the following raw materials: 1.2 to 1.5 percent of oxalic acid dihydrate, 2 to 2.99 percent of sulfamic acid, 11.5 to 13 percent of barium sulfate, 9 to 10 percent of barium fluoride, 0.02 to 0.1 percent of calcium fluoride, 7.5 to 8.4 percent of ammonium fluoride, 1.6 to 2.5 percent of sodium fluoride, 0.05 to 0.2 percent of potassium fluoride dihydrate, 1 to 3 percent of aluminum fluosilicate, 0.4 to 1.2 percent of sodium dodecyl sulfonate and 58.5 to 60.38 percent of ammonium bifluoride in balance.

According to different components and contents of the medicine, two frosting solutions are prepared, the frosting roughness of the glass is measured, the roughness of the glass is measured by adopting a surface roughness measuring instrument with model SJ-210, and the two frosting solutions are respectively called AG (anti-glass) powder frosting solution and B powder frosting solution. The AG powder frosting solution is prepared by dissolving and dispersing 100g of frosting powder in 30-35 parts of deionized water, and the B powder frosting solution is prepared by dissolving and dispersing 100g of frosting powder and 30 parts of hydrochloric acid.

The invention provides a preparation method of glass frosting liquid, which comprises the following steps: accurately weighing the raw materials according to the mass percentage, grinding and crushing the raw materials, adding the ground raw materials into deionized water or hydrochloric acid, uniformly dispersing the ground raw materials, heating the mixture in a water bath under the stirring condition, and continuing stirring after the water bath is finished.

Preferably, the water bath heating temperature in the preparation method of the glass frosting solution is 30-50 ℃, and the water bath heating time is 20-40 min.

Preferably, the continuous stirring time in the preparation method of the glass frosting solution is 20-30 h.

The invention also provides frosted glass prepared from the glass frosting liquid.

The method for preparing the frosted glass by adopting the frosting liquid comprises the following steps: after glass is pretreated, the pretreated glass is immersed in a frosting solution and cleaned.

The invention discloses the following technical effects:

a large number of fluosilicate crystal grains are formed on the surface of the frosted glass obtained after the glass frosting liquid is treated, and the crystal grains can be regarded as convex lenses. Therefore, when the glare light source passes through the frosted glass, the glare light source is equivalent to passing through the convex lenses which are respectively composed of the fluosilicate crystal grains, so that the high diffuse reflection phenomenon is generated, the glare is effectively eliminated, and the anti-glare purpose is achieved.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.

FIG. 1 is a scanning electron micrograph of frosted glass prepared 3 minutes after dipping glass with the frosting solution of example 1;

FIG. 2 is a scanning electron micrograph of frosted glass prepared 3 minutes after dipping glass with the frosting solution of example 2;

FIG. 3 is a scanning electron micrograph of frosted glass prepared 3 minutes after dipping glass with the frosting solution of example 3;

FIG. 4 is a scanning electron micrograph of frosted glass prepared 3 minutes after dipping glass with the frosting solution of example 4;

FIG. 5 is a scanning electron micrograph of frosted glass prepared 3 minutes after dipping glass with the frosting solution of example 5;

FIG. 6 is a scanning electron micrograph of frosted glass prepared 3 minutes after dipping glass with the frosting solution of example 6;

FIG. 7 is a scanning electron micrograph of frosted glass prepared 3 minutes after dipping glass with the frosting solution of example 7;

FIG. 8 is a scanning electron micrograph of frosted glass prepared 3 minutes after dipping glass with the frosting solution of example 8;

FIG. 9 is a graph showing the effect of frosted glass prepared after the frosting liquid of example 1 is immersed for 3 minutes;

FIG. 10 is a graph showing the effect of frosted glass prepared after the frosting liquid of example 2 is immersed for 3 minutes;

FIG. 11 is a graph showing the effect of frosted glass prepared after the frosting liquid of example 4 is immersed for 3 minutes;

FIG. 12 is a graph showing the effect of frosted glass prepared by dipping the frosting solution of example 5 for 3 minutes;

FIG. 13 is a graph showing the effect of frosted glass prepared by dipping the frosting solution of example 6 for 3 minutes;

FIG. 14 is an electron micrograph of frosted glass prepared 2 minutes after treating glass with the frosted glass frit of example 9;

FIG. 15 is an electron micrograph of frosted glass prepared 2 minutes and 30 seconds after the glass has been treated with the frosted glass frit of example 9;

FIG. 16 is an electron micrograph of frosted glass prepared 2 minutes 35 seconds after treatment of glass with the frosted glass frit of example 9;

FIG. 17 is an electron micrograph of frosted glass prepared 2 minutes 40 seconds after treatment of glass with the frosted glass frit of example 9;

FIG. 18 is an electron micrograph of frosted glass prepared 3 minutes after treatment of glass with the frosted glass frit of example 9;

FIG. 19 is an electron micrograph of frosted glass prepared 3 minutes and 30 seconds after treatment of glass with the frosted glass frit of example 9;

FIG. 20 is a graph showing the effect of different frosting times on the roughness of frosted glass in the frosting solution prepared in example 4;

FIG. 21 is a graph showing the effect of different pH values on the roughness of frosted glass from the frosting solution prepared in example 4.

Detailed Description

Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.

It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.

It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.

As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.

The raw materials in the glass frosting solution are purchased.

EXAMPLES 1-8AG glass frosting liquid

The formula of the frosting powder of the embodiments 1 to 8 is shown in table 1, the frosting liquid of the embodiments 1 to 8 is obtained by dispersing 100g of frosting powder in 35g of deionized water, and the specific preparation method comprises the following steps: accurately weighing ammonium bifluoride, ammonium fluoride, oxalic acid dihydrate, sulfamic acid, white granulated sugar, sucrose, barium sulfate, barium fluoride, calcium fluoride, sodium fluoride, potassium fluoride dihydrate, potassium chloride, aluminum fluosilicate, sodium dodecyl sulfate and magnesium fluosilicate according to the mass parts, finely grinding (grinding is needed because many medicines are in crystal blocks) in a ceramic mortar for about 10 minutes (grinding is needed until the medicines are dispersible powder and have no caking phenomenon), transferring all the medicines in the mortar to a 1000mL large beaker (the mortar needs to be kept in a clean and anhydrous state before use, and is cleaned in time after use to treat residual samples) after grinding is finished, adding deionized water into the beaker (note that stirring is needed by a plastic stirring rod while adding water), fully dispersing the beaker, putting the beaker into a water bath of an intelligent constant-temperature timing magnetic stirrer, the temperature was set at 40 ℃ and the water bath time was 30 minutes. After the completion of the water bath, the beaker was taken out and continuously stirred for 24 hours to obtain a white and viscous paste, i.e., a frosting solution, which was recorded as AG glass frosting solution in examples 1 to 8.

TABLE 1 EXAMPLES 1-8AG GLASS MASKING LIQUID MASKING POWDER MATERIAL AND ITS MIXTURE

Note: "-" indicates no addition.

The glass pretreatment is to add an adhesive tape on the surface of the glass with the sticker so as to be convenient to clean and carry out subsequent frosting experiments. Then the cleaning process of acid cleaning and alcohol cleaning is carried out. The articles required were: two 500mL plastic beaker with handle, plate glass, transparent adhesive tape, 5cm by 3mm plate glass, non-woven fabric.

Preparing hydrochloric acid cleaning solution in advance: hydrochloric acid solution and absolute ethyl alcohol. 150mL of hydrochloric acid was poured into a 500mL plastic beaker with a handle, and then water was added to a diluted hydrochloric acid concentration of 500 mL.

Putting the glass adhered with the transparent adhesive tape into hydrochloric acid cleaning liquid to ensure that the surface of the glass is completely immersed in the hydrochloric acid cleaning liquid, taking out the acid-cleaned glass after 3 minutes of hydrochloric acid cleaning, repeatedly washing and cleaning with water, then putting the glass on non-woven fabric until the surface of the glass is dried to be free of water drops, and then putting the glass into absolute ethyl alcohol again to clean for 1 minute. And repeatedly washing with water again, drying on the non-woven fabric, and using the glass for frosting experiments after no water beads exist.

Dipping the pretreated glass into the frosting liquid prepared in the embodiment 1-8, starting timing, holding a plastic stirring rod by a left hand to perform manual stirring, holding the glass by a right hand, slowly moving the glass up and down, frosting the glass for a certain time, taking out the frosting glass to clean the surface of the glass, repeatedly washing the glass by using a laboratory high-pressure water gun, after washing the glass completely, removing adhesive tapes and stickers on the glass, wiping and drying the glass by using non-woven fabrics, observing the frosting effect of the glass, testing the roughness of the frosting glass, and performing parallel test for 6 times. The results of glass roughness after 3 minutes treatment with the frosting solutions prepared in examples 1-8 are shown in Table 2.

TABLE 2 AG glass frosting fluid treatment 3 minutes later glass roughness

Example 1 compared to example 2, the AG powder frosted glass appearance of example 1: the glass is very smooth, the content of aluminum fluosilicate is increased, and the flatness of the frosted glass is improved.

As shown in the upper left corner of figure 1, after silicic acid in glass is dissolved, aluminum fluosilicate is used as a silicic acid gel promoter to accelerate the polymerization of silicic acid dissolved by ammonium bifluoride on the surface of the glass to form uniform gel particles. The aluminum fluosilicate content decreased in example 2, resulting in no uniform gel particles observed in fig. 2. A slight increase in ammonium bifluoride compared to example 3 and example 4 resulted in an increase in AG powder frosted glass apparent roughness from an average of 0.359 to 0.532. In example 4 compared to example 5, the aluminum fluosilicate content increased from 3.872% to 4.350%, resulting in an increase in AG powder frosted glass apparent roughness from an average of 0.532 to 0.555. However, the amount of silicic acid dissolved in the ammonium bifluoride on the glass surface and the number of gel particles generated by polymerization are reduced due to the decrease in the amount of aluminum fluorosilicate as compared with the surface morphologies of examples 1 and 2, and as shown in fig. 3 and 4, the surface roughness is reduced.

Different from the examples 1-5, the addition of 0.192% ammonium fluoride in the example 8 effectively controls the roughness of the AG powder frosted glass to be about 0.6, and has great innovation. Ammonium bifluoride and a small amount of ammonium fluoride form a conjugate acid-base pair, and the etching capability of the AG powder frosting liquid is effectively controlled in the aqueous frosting liquid. In the upper left corner of fig. 8, the number of gel particles on the surface of fig. 8 was significantly increased, maintaining the frosted glass apparent roughness at around 0.6.

In examples 6 to 7, unlike examples 1 to 5 and 8, the roughness of the glass frosted with AG powder was greatly improved by adding magnesium fluosilicate to the AG powder frosting powder. Example 6 the amount of magnesium fluosilicate added is large, the roughness is obviously increased, and the average roughness value is 0.970; whereas when the amount of magnesium fluorosilicate was small, only 0.5%, the average roughness value of example 7 increased only to 0.810. The topography scans of fig. 6 and 7 also show that the AG powder frosted glass has obviously increased apparent roughness due to the increase of magnesium fluosilicate, which is used as an accelerating agent to promote the rapid solidification of the silicic acid sol. Moreover, the higher the content of magnesium fluorosilicate, the lower the uniformity of the surface gel particles, and the coexistence of large-particle gel and small-particle gel in fig. 6 directly leads to the increase of the roughness of the AG powder frosted glass.

Scanning electron micrographs of frosted glass prepared 3 minutes after dipping the glass in the frosting solutions of examples 1-8 are shown in FIGS. 1-8.

The effect graph of the frosted glass prepared after the frosted liquid of the example 1 is immersed for 3 minutes is shown in fig. 9, the effect graph of the frosted glass prepared after the frosted liquid of the example 2 is immersed for 3 minutes is shown in fig. 10, the effect graph of the frosted glass prepared after the frosted liquid of the example 4 is immersed for 3 minutes is shown in fig. 11, the effect graph of the frosted glass prepared after the frosted liquid of the example 5 is immersed for 3 minutes is shown in fig. 12, and the effect graph of the frosted glass prepared after the frosted liquid of the example 6 is immersed for 3 minutes is shown in fig. 13.

Examples 9-12B glass frosting solutions

The formulation of the frosting powder of examples 9-12 is shown in Table 3, the frosting solution of examples 9-12 is prepared by dispersing 100g of frosting powder in 30g of hydrochloric acid, and the preparation method comprises the following steps: accurately weighing ammonium bifluoride, ammonium fluoride, oxalic acid dihydrate, sulfamic acid, barium sulfate, barium fluoride, calcium fluoride, sodium fluoride, potassium fluoride dihydrate, aluminum fluosilicate and sodium dodecyl sulfate into a ceramic mortar according to the mass parts, finely grinding (grinding is needed because many medicines are in crystal blocks), grinding for about 10 minutes (grinding is needed until the medicines are dispersible powder and have no caking phenomenon), transferring all the medicines in the mortar into a 1000mL big beaker after grinding is finished (the mortar needs to be kept in a clean and anhydrous state before use, and is cleaned in time after use, treating residual samples), adding hydrochloric acid into the beaker (note that the adding of hydrochloric acid needs to be stirred by a plastic stirring rod while adding, the adding of hydrochloric acid needs to be operated in a fume hood, and protective measures are taken), fully dispersing, the beaker is placed into a water bath kettle of an intelligent constant-temperature timing magnetic stirrer, the temperature is set to be 40 ℃, and the water bath time is 30 minutes. After the water bath was completed, the beaker was taken out and stirred for 24 hours to obtain a white and viscous paste, i.e., a frosting solution, which was recorded as B glass frosting solution in examples 9 to 12.

TABLE 3 example 9-12B glass frosting liquid frosting powder raw material and compounding ratio

The pretreated glass was immersed in the B frosting solution prepared in examples 9 to 12, the glass pretreatment method and the immersion method were the same as those of examples 1 to 8, the roughness of the glass after the treatment with the B frosting solution was measured and measured 6 times in parallel, and the roughness of the glass after the treatment with the B frosting solution for 2 minutes and 35 seconds is shown in Table 4.

TABLE 4B roughness of frosted glass after 2 min 35 sec treatment with frosting liquid

From the roughness test, it can be seen that the particles of example 9 are very uniformly distributed and the roughness is also very uniform and consistent.

Example 10 roughness decreased somewhat as the amount of aluminum fluorosilicate was increased. The aluminum fluosilicate is used as a silicic acid gel promoter to accelerate the polymerization of silicic acid dissolved by ammonium bifluoride on the surface of glass, but the dosage of the aluminum fluosilicate is increased, so that the polymerization speed is too high, the surface part is coagulated, and the surface roughness is reduced.

Example 11 because the concentration of ammonium bifluoride is reduced, the concentration of sulfamic acid is also reduced, the dosage of aluminum fluosilicate is continuously increased, the acidity of the whole system is reduced, the concentration of hydrogen fluoride in the system is also reduced, and the etching degree of the frosting liquid to the glass surface is reduced. In example 12, because the concentration of ammonium bifluoride continues to decrease, the dosage of aluminum fluosilicate is relatively high, not only the etching degree of the frosting solution to the glass surface decreases, but also the polymerization speed is too high due to the high dosage of aluminum fluosilicate, so that the surface part generates a condensation phenomenon, and the surface roughness decreases; thus the roughness is reduced to a minimum of 0.534.

Determining the optimal range of the formula of the B powder frosting solution by measuring the roughness: 58.5 to 60.38 percent of ammonium bifluoride; 1.2 to 1.5 percent of oxalic acid dihydrate; 2.5 to 2.99 percent of sulfamic acid; 7.5 to 8.4 percent of ammonium fluoride; 11.5 to 13 percent of barium sulfate; 9-10% of barium fluoride; 0.05 to 0.1 percent of calcium fluoride; 1.6 to 2.5 percent of sodium fluoride; 0.03-0.1% of potassium fluoride dihydrate; 0.5 to 1 percent of sodium dodecyl sulfate; 1.6 to 2.6 percent of aluminum fluosilicate.

The frosted glass prepared at different times was tested for roughness using the frosting solution of example 9 and measured in parallel 6 times, the results are shown in table 5.

TABLE 5 roughness of frosted glass prepared by different time periods with frosting solution of example 9

An electron micrograph of a frosted glass surface prepared by treating glass with the frosted glass frit prepared in example 9 for 2 minutes is shown in FIG. 14, and the average size of the surface-distributed particles of the frosted glass is 0.030 μm after 2 minutes; an electron microscope image of the surface of the frosted glass prepared after treating the glass for 2 minutes and 30 seconds is shown in figure 15, and the average size of the distributed particles on the surface of the frosted glass for 2 minutes and 30 seconds is 0.050 mu m; an electron micrograph of the frosted glass surface prepared 2 minutes and 35 seconds after the glass is treated is shown in FIG. 16, and the average size of the distributed particles on the surface of the frosted glass 2 minutes and 35 seconds is 0.075 μm; from FIGS. 14-16, it can be seen that the particle distribution is very uniform, indicating that the roughness is also very uniform; an electron microscope image of the surface of the frosted glass prepared after frosting for 2 minutes and 40 seconds is shown in figure 17, the average size of the surface distributed particles is 0.085 mu m, the roughness is increased, and the nonuniformity is increased; an electron microscope image of the surface of the frosted glass prepared after 3 minutes of frosting is shown in figure 18, the average size of the surface distribution particles is 0.105 mu m, the roughness is increased, and the nonuniformity is increased; an electron microscope image of the surface of the frosted glass prepared 3 minutes after 30 seconds of frosting is shown in FIG. 19, the average size of the surface-distributed particles is about 0.141-0.150 μm, the roughness is increased, and the unevenness is increased.

EXAMPLE 13 determination of optimum frosting time for AG powder frosting liquid

In order to obtain the optimum frosted glass, the glass was subjected to the frosting treatment using the frosting solution prepared in example 4 at a frosting temperature of 25 ℃ and a pH of 2.5, and the surface roughness of the frosted glass was measured at different frosting times, respectively, and the results are shown in fig. 20. It can be seen that the glass roughness trend with frosting time is: when the frosting time is between 1.5 and 3 minutes, the roughness is reduced along with the increase of the frosting time, and negative correlation is shown; between 3 and 5 minutes, roughness increased with increasing frosting time, showing a positive correlation. It can be found that the lowest point is frosting time of 3 minutes, namely, the roughness is lowest, the frosting effect is best, and the roughness is 0.618 μm. The reason may be that when the frosting time is short, the frosting finish degree is low, and the glass surface generates an uneven phenomenon, which is particularly reflected by large roughness; with the increase of the frosting time, the frosting is basically finished, the surface of the glass becomes gradually smooth, the roughness is reduced, and the minimum value is reached when the frosting time is 3 minutes; as the frosting time continues to increase, the glass surface grains continue to grow, which causes the glass surface roughness to continue to increase.

EXAMPLE 14 determination of the optimum pH of the AG powder frosting solution

The glass was frosted with the frosting solution prepared in example 4 at a frosting temperature of 25 ℃ for 3 minutes, the pH of the frosting solution was adjusted, and the surface roughness after frosting the glass was plotted against the pH of the frosting solution, and the results are shown in fig. 21. As can be seen from fig. 21, the glass roughness trend with the pH of the frosting solution is: when the pH value of the frosting solution is between 0.5 and 1, the roughness is increased along with the increase of the pH value of the frosting solution, and positive correlation is shown; at pH between 1 and 2.5, roughness decreases with increasing pH, showing a negative correlation; when the pH value is increased from 2.5, the roughness of the glass is increased continuously, and a positive correlation is shown. It can be found that the lowest point is when the pH value of the frosting liquid is 2.5, namely the roughness is the lowest, the frosting effect is the best, and the roughness is 0.618 μm. The reason may be that when the pH is too low, the solution is too acidic, and the fluorosilicate particles adhered to the glass surface are dissolved away, but the frosting effect is poor; when the pH value is 2.5, the acidity of the frosting liquid is moderate, the frosting completion degree is high, and the glass surface becomes smooth; when the pH value is increased again, the acidity of the frosting solution is reduced, and fluorosilicate grains with different sizes can be formed on the surface of the glass, which is the reason of increasing the roughness.

The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims

1. The glass frosting solution is characterized by comprising frosting powder and a solvent, wherein the total content of the frosting powder is 100% by mass, and the glass frosting solution comprises the following raw materials: oxalic acid dihydrate 1.0-5.0%, sulfamic acid 2.0-8.0%, white granulated sugar 0-2.0%, sucrose 0-3.0%, barium sulfate 11.0-14.0%, barium fluoride 5.0-11.0%, calcium fluoride 0.02-0.5%, sodium fluoride 0.1-2.5%, potassium fluoride dihydrate 0.05-4.0%, potassium chloride 0-3.0%, aluminum fluosilicate 1.5-6.0%, sodium dodecyl sulfonate 0.5-1.5%, ammonium fluoride 0-9%, magnesium fluosilicate 0-3.0% and ammonium hydrogen fluoride in balance.

2. The glass frosting solution according to claim 1, which comprises a frosting powder and a solvent, wherein the frosting powder comprises the following raw materials in percentage by mass, and the total is 100 percent: 1.2 to 4.9 percent of oxalic acid dihydrate, 2.0 to 8.0 percent of sulfamic acid, 0 to 1.95 percent of white granulated sugar, 0 to 2.92 percent of cane sugar, 11.72 to 13.63 percent of barium sulfate, 5.65 to 9.98 percent of barium fluoride, 0.05 to 0.4 percent of calcium fluoride, 0.1 to 2.5 percent of sodium fluoride, 0.05 to 3.7 percent of potassium fluoride dihydrate, 0 to 2.5 percent of potassium chloride, 1.6 to 5.57 percent of aluminum fluosilicate, 0.5 to 1.2 percent of sodium dodecyl sulfonate, 0.1 to 8.4 percent of ammonium fluoride, 0.5 to 2.8 percent of magnesium fluosilicate and the balance of ammonium bifluoride.

3. A method for preparing the glass frosting solution according to claim 1 or 2, comprising the steps of: accurately weighing the raw materials according to the mass percentage, grinding and crushing, adding a solvent, wherein the solvent is deionized water or hydrochloric acid, dispersing uniformly, heating in a water bath under the stirring condition, and continuing stirring after the water bath is finished.

4. The method for preparing glass frosting solution according to claim 3, wherein the water bath heating temperature is 30-50 ℃ and the water bath heating time is 20-40 min.

5. The method of claim 3, wherein the stirring is continued for a period of 20 to 30 hours.

6. Frosted glass prepared from the glass frosting solution of claim 1 or 2.

7. A method of making the frosted glass of claim 3, comprising the steps of: after glass is pretreated, the pretreated glass is immersed in a frosting solution and cleaned.