CN112645577B - Preparation process of acid-resistant rock plate glass and acid-resistant rock plate glass - Google Patents
Preparation process of acid-resistant rock plate glass and acid-resistant rock plate glass Download PDFInfo
- Publication number
- CN112645577B CN112645577B CN202011505655.6A CN202011505655A CN112645577B CN 112645577 B CN112645577 B CN 112645577B CN 202011505655 A CN202011505655 A CN 202011505655A CN 112645577 B CN112645577 B CN 112645577B
- Authority
- CN
- China
- Prior art keywords
- acid
- glass
- resistant
- rock plate
- plate glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/04—Tempering or quenching glass products using gas
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/119—Deposition methods from solutions or suspensions by printing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a preparation process of acid-resistant rock plate glass and the acid-resistant rock plate glass. Firstly, carrying out slicing, edging, cleaning and drying treatment on a glass substrate to be treated; then, printing ground color and patterns on the surface of the pretreated glass substrate by acid-resistant glass ink through screen printing; wherein the acid-resistant glass ink comprises bismuth oxide and silicon dioxide in a mass ratio of (1.2-1.8) to 1; and then, placing the printed glass substrate in a tempering furnace, carrying out heating sintering treatment at 620-780 ℃, and then sequentially carrying out air cooling to room temperature by adopting hot air and cold air to obtain the acid-resistant rock plate glass. According to the invention, the bismuth oxide in the acid glass ink is reasonably controlled to be 1.2-1.8 times of the mass content of the silicon dioxide, and based on the composition, the sintering process and the air cooling process are finely adjusted, so that bismuth ions are promoted to enter a glass network structure to form a glass body, and the acid resistance of the rock plate glass is obviously improved.
Description
Technical Field
The invention relates to the technical field of glass preparation, in particular to a preparation process of acid-resistant rock plate glass and the acid-resistant rock plate glass.
Background
The rock plate is mainly characterized in that the front surface of glass is subjected to screen printing, high-temperature spray painting, spraying and other means, acid-resistant and high-temperature-resistant ink is used as a raw material to produce a natural stone imitation or other texture effects, and then the natural stone imitation or other texture effects are sintered and subjected to wind steel treatment in a high-temperature furnace, so that the rock plate glass which takes glass as a carrier and has the existing rock touch feeling on the front surface can be achieved, and meanwhile, the rock plate glass can have the toughened glass characteristic. The high-temperature glass ink is also called high-temperature toughened glass ink, the sintering temperature is 650 plus one year at 850 ℃, after high-temperature sintering, the ink and the glass are firmly fused together, the color is bright, and the ink is not easy to fade or fade. The glass fiber reinforced plastic composite material is widely applied to the fields of building glass curtain walls, automobile glass, glass floor tiles and the like.
According to the crystallization principle of glass, the crystals of the glass in the sintering method are formed by the aggregation and growth of ions on the surfaces of glass powder particles, and the crystals are subjected to the processes of crystal nucleus formation, crystal growth, crystal precipitation and the like, and are subjected to crystal analysis at higher temperature. The glass can be crystallized only in a certain temperature interval, and has an optimal crystallization temperature and proper crystal growth time, which can be determined by means of DSC, SEM, XRD and other analysis means. The crystallization of the glass has a large relationship with factors influencing the ion migration rate and the migration quantity, such as the grain size of the glass powder, the heating rate in the sintering process, the heat preservation time during the crystal growth, the viscosity and the temperature of the system, and the like.
In view of the above, there is a need for an improved process for producing acid-resistant rock plate glass to produce a rock plate glass having excellent acid resistance.
Disclosure of Invention
The invention aims to provide a preparation process of acid-resistant rock plate glass and the acid-resistant rock plate glass. The preparation process comprises the steps of screen printing acid-resistant glass ink on the surface of a glass substrate, heating and sintering in stages, and cooling by hot air and cold air in sequence to obtain the rock plate glass with excellent acid resistance.
In order to realize the purpose, the invention provides a preparation process of acid-resistant rock plate glass, which comprises the following steps:
s1, glass pretreatment: carrying out slicing, edging, cleaning and drying treatment on a glass substrate to be treated;
s2, printing ground color and patterns on the surface of the pretreated glass substrate by using acid-resistant glass ink through screen printing; the acid-resistant glass ink comprises bismuth oxide and silicon dioxide in a mass ratio of (1.2-1.8) to 1;
s3, placing the glass substrate printed in the step S2 in a tempering furnace, heating and sintering at 620-780 ℃, and then air-cooling to room temperature to obtain the acid-resistant rock plate glass.
In a further improvement of the present invention, in step S2, the mass ratio of bismuth oxide to silicon dioxide is (1.45-1.65): 1.
As a further improvement of the present invention, in step S2, a polyborosiloxane and/or a polysilsesquioxane is further added to the acid-resistant glass ink.
As a further improvement of the invention, the addition amount of the polyborosiloxane is 28-42% of the mass of the bismuth oxide; the addition amount of the polysilsesquioxane is 12-24% of the mass of the bismuth oxide.
As a further improvement of the present invention, the polysilsesquioxane is a polyphenylsilsesquioxane.
As a further improvement of the invention, the preparation method of the polyborosiloxane comprises the following steps:
s21, adding cyclotetrasiloxane, trifunctional siloxane and boric acid into a diethylene glycol dimethyl ether solvent respectively, adding an acid catalyst, stirring for 10-20 min at 25-35 ℃, then heating to 80-100 ℃, reacting for 0-2 h, continuing heating to 120-150 ℃, and reacting for 2-3 h in a heat preservation manner; the acid catalyst is one or more of sulfuric acid, hydrochloric acid and silicotungstic acid;
s22, after the reaction is finished, cooling to normal temperature to precipitate excessive boric acid, performing centrifugal separation to obtain a mixed solution, then raising the temperature to 90-105 ℃, performing reduced pressure distillation for 30-60 min, and removing a solvent and low-molecular byproducts;
s23, carrying out reduced pressure distillation, adding toluene to dissolve the product, then adding a sodium bicarbonate solution, stirring and washing, carrying out liquid separation and rotary evaporation to obtain a product, and drying to constant weight to obtain the polyborosiloxane.
As a further improvement of the invention, the acid-resistant glass ink comprises the following components in percentage by mass: 25 to 42 percent of silicon dioxide, 40 to 70 percent of bismuth oxide, 1.8 to 5.5 percent of barium oxide, 1.2 to 2.5 percent of aluminum oxide, 0.8 to 3.5 percent of titanium dioxide and 0.65 to 1.5 percent of sodium oxide, wherein the sum of the components is 100 percent.
As a further improvement of the present invention, in step S3, the step of heat sintering treatment includes: heating to 620-680 ℃ at a heating rate of 5 ℃/min, then preserving heat for 1-3 h, heating to 720-780 ℃ at a heating rate of 8 ℃/min, and preserving heat for 20-40 min.
As a further improvement of the present invention, in step S3, the air cooling step includes: firstly, hot air with the temperature of 120-200 ℃ and the air speed of 1.4-1.8 m/s is adopted to cool to 180-250 ℃, and then cold air with the temperature of 15-35 ℃ is adopted to cool to the room temperature.
The acid-resistant rock plate glass is prepared by the preparation method.
The invention has the beneficial effects that:
1. according to the preparation process of the acid-resistant rock plate glass, the mass content of bismuth oxide in the acid-resistant glass ink is reasonably controlled to be 1.2-1.8 times of that of silicon dioxide, based on the composition, the sintering process and the air cooling process are finely adjusted, bismuth ions are promoted to enter a glass network structure to form a glass body, and metal Bi is utilized to form a glass body in the SiO (silicon dioxide) network structure2The promotion effect in the molecular chain of the structure of the glass reduces and reduces the damage of-OH in the glass structure by acid, thereby obviously improving the acid resistance of the rock plate glass.
2. The preparation process of the acid-resistant rock plate glass provided by the invention is based on the component design of acid-resistant ink, adopts segmented temperature rise thermal sintering, keeps the bonding rate of glass powder and the thermal degradation rate of organic components optimal, and effectively prevents the problem that the bonding effect is reduced due to the rapid thermal decomposition of the organic components in the ink or the rapid bonding of glass powder particles, thereby preparing the high acid-resistant rock plate glass.
3. According to the preparation process of the acid-resistant rock plate glass, provided by the invention, hot air and cold air are sequentially adopted for cooling, so that the problems of glass body structure transformation, ink caking property reduction and the like caused by quenching are prevented, and the acid resistance of the rock plate glass is improved.
4. According to the invention, the acid resistance of the glass ink is further improved by adding a proper amount of polyborosiloxane or polysilsesquioxane into the acid-resistant ink. Printing on the surface of glass, and hot bending and sinteringIn the process, the polyborosiloxane and the polysilsesquioxane are thermally decomposed to obtain a cross-linked network structure of Si-O-B, Si-O-Si and B-O-B, Si-O-Si, and bismuth ions can enter the glass network structure to form a glass body, so that the structure is favorable for improving the acid resistance of the glass ink. In the process, the molten and softened bismuth ions can enter the glass network structure to form a glass body, and the structure can obviously improve the acid resistance of the glass ink. Compared with pure SiO2The network is formed by the thermal decomposition of polyborosiloxane and polysilsesquioxane, so that the embedding of bismuth ions is facilitated, and the acid resistance is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme of the present invention are shown in the specific embodiments, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation process of acid-resistant rock plate glass, which comprises the following steps:
s1, glass pretreatment: carrying out slicing, edging, cleaning and drying treatment on a glass substrate to be treated;
s2, printing ground color and patterns on the surface of the pretreated glass substrate by using acid-resistant glass ink through screen printing; the acid-resistant glass ink comprises bismuth oxide and silicon dioxide in a mass ratio of (1.2-1.8) to 1; in actual preparation, in order to ensure that the product has good printing adaptability, the ink must have appropriate fineness, concentration and viscosity, and also has good properties of fluidity, thixotropy, plasticity and the like.
And S3, placing the glass substrate printed in the step S2 in a tempering furnace, heating and sintering at 620-780 ℃, and then air-cooling to room temperature to obtain the acid-resistant rock plate glass.
In step S3, the step of heat sintering treatment includes: heating to 620-680 ℃ at a heating rate of 5 ℃/min, then preserving heat for 1-3 h, heating to 720-780 ℃ at a heating rate of 8 ℃/min, and preserving heat for 20-40 min.
In step S3, the air cooling step includes: firstly, hot air with the temperature of 120-200 ℃ and the wind speed of 1.4-1.8 m/s is adopted to cool to 180-250 ℃, and then cold air with the temperature of 15-35 ℃ is adopted to cool to the room temperature.
In order to ensure that the product has good sintering performance, the thermal expansion coefficient of the acid-resistant glass powder in the ink needs to be matched with that of the glass substrate, and the softening temperature of the glass powder is proper, so that the ink can be just melted completely at the hot bending tempering temperature of the glass, and a compact and continuous ink layer is formed.
When not sintered, the ink mainly comprises glass powder particles which are randomly distributed, organic components which play a role in bonding and a small amount of air; in the initial stage of sintering, the organic components are gradually decomposed, the glass powder particles are mutually bonded and rearranged, the gaps among the particles are deformed and reduced, and the mutual contact is mainly point contact; in the middle stage of sintering, the organic components are further decomposed, the glass substrate to be printed is about to be softened, the glass powder particles are gradually melted and diffused, the glass powder particles are gradually enlarged from point contact to surface contact, but gaps among the particles are not filled, and some closed air holes can appear in the ink; at the final stage of sintering, the organic components are completely decomposed, the air holes in the ink gradually become smaller and are finally isolated and discharged, and a compact and continuous sintered body is formed among the glass powder particles and covers and is adhered to the surface of the just softened printing glass substrate.
In step S2, the mass ratio of bismuth oxide to silicon dioxide is (1.45-1.65): 1.
In step S2, polyborosiloxane and/or polysilsesquioxane is further added to the acid-resistant glass ink. The polysilsesquioxane is preferably a polyphenylsilsesquioxane. The addition amount of the polyborosiloxane is 28-42% of the mass of the bismuth oxide; the addition amount of the polysilsesquioxane is 12-24% of the mass of the bismuth oxide.
The preparation method of the polyborosiloxane comprises the following steps:
s21, adding cyclotetrasiloxane, trifunctional siloxane and boric acid into a solvent diethylene glycol dimethyl ether respectively, adding an acid catalyst, stirring for 10-20 min at 25-35 ℃, then heating to 80-100 ℃, reacting for 0-2 h, continuing heating to 120-150 ℃, and preserving heat for reacting for 2-3 h; the acid catalyst is one or more of sulfuric acid, hydrochloric acid and silicotungstic acid;
s22, after the reaction is finished, cooling to normal temperature to precipitate excessive boric acid, performing centrifugal separation to obtain a mixed solution, then raising the temperature to 90-105 ℃, performing reduced pressure distillation for 30-60 min, and removing a solvent and low-molecular byproducts;
s23, carrying out reduced pressure distillation, adding toluene to dissolve the product, then adding a sodium bicarbonate solution, stirring and washing, carrying out liquid separation and rotary evaporation to obtain a product, and drying to constant weight to obtain the polyborosiloxane.
The acid-resistant glass ink comprises the following components in percentage by mass: 25 to 42 percent of silicon dioxide, 40 to 70 percent of bismuth oxide, 1.8 to 5.5 percent of barium oxide, 1.2 to 2.5 percent of aluminum oxide, 0.8 to 3.5 percent of titanium dioxide and 0.65 to 1.5 percent of sodium oxide, wherein the sum of the components is 100 percent.
The liquid phase component of the acid-resistant glass ink comprises 68-78% of ink adjusting oil, 14-20% of dispersing agent, 7-11% of surfactant and 0.1-2% of light stabilizer by mass percent, and the sum of the components is 100%. The ink adjusting oil is selected from one or more of 1, 2-propylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol phenyl ether and cyclohexanone; the dispersing agent comprises diethylene glycol butyl ether and acrylic resin, and the average molecular weight of the acrylic resin is 5000-8000; the surfactant is 1, 2-propylene glycol diacetate; the light stabilizer is sebacic acid bis (1,2,2,6, 6-pentamethyl-4-piperidyl) ester (HS-508).
The invention also provides acid-resistant rock plate glass prepared by the preparation method.
Example 1
A preparation process of acid-resistant rock plate glass comprises the following steps:
(1) slicing: cutting the glass substrate by using an automatic glass cutting table according to a set drawing;
(2) edging: using a double-edge grinder to continuously edge the edge;
(3) cleaning: cleaning and drying the glass by using a flat plate cleaning machine;
(4) printing: printing base color and patterns on the surface of the pretreated glass substrate by using acid-resistant glass ink through screen printing, wherein the patterns can be printed or can be printed by using a high-temperature inkjet printer;
the acid-resistant glass ink comprises acid-resistant glass powder, inorganic pigment, varnish, dispersant, surfactant and light stabilizer. The acid-resistant glass powder comprises the following components in percentage by mass: 35.5% of silicon dioxide, 55.0% of bismuth oxide (the mass ratio of bismuth oxide to silicon dioxide is 1.56), 1.7% of aluminum oxide, 1.2% of sodium oxide, 2.4% of titanium dioxide, 3.7% of barium oxide and 0.5% of magnesium oxide.
(5) Cleaning: cleaning and cleaning the edge of the glass due to poor printing;
(6) tempering: and (3) placing the printed glass substrate in a tempering furnace, heating to 650 ℃ at a heating rate of 5 ℃/min, then preserving heat for 2h, heating to 750 ℃ at a heating rate of 8 ℃/min, then preserving heat for 30min, cooling to 200 ℃ by adopting hot air with the temperature of 150 ℃ and the air speed of 1.6m/s, and then cooling to room temperature by adopting cold air with the temperature of 25 ℃ to obtain the acid-resistant rock plate glass.
(7) Cleaning and packaging: and cleaning and packaging the glass.
Example 2
Compared with the example 1, the difference of the preparation process of the acid-resistant rock plate glass is that polyborosiloxane accounting for 32 percent of the mass of the bismuth oxide is added into the acid-resistant glass ink. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Wherein the polyborosiloxane is prepared by the steps of:
(1) adding cyclotetrasiloxane, trifunctional siloxane and boric acid into a solvent diethylene glycol dimethyl ether respectively, adding an acid catalyst, stirring for 10-20 min at 25-35 ℃, then heating to 90 ℃, reacting for 1h, continuing heating to 130 ℃, and preserving heat for reacting for 2-3 h; the acid catalyst is one or more of sulfuric acid, hydrochloric acid and silicotungstic acid;
(2) after the reaction is finished, cooling to normal temperature to precipitate excessive boric acid, performing centrifugal separation to obtain a mixed solution, then raising the temperature to 90-105 ℃, performing reduced pressure distillation for 30-60 min, and removing a solvent and a low-molecular byproduct;
(3) and (3) after reduced pressure distillation, adding toluene to dissolve the product, then adding a sodium bicarbonate solution, stirring and washing, separating liquid, carrying out rotary evaporation to obtain a product, and drying to constant weight to obtain the polyborosiloxane.
Example 3
Compared with the example 1, the difference of the preparation process of the acid-resistant rock plate glass is that polyborosiloxane accounting for 32 percent of the mass of bismuth oxide and polysilsesquioxane accounting for 18 percent of the mass of bismuth oxide are added into the acid-resistant glass ink. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Dilute sulfuric acid having a concentration of 5% was dropped on the surface of the prepared rock plate glass, and the acid resistance was tested.
Table 1 results of acid resistance test of examples 1 to 3
As can be seen from table 1, the rock plate glass prepared by the present invention is excellent in acid resistance. The acid resistance of the glass ink is further improved by adding an appropriate amount of polyborosiloxane or polysilsesquioxane. In the process of printing on the surface of glass and carrying out hot bending sintering, the polyborosiloxane and the polysilsesquioxane are thermally decomposed to obtain a cross-linked network structure of Si-O-B, Si-O-Si and B-O-B, Si-O-Si, and bismuth ions can enter the glass network structure to form a glass body, so that the structure is helpful for improving the glass bodyHigh acid resistance of the glass ink. In the process, the molten and softened bismuth ions can enter the glass network structure to form a glass body, and the structure can obviously improve the acid resistance of the glass ink. Compared with pure SiO2The network is formed by the thermal decomposition of polyborosiloxane and polysilsesquioxane, so that the embedding of bismuth ions is facilitated, and the acid resistance is improved.
Examples 4 to 7
A process for producing acid-resistant rock plate glass, which is different from that of example 1 in that, in step S2, the mass ratio of bismuth oxide to silica is as shown in table 2. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Table 2 results of acid resistance test of examples 4 to 7
As can be seen from table 2, when the content ratio of bismuth oxide and silicon dioxide is higher or lower than the preferable value of the compounding ratio range defined in the present invention, the acid resistance is reduced, and particularly, when the content ratio is lower than the compounding ratio range defined in the present invention, the acid resistance is more significantly reduced. Therefore, the mass content of the bismuth oxide is controlled to be 1.45-1.65 times of that of the silicon dioxide, and the bismuth oxide is matched with other additives, so that metal Bi is utilized in SiO2The acid-resistant high-temperature ink has a promoting effect in a molecular chain of the structure, and reduces the damage of-OH in the glass structure by acid, so that the acid-resistant effect is realized, and the acid-resistant high-temperature ink with excellent acid resistance is obtained.
Examples 8 to 12
A process for producing an acid-resistant rock plate glass, which is different from that of example 1 in that the first and second holding temperatures in step S3 are shown in Table 3. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Table 3 results of acid resistance test of examples 8 to 12
As can be seen from table 3, the acid resistance of the rock plate glass was reduced when the stepwise temperature rise sintering was not employed. This is because when the temperature is directly raised to 750 ℃ for sintering, organic components in the ink are rapidly thermally decomposed, and glass frit particles are also rapidly bonded, resulting in a decrease in the bonding effect.
Examples 13 to 17
A process for producing acid-resistant slate glass, which is different from example 1 in that the hot air temperature and the hot air cooling end point temperature in step S3 are shown in Table 4. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Table 4 results of acid resistance test of examples 13 to 17
As can be seen from table 4, when sintering was performed directly with cold air instead of hot air, the acid resistance of the rock plate glass was significantly reduced. Further, when the hot air cooling end temperature is increased, the acid resistance is also decreased. The invention combines the component design of the acid-resistant printing ink, and adopts hot air and cold air cooling in sequence, so that the sintering bonding effect of the glass powder is improved, and the acid resistance of the rock plate glass is improved.
In conclusion, according to the preparation process of the acid-resistant rock plate glass, the base color and the patterns are printed on the surface of the pretreated glass substrate by the acid-resistant glass ink through screen printing; wherein the acid-resistant glass ink comprises bismuth oxide and silicon dioxide in a mass ratio of (1.2-1.8) to 1; and then placing the printed glass substrate in a tempering furnace, carrying out heating sintering treatment at 620-780 ℃, and then sequentially carrying out air cooling to room temperature by adopting hot air and cold air to obtain the acid-resistant rock plate glass. According to the invention, the bismuth oxide in the acid glass ink is reasonably controlled to be 1.2-1.8 times of the mass content of the silicon dioxide, and based on the composition, the sintering process and the air cooling process are finely adjusted, so that bismuth ions are promoted to enter a glass network structure to form a glass body, and the acid resistance of the rock plate glass is obviously improved.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (9)
1. The preparation process of the acid-resistant rock plate glass is characterized by comprising the following steps of:
s1, glass pretreatment: carrying out slicing, edging, cleaning and drying treatment on a glass substrate to be treated;
s2, printing ground color and patterns on the surface of the pretreated glass substrate by using acid-resistant glass ink through screen printing; the acid-resistant glass ink comprises the following components in percentage by mass: 25 to 42 percent of silicon dioxide, 40 to 70 percent of bismuth oxide, 1.8 to 5.5 percent of barium oxide, 1.2 to 2.5 percent of aluminum oxide, 0.8 to 3.5 percent of titanium dioxide and 0.65 to 1.5 percent of sodium oxide, wherein the sum of the components is 100 percent; the mass ratio of the bismuth oxide to the silicon dioxide is (1.2-1.8): 1;
s3, placing the glass substrate printed in the step S2 in a tempering furnace, heating and sintering at 620-780 ℃, and then air-cooling to room temperature to obtain the acid-resistant rock plate glass.
2. The process for producing acid-resistant rock plate glass according to claim 1, wherein in step S2, the mass ratio of bismuth oxide to silicon dioxide is (1.45-1.65): 1.
3. The process of manufacturing acid-resistant slate glass of claim 1, wherein in step S2, a polyborosiloxane and/or a polysilsesquioxane is further added to said acid-resistant glass ink.
4. The process for preparing acid-resistant rock plate glass according to claim 3, wherein the polyborosiloxane is added in an amount of 28-42% by mass of the bismuth oxide; or the addition amount of the polysilsesquioxane is 12-24% of the mass of the bismuth oxide.
5. The process of making acid resistant rock panel glass according to claim 3, wherein said polysilsesquioxane is a polyphenylsilsesquioxane.
6. The process for preparing acid-resistant slate glass according to claim 5, wherein said polyborosiloxane is prepared by:
s21, adding cyclotetrasiloxane, trifunctional siloxane and boric acid into a solvent diethylene glycol dimethyl ether respectively, adding an acid catalyst, stirring for 10-20 min at 25-35 ℃, then heating to 80-100 ℃, reacting for 0-2 h, continuing heating to 120-150 ℃, and preserving heat for reacting for 2-3 h; the acid catalyst is one or more of sulfuric acid, hydrochloric acid and silicotungstic acid;
s22, after the reaction is finished, cooling to normal temperature to precipitate excessive boric acid, performing centrifugal separation to obtain a mixed solution, then raising the temperature to 90-105 ℃, performing reduced pressure distillation for 30-60 min, and removing a solvent and low-molecular byproducts;
s23, carrying out reduced pressure distillation, adding toluene to dissolve the product, then adding a sodium bicarbonate solution, stirring and washing, carrying out liquid separation and rotary evaporation to obtain a product, and drying to constant weight to obtain the polyborosiloxane.
7. The process for producing acid-resistant rock plate glass according to claim 1, wherein in step S3, the step of heat-sintering treatment comprises: heating to 620-680 ℃ at a heating rate of 5 ℃/min, then preserving heat for 1-3 h, heating to 720-780 ℃ at a heating rate of 8 ℃/min, and preserving heat for 20-40 min.
8. The process for preparing acid-resistant slate glass of claim 1, wherein in step S3, the step of air-cooling comprises: firstly, hot air with the temperature of 120-200 ℃ and the air speed of 1.4-1.8 m/s is adopted to cool to 180-250 ℃, and then cold air with the temperature of 15-35 ℃ is adopted to cool to the room temperature.
9. An acid-resistant rock plate glass, characterized by being produced by the production process according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011505655.6A CN112645577B (en) | 2020-12-18 | 2020-12-18 | Preparation process of acid-resistant rock plate glass and acid-resistant rock plate glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011505655.6A CN112645577B (en) | 2020-12-18 | 2020-12-18 | Preparation process of acid-resistant rock plate glass and acid-resistant rock plate glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112645577A CN112645577A (en) | 2021-04-13 |
| CN112645577B true CN112645577B (en) | 2022-05-13 |
Family
ID=75354894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011505655.6A Active CN112645577B (en) | 2020-12-18 | 2020-12-18 | Preparation process of acid-resistant rock plate glass and acid-resistant rock plate glass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112645577B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292251A (en) * | 2021-06-10 | 2021-08-24 | 宁波兴港必利来玻璃科技有限公司 | Processing method of slate glass |
| CN115043595A (en) * | 2022-04-29 | 2022-09-13 | 珠海拾比佰彩图板股份有限公司 | Method for manufacturing rock plate glass with invisible window |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209903A (en) * | 2007-12-21 | 2008-07-02 | 东华大学 | High-temperature resistant lead-less glass powder for glass fiber net printing ink, preparation and application thereof |
| CN105753335A (en) * | 2014-12-18 | 2016-07-13 | 上海宝银电子材料有限公司 | Acid-resistant and antioxidant silver paste for automotive glass and method for preparing acid-resistant and antioxidant silver paste |
| CN106830701A (en) * | 2017-03-08 | 2017-06-13 | 湖南云平环保科技有限公司 | The preparation method of self-cleaning glass |
| CN107572835A (en) * | 2017-08-31 | 2018-01-12 | 江苏拜富科技有限公司 | A kind of high acid resistant automotive glass ink flux and preparation method thereof |
| CN110563346A (en) * | 2019-10-14 | 2019-12-13 | 陈圆圆 | automobile glass inking process |
| CN111018330A (en) * | 2019-11-21 | 2020-04-17 | 苏州市灵通玻璃制品有限公司 | Method for strengthening high borosilicate glass |
-
2020
- 2020-12-18 CN CN202011505655.6A patent/CN112645577B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209903A (en) * | 2007-12-21 | 2008-07-02 | 东华大学 | High-temperature resistant lead-less glass powder for glass fiber net printing ink, preparation and application thereof |
| CN105753335A (en) * | 2014-12-18 | 2016-07-13 | 上海宝银电子材料有限公司 | Acid-resistant and antioxidant silver paste for automotive glass and method for preparing acid-resistant and antioxidant silver paste |
| CN106830701A (en) * | 2017-03-08 | 2017-06-13 | 湖南云平环保科技有限公司 | The preparation method of self-cleaning glass |
| CN107572835A (en) * | 2017-08-31 | 2018-01-12 | 江苏拜富科技有限公司 | A kind of high acid resistant automotive glass ink flux and preparation method thereof |
| CN110563346A (en) * | 2019-10-14 | 2019-12-13 | 陈圆圆 | automobile glass inking process |
| CN111018330A (en) * | 2019-11-21 | 2020-04-17 | 苏州市灵通玻璃制品有限公司 | Method for strengthening high borosilicate glass |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112645577A (en) | 2021-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112645577B (en) | Preparation process of acid-resistant rock plate glass and acid-resistant rock plate glass | |
| CN112724716B (en) | High-reflection glass slurry for photovoltaic module glass backboard and preparation method thereof | |
| JP6342528B2 (en) | Decorative porous inorganic layer suitable for ion exchange process | |
| CN113860737B (en) | Matte dry particle material and preparation method thereof | |
| CN115010367B (en) | Low-temperature quick-firing full-polished crystal glaze, artistic rock plate containing full-polished crystal glaze and preparation method | |
| CN112225526B (en) | Stone dry particles and rock plate with simulation effect and preparation method and application thereof | |
| CN112551910B (en) | Acid-resistant high-temperature ink for glass and preparation method thereof | |
| CN113248286A (en) | Preparation process of glazed tile capable of forming plaque-shaped random crystallization effect and product thereof | |
| CN105130196B (en) | Process for the preparation of a ceramic glass plate, plate obtained by this process and its use | |
| CN114605074A (en) | Microcrystalline glass and preparation method thereof | |
| CN108395231A (en) | Low-expansion heat-resisting ceramic wafer and preparation method thereof | |
| CN112851118A (en) | Tellurate glass with high refractive index and preparation method thereof | |
| CN1053047A (en) | Crystal glass and production method thereof with natural-marble-like surface patterns | |
| CN110922058A (en) | Preparation method for sintering microcrystalline glass plate by using multi-tube distribution | |
| CN108863304B (en) | Ceramic blank, ceramic vessel and preparation method thereof | |
| CN109265001A (en) | Ice-crack-like glaze, ice-crack-like glaze ceramic and production method | |
| CN103304277B (en) | Microcrystal glass ceramic composite plate and one-time rapid sintering method thereof | |
| CN101549947A (en) | Method for integrally producing micro-crystalline ceramic composite plate | |
| CN106565101A (en) | Vacuum glass supporting material, preparation method and vacuum glass | |
| CN113772954B (en) | Ceramic tile with fine wavy surface and preparation method thereof | |
| CN113955943A (en) | Complex phase glass ceramics and preparation method thereof | |
| CN110451806B (en) | Uniform crystallization control method of glass ceramic | |
| CN112592208A (en) | Silk glaze ceramic tile and preparation method thereof | |
| KR101141536B1 (en) | The fabrication methods for mixed indium tin oxide sol and indium tin oxide film | |
| CN110357430B (en) | Potassium feldspar-diopside superimposed crystal glaze as well as preparation method and use method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |