CN114538786A - Frosting liquid and preparation method thereof, frosted glass and glass cover plate - Google Patents
Frosting liquid and preparation method thereof, frosted glass and glass cover plate Download PDFInfo
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- CN114538786A CN114538786A CN202011310558.1A CN202011310558A CN114538786A CN 114538786 A CN114538786 A CN 114538786A CN 202011310558 A CN202011310558 A CN 202011310558A CN 114538786 A CN114538786 A CN 114538786A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
Abstract
The application discloses a frosting solution and a preparation method thereof, frosted glass and a glass cover plate, wherein the frosting solution comprises the following components in parts by weight: 55-81 parts of fluoride; 22-42 parts of fluorosilicate; 21-32 parts of inorganic salt, wherein the inorganic salt comprises soluble calcium salt; 17-29 parts of an acid agent, wherein the acid agent comprises a weak acid agent; 3-10 parts of a dispersing agent; and 40-60 parts of water. The frosting liquid component is favorable for improving the viscosity and the suspension property of the frosting liquid, and the soluble calcium salt reacts with fluoride and fluosilicate to control the crystal growth speed of the surface of the frosting, so that crystal grains are very fine, and the frosting surface has lower roughness.
Description
Technical Field
The invention relates to the technical field of glass surface treatment, in particular to a frosting liquid and a preparation method thereof, frosted glass and a glass cover plate.
Background
At present, cover plate glass mainly adopts the continuous spray mode to carry out the frosting, has developed multiple frosting liquid that is applicable to and sprays the frosting simultaneously, and in order to adapt to the frosting line body, this type of frosting generates the requirement and often is harsher, for example: on one hand, the suspension property of the frosting solution is good, and the good suspension property can ensure that the liquid medicine does not precipitate and block the pipeline because the liquid medicine is sprayed through the pipeline with the diameter of about 15mm-25mm in the frosting process; on the other hand, the viscosity of the frosting liquid is high, and in order to ensure that the reaction time of the frosting liquid and the glass surface is sufficient, the frosting liquid needs to have certain viscosity, and the frosting liquid can stay for a long time when the liquid medicine is sprayed on a product.
The prior frosting liquid formula has the problems that partial components have stronger volatility and reduce the effect of the frosting liquid, or the frosting liquid has large viscosity, poor suspension property and poor fluidity, so that the frosting liquid cannot be suitable for the frosting soaking process, or the powder particles of the frosting liquid are larger, so that larger crystal particles are formed on the surface of glass in the frosting process, so that the roughness of the frosted glass is too high.
Disclosure of Invention
In view of the above-mentioned drawbacks and deficiencies of the prior art, it is desirable to provide a frosting solution, a preparation method thereof, a frosted glass and a glass cover plate.
In a first aspect, the invention provides a frosting solution, which comprises the following components in parts by weight:
55-81 parts of fluoride;
22-42 parts of fluorosilicate;
21-32 parts of inorganic salt, wherein the inorganic salt comprises soluble calcium salt;
17-29 parts of an acid agent, wherein the acid agent comprises a weak acid agent;
3-10 parts of a dispersing agent;
and 40-60 parts of water.
Alternatively, the fluoride comprises ammonium bifluoride and/or ammonium fluoride.
Alternatively, the fluorosilicate salt comprises ammonium fluorosilicate and/or potassium fluorosilicate.
Alternatively, the soluble calcium salt comprises calcium oxide or calcium chloride; the inorganic salt further includes at least one of sodium chloride, ferrous sulfate, sodium nitrate, and ferrous nitrate.
Optionally, the acid agent further comprises hydrofluoric acid, wherein the weak acid agent comprises oxalic acid and/or methanesulfonic acid.
Alternatively, the dispersant comprises sodium dodecylbenzene sulfonate and/or sodium polyacrylate.
As an optional scheme, the frosting solution comprises the following components in parts by weight:
25-35 parts of ammonium bifluoride, 30-46 parts of ammonium fluoride, 14-30 parts of ammonium fluosilicate, 8-12 parts of potassium fluosilicate, 8-10 parts of sodium chloride, 8-10 parts of ferrous sulfate, 5-12 parts of calcium oxide and/or calcium chloride, 7-12 parts of oxalic acid, 10-17 parts of methanesulfonic acid, 2-5 parts of sodium dodecyl benzene sulfonate, 1-5 parts of sodium polyacrylate and 40-60 parts of water.
In a second aspect, the present invention provides a method for preparing a frosting solution according to the first aspect, comprising:
mixing and crushing fluoride, fluorosilicate, inorganic salt and part of acid agent according to a weight ratio to obtain a mixture I;
adding the rest acid agent and the dispersing agent into water according to the weight ratio, heating and stirring the mixture evenly to obtain a mixture II;
and uniformly dispersing the mixture I in the mixture II to obtain the frosting solution.
Alternatively, the average particle size of mixture I is from 2 μm to 8 μm.
In a third aspect, the invention provides frosted glass, which is obtained by performing frosting treatment on glass by using the frosting liquid of the first aspect.
As an optional scheme, the frosting surface of the frosting glass is in a pointed convex structure.
Alternatively, the frosted glass has a roughness of 0.1 μm to 0.3. mu.m.
Alternatively, the frosted glass has a haze of 70% to 95%.
In a fourth aspect, the present invention provides a glass cover plate, at least a portion of which is made of the frosted glass of the second aspect.
The soluble calcium salt is added into the frosting solution, and the viscosity and the suspension property of the frosting solution can be improved in the aqueous solution of the soluble calcium salt, so that the frosting solution can be suitable for the soaking frosting process; under the weak acid condition, the soluble calcium salt, fluoride and fluosilicate further react to control the crystal growth speed of the frosting surface, so that the crystal grains are very fine, and the frosting surface has low roughness.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:
FIG. 1 is an electron microscope photograph of a frosted surface of a frosted glass prepared in example 1 of the present invention;
FIG. 2 is an electron microscope photograph of a frosted surface of a frosted glass prepared in example 2 of the present invention;
FIG. 3 is an electron microscope photograph of a frosted surface of a frosted glass prepared in example 3 of the present invention.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention. It should be noted that, for convenience of description, only the portions related to the present invention are shown in the drawings.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.
The invention provides a novel frosting solution which has better fluidity and suspension property, can be suitable for soaking type frosting treatment, reduces the frosting treatment process and improves the frosting efficiency.
The embodiment of the invention provides a frosting solution, which comprises the following components in parts by weight:
55-81 parts of fluoride;
22-42 parts of fluorosilicate;
21-32 parts of inorganic salt, wherein the inorganic salt comprises soluble calcium salt;
17-29 parts of an acid agent, wherein the acid agent comprises a weak acid agent;
3-10 parts of a dispersing agent;
and 40-60 parts of water.
The soluble calcium salt is added into the frosting solution provided by the invention, and the viscosity and the suspension property of the frosting solution can be improved in the aqueous solution of the soluble calcium salt, so that the frosting solution can be suitable for the soaking frosting process; under the weak acid condition, the soluble calcium salt, fluoride and fluosilicate further react to control the crystal growth speed of the frosting surface, so that the crystal grains are very fine, and the frosting surface has low roughness.
It should be noted that, in the following description,
the fluoride can be at least one of magnesium fluoride, hydrogen fluoride, ammonium fluoride, sodium fluoride, ammonium bifluoride, potassium fluoride and sodium bifluoride; the fluorosilicate can be at least one of ammonium fluorosilicate, sodium fluorosilicate, potassium fluorosilicate, magnesium fluorosilicate, iron fluorosilicate, and calcium fluorosilicate; the inorganic salt can be at least one of sodium chloride, sodium nitrate, sodium sulfate, ferrous nitrate, ferrous sulfate, calcium oxide, calcium chloride, calcium nitrate and calcium carbonate; the acid agent can be any mixture of weak acid and/or strong acid, wherein the weak acid can be at least one of oxalic acid, citric acid and methanesulfonic acid, the strong acid can be at least one of acetic acid, hydrochloric acid, nitric acid and hydrofluoric acid, and the strong acid is favorable for accelerating the reaction speed; the dispersant may be at least one of sodium dodecylbenzene sulfonate, sodium polyacrylate, etc. with the molecular weight of the sodium polyacrylate being in the range of about 200-.
Preferably, the fluoride comprises ammonium bifluoride and/or ammonium fluoride.
Preferably, the fluorosilicate salt comprises ammonium fluorosilicate and/or potassium fluorosilicate.
Preferably, the soluble calcium salt comprises calcium oxide or calcium chloride.
Preferably, the acid agent further comprises hydrofluoric acid, wherein the weak acid agent comprises oxalic acid and/or methanesulfonic acid.
Preferably, the dispersant comprises sodium dodecylbenzene sulfonate and/or sodium polyacrylate.
In a preferred embodiment, the frosting solution comprises the following components in parts by weight:
25-35 parts of ammonium bifluoride and 30-46 parts of ammonium fluoride;
14-30 parts of ammonium fluosilicate and 8-12 parts of potassium fluosilicate;
8-10 parts of sodium chloride and 8-10 parts of ferrous sulfate;
5-12 parts of calcium oxide;
7-12 parts of oxalic acid and 10-17 parts of methanesulfonic acid;
2-5 parts of sodium dodecyl benzene sulfonate and 1-5 parts of sodium polyacrylate;
and 40-60 parts of water.
It should be noted that, in the following description,
the ammonium bifluoride and the ammonium fluoride are used as a fluorine ion etching agent and play a role in providing water-soluble fluorine ions; ammonium fluosilicate and potassium fluosilicate are used as a particle sanding agent and are attached to the surface of glass after etching reaction, and then a 'sand layer' is formed on the surface after etching through chemical reaction; the sodium chloride is used as a sodium ion providing agent, sodium ions are ionized from the sodium chloride in the solution, the sodium ions are combined with fluosilicic acid radical ions in the frosting solution and further attached to the surface of the glass body to form a 'sand layer', and the sodium fluosilicate is in an angular shape, so that the improvement of the crystal form of the sand layer on the surface of the glass is facilitated.
On one hand, calcium oxide reacts with water to generate suspension, so that the viscosity and the suspension property of the frosting liquid are improved, and the frosting liquid is stabilized; on the other hand, suspension generated by the reaction of calcium oxide and water further reacts with fluoride to generate calcium fluoride crystals, and the calcium fluoride crystals form a fine crystal form on the surface of the glass; on the other hand, calcium oxide reacts with water to generate calcium ions, the calcium ions and fluoride ions can slowly generate calcium fluosilicate crystals on the surface of glass in the frosting process, the control of the grain size and the crystal form on the surface of the frosting is facilitated, and the specific reaction principle is as follows:
CaO+H2O＝Ca(OH)2(white suspension)
Ca(OH)2+2H+＝Ca2++H2O
Ca(OH)2The suspension can beThe viscosity and the suspension property of the liquid medicine are improved, and the stability of the liquid medicine is facilitated;
Ca(OH)2the solution can be dissolved in ammonium bifluoride solution to generate calcium fluoride crystals, and fine crystal forms are formed on the surface of the glass;
Ca2+with SiF in the liquid medicine6 2-Reacting, namely slowly and uniformly generating calcium fluosilicate crystals in the frosting process, wherein the calcium fluosilicate crystals generated in the mode have low growth speed, so that the particles are very fine and can obtain very low roughness; when calcium chloride is selected, the principle is basically the same as that of calcium oxide, free calcium ions are ionized in an aqueous solution, and calcium ions and fluosilicic acid radical ions form calcium fluosilicate crystals.
If the calcium fluosilicate or the calcium fluoride is directly added, because the grains of the substances are larger, the grains can be continuously crystallized in the reaction process, and larger grains are generated, so that the frosted surface cannot form the roughness of less than 0.3 mu m.
The ferrous sulfate is combined with fluosilicic acid radical ions to generate the ferrous fluosilicate, which is beneficial to controlling the crystal form of the frosted surface.
Oxalic acid and methanesulfonic acid are used as acidity regulators, can provide hydrogen ions, play a role in acidity regulation, can generate hydrofluoric acid with fluoride ions for etching reaction of glass, and simultaneously control the acidity degree and etching efficiency of an etching solution, so that the uniform and fine frosting effect on the surface of the frosting is ensured, and the problems that the reaction rate is too high, the hydrofluoric acid is volatile and has strong corrosivity, a low-roughness frosting surface cannot be formed and the use is unsafe due to the fact that the hydrofluoric acid is directly added into the frosting solution and is used as the acidity regulators are solved.
The sodium dodecyl benzene sulfonate and the sodium polyacrylate in the additive are used in a matching way and are used as a dispersing agent, so that on one hand, the uniform generation of particles on the surface of glass can be controlled, and meanwhile, the growth speed of crystal grains is controlled, thereby being beneficial to ensuring the fine particles and obtaining a frosted surface with low roughness; on the other hand, the sodium dodecyl benzene sulfonate with the weight of 1-1000 is matched with sodium polyacrylate, so that the frosting solution has lower viscosity after being cured in curing agent water, has better fluidity in the frosting treatment process, ensures the uniformity and stability of the whole system, and is favorable for being applied to the soaking type frosting process.
According to the frosting solution provided by the embodiment of the invention, under the synergistic effect of fluoride, fluosilicate, inorganic salt, calcium oxide, ferrous sulfate, organic acid and additive, the frosting solution has strong suspension property and fluidity, is suitable for the soaking type frosting treatment process, and is beneficial to controlling the frosting solution to generate precipitates on the glass surface uniformly and slowly during frosting treatment and controlling the crystal form and particle size of the precipitates, so that the frosting surface has low roughness.
Wherein, the weight ratio of the ammonium bifluoride is 25-35 parts, such as: 25 parts, 27 parts, 28 parts, 30 parts, 32 parts, 33 parts and 35 parts; the weight ratio of the ammonium fluoride is 30-46 parts, for example: 30 parts, 32 parts, 33 parts, 35 parts, 36 parts, 40 parts, 43 parts and 46 parts; the weight ratio of the ammonium fluosilicate is 14-30 parts, for example: 14 parts, 15 parts, 17 parts, 20 parts, 25 parts, 27 parts, 28 parts and 30 parts; the weight ratio of the potassium fluosilicate is 8-12 parts, for example: 8 parts, 9 parts, 10 parts, 11 parts and 12 parts; the weight ratio of the sodium chloride is 8-10 parts, such as: 8 parts, 9 parts and 10 parts; the weight ratio of the ferrous sulfate is 8-10 parts, such as: 8 parts, 9 parts and 10 parts; the weight ratio of the calcium oxide is 5-12 parts, for example: 5 parts, 6 parts, 8 parts, 9 parts, 10 parts, 11 parts and 12 parts; the weight ratio of the oxalic acid is 26 to 38 parts, such as: 26 parts, 27 parts, 29 parts, 30 parts, 32 parts, 35 parts, 36 parts and 38 parts; the weight ratio of the methanesulfonic acid is 20-30 parts, for example: 20 parts, 21 parts, 23 parts, 24 parts, 26 parts, 28 parts, 29 parts and 30 parts; the weight ratio of the sodium dodecyl benzene sulfonate is 2-5 parts, for example: 2 parts, 3 parts, 4 parts and 5 parts; the weight ratio of the sodium polyacrylate is 1-5 parts, for example: 1 part, 2 parts, 3 parts, 4 parts and 5 parts.
In summary, according to the frosting solution provided by the embodiment of the invention, oxalic acid and methanesulfonic acid are used as acidity regulators, so that acidity is continuously provided for the frosting solution, and the reaction rate of frosting treatment is controlled to be uniform and slow; the calcium oxide reacts in the frosting liquid to generate smaller-grain precipitate calcium fluoride or calcium fluosilicate, so that the problem that the prior art cannot form a low-roughness frosting surface because the calcium fluoride or calcium fluosilicate with larger grains is directly added is avoided; the low-molecular-weight additive is selected, so that the viscosity of the frosting solution is reduced, the flowability is good, the frosting solution is suitable for the soaking type frosting treatment process, and meanwhile, the frosting solution is beneficial to controlling precipitates to be uniformly and slowly generated on the surface of glass during frosting treatment and controlling the crystal form and the particle size of the precipitates, so that the frosting surface has low roughness.
Furthermore, the average grain diameter of a solid mixture consisting of fluoride, fluosilicate, inorganic salt, calcium oxide and oxalic acid in the frosting liquid is 2-8 μm.
In a second aspect, an embodiment of the present invention provides a method for preparing a frosting solution, including:
mixing and crushing the fluoride, the fluosilicate, the inorganic salt and part of the acid agent according to the weight ratio to obtain a mixture I;
adding the rest acid agent and the dispersant into water according to the weight ratio, heating and stirring the mixture evenly to obtain a mixture II;
and uniformly dispersing the mixture I in the mixture II to obtain the frosting solution.
It should be noted that the fluoride, the fluorosilicate, the inorganic salt and a part of the acid agent may be ground and pulverized by a mortar, or may be ground and pulverized by a ball mill, which is not specifically limited in the embodiment of the present invention;
the procedure of pulverizing the fluoride, fluorosilicate, inorganic salt and a part of the acid agent and the procedure of mixing the remaining acid agent and the dispersant in hot water are not limited to the above two procedures, but may be a procedure of mixing the remaining acid agent and the dispersant in hot water.
Further, the average particle diameter of the mixture I is 2 μm to 8 μm. The problems of uneven distribution caused by overlarge average particle size of the mixture, uneven frosting surface formed on the surface of the glass, abnormal color, flow marks and the like are avoided; meanwhile, the problem that the average particle size of the mixture is too small to form a fixed crystal form on glass is avoided, and the frosting effect is reduced. The average particle size range of the embodiment of the invention is beneficial to forming uniform and fine crystals on glass by precipitates generated on the surface of the glass by the frosting solution in the frosting process, and is beneficial to uniform frosting surface and improving frosting effect.
In particular, the method comprises the following steps of,
adding ammonium bifluoride, ammonium fluoride, ammonium fluosilicate, potassium fluosilicate, sodium chloride, ferrous sulfate, calcium oxide and oxalic acid into a grinder according to the proportion, stirring and grinding for 2-4 h until the average particle size is 2-8 μm, and obtaining a mixture I;
heating water to 70-90 ℃, adding methanesulfonic acid, sodium dodecyl benzene sulfonate and sodium polyacrylate into hot water, and stirring for 3-8 min to obtain a mixture II;
and adding the mixture I into the mixture II, and continuously stirring for 10min-20min to uniformly disperse to obtain the frosting liquid.
According to the preparation method of the frosting solution provided by the embodiment of the invention, ammonium bifluoride, ammonium fluoride, ammonium fluorosilicate, potassium fluosilicate, sodium chloride, ferrous sulfate, calcium oxide and oxalic acid are firstly crushed, so that the average particle size of the powder can be ensured to be in an appropriate range, and then the powder is dispersed in the additive, so that the frosting solution can be uniformly mixed, and the frosting effect is improved.
In a third aspect, the invention provides frosted glass, which is obtained by performing frosting treatment on glass by using the frosting solution of the first aspect.
The frosting treatment may be any treatment method, such as soaking, showering, or the like. This embodiment is not particularly limited thereto.
As a preferred embodiment, the glass is subjected to a frosting treatment by using the frosting solution of the first aspect, which is as follows:
putting the prepared frosting liquid into a stirrer for curing, opening the stirrer every 3-4 hours, stirring for 10-20 min, and taking after 72-96 hours;
pretreating glass, removing oil stains, impurities and a silicon oxide film on the surface of the glass, and washing the glass clean by using clear water;
soaking the pretreated glass in the cured frosting solution, continuously stirring the frosting solution, and swinging the glass to perform frosting treatment on the glass;
and cleaning the glass after the frosting treatment to obtain the frosted glass.
As a realizable mode, the frosted surface of the frosted glass is in a pointed convex structure.
Fig. 1-3 show electron micrographs of three frosted surfaces at 100 x magnification, respectively. As shown in the figure, the frosted surface of the frosted glass is in a pointed convex structure. The frosted glass has a pointed convex structure on the surface, so that on one hand, the frosted glass has a frosting effect, light irradiates the whole frosted surface to generate diffuse reflection, the light pollution caused by the glass surface is favorably reduced, and meanwhile, the product of the frosted glass can realize the effects of fingerprint prevention and glare prevention; on the other hand, each convex surface of the pointed convex structure can cause light rays to generate mirror reflection on the convex surface, so that the pearly luster effect of the frosted glass is more obvious. Therefore, the frosted glass provided by the embodiment of the invention has the characteristics of light pollution reduction and good pearling effect, and is multipurpose.
It should be noted that the pointed convex structure may be any one or two or three of a pyramid, a pyramid-like structure and a cone. The pyramid structure and the pyramid-like structure may be at least one of a triangular pyramid, a rectangular pyramid, a pentagonal pyramid, a triangular pyramid-like, a rectangular pyramid-like, a pentagonal pyramid-like, and the like. It should be noted that the pyramid-like structure refers to a structure similar to a pyramid structure, for example, the top of the pyramid-like structure is not sharp, but is planar or one or more surfaces of the pyramid-like structure are curved, and so on.
Further, the frosted glass has a roughness of 0.1 μm to 0.3. mu.m. For example: 0.1 μm, 0.2 μm, 0.3 μm. The frosted glass provided by the embodiment of the invention has lower roughness, can be widely applied to electronic industries, such as a rear cover of electronic equipment, and the like, is beneficial to preventing fingerprints and glare, has a good pearling effect, and improves the practicability and the attractiveness.
Furthermore, the haze of the frosted glass is 70-95%. E.g., 70%, 75%, 76%, 78%, 80%, 82%, 83%, 85%, 87%, 89%, 90%, 92%, 93%, and 95%. The frosted glass provided by the embodiment of the invention has a good frosting effect, namely, has good fingerprint prevention and anti-dazzle effects.
In a fourth aspect, embodiments of the present invention provide a glass cover plate, at least a portion of which is formed from the frosted glass of the third aspect. It will be appreciated by those skilled in the art that the frosted glass has all the features and advantages of the method of making a frosted glass as described above and will not be described in any greater detail herein.
The present invention is illustrated below by way of specific examples, which are intended to be illustrative only and not to limit the scope of the present invention in any way, and reagents and materials used therein are commercially available, unless otherwise specified, and conditions or steps thereof are not specifically described.
Example 1
Selecting the raw materials of the frosting liquid according to the following weight ratio:
27 parts of ammonium bifluoride; 35 parts of ammonium fluoride;
18 parts of ammonium fluosilicate and 8 parts of potassium fluosilicate;
8 parts of sodium chloride and 9 parts of ferrous sulfate;
7 parts of calcium oxide;
12 parts of oxalic acid and 10 parts of methanesulfonic acid;
3 parts of sodium dodecyl benzene sulfonate (molecular weight is 348.48, CAS number 25155-30-0), 2 parts of sodium polyacrylate (molecular weight is 1250, CAS number 9003-04-7);
water: 50 parts of the raw materials.
Preparing a frosting solution:
adding ammonium bifluoride, ammonium fluoride, ammonium fluorosilicate, potassium fluosilicate, sodium chloride, ferrous sulfate, calcium oxide and oxalic acid into a pulverizer, stirring and pulverizing for 2h until the average particle size is 7 μm to obtain a mixture I;
heating water to 80 ℃, adding methanesulfonic acid, sodium dodecyl benzene sulfonate and sodium polyacrylate into the water, and stirring for 5min to obtain a mixture II;
adding the mixture I into the mixture II, and continuously stirring for 15min to obtain a frosting solution;
curing the frosting solution:
placing the prepared frosting liquid in a stirrer, opening the stirrer every 4 hours, stirring for 15min, and curing after lasting for 72 hours;
glass pretreatment:
soaking glass in 15% alkaline detergent for 5min to clean oil stain on the surface, then cleaning the glass in 5% hydrofluoric acid detergent for 5min to remove a silicon oxide film on the surface of the glass, and rinsing the glass with pure water for 1 min to remove residual acid liquor on the surface of the pickled glass;
glass frosting treatment:
mounting the pretreated glass on a mechanical arm, putting the glass into the frosting solution, soaking for 90s, continuously stirring the frosting solution, controlling the mechanical arm to continuously swing the glass, and keeping the glass frosting temperature at 10 ℃ and the swinging speed at 18 m/min;
cleaning treatment:
and putting the frosted glass into a 10% sodium carbonate solution for first rinsing for 15s, and then performing second rinsing in pure water for 30 s.
Example 2
This embodiment is different from embodiment 1 in that,
selecting the raw materials of the frosting liquid according to the following weight ratio:
30 parts of ammonium bifluoride; 40 parts of ammonium fluoride;
22 parts of ammonium fluosilicate and 8 parts of potassium fluosilicate;
10 parts of sodium chloride and 9 parts of ferrous sulfate;
5 parts of calcium oxide;
oxalic acid 9 parts and methanesulfonic acid 17 parts;
5 parts of sodium dodecyl benzene sulfonate and 4 parts of sodium polyacrylate;
water: 40 parts of the components.
Preparing a frosting solution:
adding ammonium bifluoride, ammonium fluoride, ammonium fluorosilicate, potassium fluosilicate, sodium chloride, ferrous sulfate, calcium oxide and oxalic acid into a pulverizer, stirring and pulverizing for 4h until the average particle size is 4 μm to obtain a mixture I;
heating water to 90 ℃, adding methanesulfonic acid, sodium dodecyl benzene sulfonate and sodium polyacrylate into the water, and stirring for 8min to obtain a mixture II;
adding the mixture I into the mixture II, and continuously stirring for 8min to obtain a frosting solution;
curing the frosting solution:
and (3) placing the prepared frosting liquid into a stirrer, opening the stirrer every 3.5 hours, stirring for 10min, and curing after lasting for 96 hours.
Example 3
This embodiment is different from embodiment 1 in that,
selecting the raw materials of the frosting liquid according to the following weight ratio:
30 parts of ammonium bifluoride; 40 parts of ammonium fluoride;
22 parts of ammonium fluosilicate and 8 parts of potassium fluosilicate;
10 parts of sodium chloride and 9 parts of ferrous sulfate;
5 parts of calcium oxide;
oxalic acid 9 parts and methanesulfonic acid 17 parts;
5 parts of sodium dodecyl benzene sulfonate and 4 parts of sodium polyacrylate;
water: 60 parts;
preparing a frosting solution:
adding ammonium bifluoride, ammonium fluoride, ammonium fluorosilicate, potassium fluosilicate, sodium chloride, ferrous sulfate, calcium oxide and oxalic acid into a pulverizer, stirring and pulverizing for 3h until the average particle size is 2 μm to obtain a mixture I;
heating water to 70 ℃, adding methanesulfonic acid, sodium dodecyl benzene sulfonate and sodium polyacrylate into the water, and stirring for 7min to obtain a mixture II;
adding the mixture I into the mixture II, and continuously stirring for 20min to obtain a frosting solution;
curing the frosting solution:
placing the prepared frosting liquid in a stirrer, opening the stirrer every 3 hours, stirring for 20min, and curing after 80 hours;
example 4
This embodiment is different from embodiment 1 in that,
selecting the raw materials of the frosting liquid according to the following weight ratio:
25 parts of ammonium bifluoride; 46 parts of ammonium fluoride;
14 parts of ammonium fluosilicate and 12 parts of potassium fluosilicate;
9 parts of sodium chloride and 8 parts of ferrous sulfate;
10 parts of calcium oxide;
7 parts of oxalic acid and 15 parts of methanesulfonic acid;
2 parts of sodium dodecyl benzene sulfonate and 5 parts of sodium polyacrylate;
water: and 45 parts of the total weight.
Example 5
This embodiment is different from embodiment 1 in that,
selecting the raw materials of the frosting liquid according to the following weight ratio:
35 parts of ammonium bifluoride; 31 parts of ammonium fluoride;
30 parts of ammonium fluosilicate and 11 parts of potassium fluosilicate;
9 parts of sodium chloride and 10 parts of ferrous sulfate;
12 parts of calcium oxide;
oxalic acid 9 parts and methanesulfonic acid 17 parts;
4 parts of sodium dodecyl benzene sulfonate and 1 part of sodium polyacrylate;
water: 40 parts of the components.
Example 6
This embodiment is different from the embodiment 1 in that,
selecting the raw materials of the frosting liquid according to the following weight ratio:
30 parts of sodium fluoride; 35 parts of potassium bifluoride;
32 parts of sodium fluosilicate and 8 parts of ammonium fluosilicate;
6 parts of sodium nitrate and 8 parts of ferrous nitrate;
15 parts of calcium chloride;
9 parts of citric acid and 17 parts of methanesulfonic acid;
4 parts of sodium dodecyl benzene sulfonate and 1 part of sodium polyacrylate;
water: 40 parts of the components.
Example 7
This embodiment is different from the embodiment 1 in that,
selecting the raw materials of the frosting liquid according to the following weight ratio:
32 parts of potassium fluoride; 28 parts of sodium hydrogen fluoride;
38 parts of potassium fluosilicate;
8 parts of sodium nitrate and 10 parts of ferrous sulfate;
12 parts of calcium nitrate;
9 parts of citric acid and 17 parts of methanesulfonic acid;
4 parts of sodium dodecyl benzene sulfonate and 1 part of sodium polyacrylate;
water: 40 parts of the components.
Comparative example 1
This comparative example 1 differs from example 1 in that the frosting solution does not include soluble calcium salts, i.e. does not contain calcium oxide.
Comparative example 2
This comparative example 1 is different from example 1 in that oxalic acid and methanesulfonic acid in the frosting solution of example 1 are replaced with the same parts by weight of nitric acid.
Comparative example 3
This comparative example 1 is different from example 1 in that calcium oxide in the frosting solution of example 1 is replaced by the same weight part of calcium fluoride.
Comparative example 4
Comparative example 1 differs from example 1 in that the weight part of calcium oxide in the frosting solution is 50 parts.
The frosted glass prepared in the above examples 1 to 7 and comparative examples 1 to 4, 5pcs glass is added in each example and comparative example, the roughness of the surface of the frosted glass is measured by GB/T131-1993, the test point is the center of the product, and the test result is shown in Table 1:
TABLE 1 roughness test results of examples 1 to 7, and comparative examples 1 to 4, in μm
Further, the frosted glass obtained in examples 1 to 7 and comparative examples 1 to 4 was subjected to haze test using GB T2410-2008, and the test results are shown in Table 2:
table 2 haze test results of examples 1 to 7, and comparative examples 1 to 4
| Product numbering | 1 | 2 | 3 | 4 | 5 | Mean value of |
| Example 1 | 75.6 | 74.3 | 76.2 | 76.9 | 77.8 | 76.2 |
| Example 2 | 79.1 | 80.2 | 81.3 | 78.8 | 79.6 | 79.8 |
| Example 3 | 86.5 | 88.2 | 84.3 | 83.9 | 87.6 | 86.1 |
| Example 4 | 78.3 | 79.7 | 80.2 | 79.8 | 80.6 | 79.7 |
| Example 5 | 85.1 | 85.7 | 84.8 | 85.3 | 84.6 | 85.1 |
| Example 6 | 90.1 | 90.3 | 89.6 | 88.6 | 89.8 | 89.7 |
| Example 7 | 86.1 | 87.5 | 86.8 | 86.9 | 87.2 | 86.9 |
| Comparative example 1 | 57.8 | 55.7 | 60.5 | 60.9 | 59.4 | 58.9 |
| Comparative example 2 | 67.1 | 59.9 | 60.3 | 66.9 | 58.8 | 62.6 |
| Comparative example 3 | 67.1 | 59.9 | 60.3 | 66.9 | 58.8 | 62.6 |
| Comparative example 4 | 66.8 | 58.5 | 56.7 | 57.2 | 63.6 | 60.1 |
FIG. 1 shows an electron micrograph of a frosted surface of a frosted glass prepared according to example 1 at 100 times magnification; FIG. 2 shows an electron micrograph of a frosted glass prepared according to example 2 at 100 times magnification; FIG. 3 shows an electron micrograph of a frosted surface of the frosted glass prepared in example 3 at 100 times magnification.
As can be seen from fig. 1 to 3, the frosted glass surfaces of examples 1 to 3 have pointed protrusions and substantially have pyramid-shaped structures, and the protrusions on the frosted glass surfaces are uniformly distributed to generate a pearl effect on the pyramid surfaces of the pyramid-shaped structures. The frosting liquid provided by the embodiment of the invention is beneficial to generating a uniform crystal structure on the surface of glass so as to improve the frosting effect of the frosted glass.
From the results of table 1, it can be seen that:
the roughness results of the frosted glasses prepared in example 1 and comparative example 1 can be found as follows: the frosting solution of comparative example 1 does not include calcium oxide, and the frosted glass prepared by the frosting solution of comparative example 1 has higher roughness than the frosted glass prepared by the frosting solution of example 1. Therefore, the synergistic effect of the calcium salt and other components in the frosting liquid of the embodiment of the invention is beneficial to reducing the roughness of the frosted glass.
Roughness results for frosted glasses prepared in example 1 and comparative example 2 can be found: the frosting solution of comparative example 1, in which a strong acid is added, produces a frosted glass having a higher roughness than the frosted glass produced by the frosting solution of example 1. Therefore, the use of the weak acid agent in the frosting solution of the embodiment of the invention is beneficial to making the frosted glass have low roughness.
Roughness results for frosted glasses prepared in example 1 and comparative example 3 can be obtained: the frosting solution of comparative example 1 contains calcium fluoride, and the roughness of the frosted glass prepared by the frosting solution is far higher than that of the frosted glass prepared by the frosting solution of example 1. Because the crystal grains of the calcium fluoride are large, the calcium fluoride can be continuously crystallized in the reaction process to generate large crystal grains, so that the frosted surface cannot form high roughness and cannot form the roughness lower than 0.3 mu m. Therefore, the calcium salt in the frosting liquid of the embodiment of the invention is beneficial to the frosted glass to have lower roughness.
Roughness results for frosted glasses prepared in example 1 and comparative example 4 can be found: the content of calcium oxide in the frosting solution of the comparative example 1 exceeds the content range of calcium salt provided by the invention, the roughness of the frosted glass prepared by the frosting solution is far higher than that of the frosted glass prepared by the frosting solution of the example 1, and larger crystal grains are generated in the reaction process due to larger calcium content, so that the frosted surface can not form higher roughness. Thus, the disclosed calcium oxide range of the present example facilitates the formation of a roughness below 0.3 μm on the surface of the frosted glass.
The frosted glasses prepared in examples 1 to 7 all had a roughness less than the frosted glasses from comparative examples 1 to 4. The results in table 1 show that the components and content change of the frosting solution provided by the invention are beneficial to reducing the roughness of the frosted glass, the roughness of the frosted surface is controlled within the range of 0.1-0.3 μm, the lower roughness is beneficial to ensuring the performance of the glass, and the good pearlescent effect of the glass is improved, and simultaneously, the light pollution, fingerprint prevention and anti-glare of the glass are reduced.
From the results of table 2, it can be seen that: the haze of the frosted glass prepared in the embodiments 1 to 7 is in the range of 70 to 95 percent, and the higher haze is beneficial to reducing the problem of light pollution caused by the glass. The frosted glass of comparative examples 1 to 4 had a haze of less than 70% compared to comparative examples 1 to 4. Therefore, the frosting solution provided by the embodiment of the invention is beneficial to improving the haze of the frosting surface.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (14)
1. The frosting solution is characterized by comprising the following components in parts by weight:
55-81 parts of fluoride;
22-42 parts of fluorosilicate;
21-32 parts of inorganic salt, wherein the inorganic salt comprises soluble calcium salt;
17-29 parts of an acid agent, wherein the acid agent comprises a weak acid agent;
3-10 parts of a dispersing agent;
and 40-60 parts of water.
2. The frosting solution of claim 1, wherein the fluoride comprises ammonium bifluoride and/or ammonium fluoride.
3. The frosting solution of claim 1, wherein the fluorosilicate comprises ammonium fluorosilicate and/or potassium fluorosilicate.
4. The frosting solution of claim 1, wherein the soluble calcium salt comprises calcium oxide and/or calcium chloride; the inorganic salt further includes at least one of sodium chloride, ferrous sulfate, sodium nitrate, and ferrous nitrate.
5. The frosting solution according to claim 1, wherein the weak acid agent comprises oxalic acid and/or methanesulfonic acid; the acid agent also includes hydrofluoric acid.
6. The frosting solution of claim 1, wherein the dispersant comprises sodium dodecylbenzene sulfonate and/or sodium polyacrylate.
7. The frosting solution according to any one of claims 1 to 6, wherein the frosting solution comprises the following components in parts by weight:
25-35 parts of ammonium bifluoride, 30-46 parts of ammonium fluoride, 14-30 parts of ammonium fluosilicate, 8-12 parts of potassium fluosilicate, 8-10 parts of sodium chloride, 8-10 parts of ferrous sulfate, 5-12 parts of calcium oxide and/or calcium chloride, 7-12 parts of oxalic acid, 10-17 parts of methanesulfonic acid, 2-5 parts of sodium dodecyl benzene sulfonate, 1-5 parts of sodium polyacrylate and 40-60 parts of water.
8. A method of preparing a frosting solution according to any of claims 1 to 7, comprising:
mixing and crushing the fluoride, the fluosilicate, the inorganic salt and part of the acid agent according to the weight ratio to obtain a mixture I;
adding the rest acid agent and the dispersant into the water according to the weight ratio, heating and stirring the mixture evenly to obtain a mixture II;
and uniformly dispersing the mixture I in the mixture II to obtain the frosting solution.
9. The method according to claim 8, wherein the mixture I has an average particle size of 2 μm to 8 μm.
10. A frosted glass obtained by subjecting a glass to a frosting treatment using the frosting solution according to any one of claims 1 to 7.
11. The frosted glass according to claim 10, wherein the frosted surface of the frosted glass is a pointed convex structure.
12. The frosted glass according to claim 10, wherein the frosted glass has a roughness of 0.1 μm to 0.3 μm.
13. The frosted glass according to claim 10, wherein the frosted glass has a haze of 70% to 95%.
14. A glass cover plate, characterized in that at least a part of the glass cover plate is composed of the frosted glass according to any of claims 10 to 13.
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| CN115108728A (en) * | 2022-07-20 | 2022-09-27 | Oppo广东移动通信有限公司 | Frosting liquid and preparation method thereof, frosted glass and preparation method thereof, and electronic equipment |
| CN115124251A (en) * | 2022-07-20 | 2022-09-30 | Oppo广东移动通信有限公司 | Frosting liquid and preparation method thereof, frosted glass and preparation method thereof, and electronic equipment |
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| CN115448606A (en) * | 2022-09-27 | 2022-12-09 | 江苏孚日玻璃科技有限公司 | Frosting treatment method for glass bottle |
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| CN116081955B (en) * | 2022-12-30 | 2024-04-05 | 咸宁南玻光电玻璃有限公司 | Frosting composition, frosting liquid, flash sand effect high-alumina glass, and preparation method and application thereof |
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