CN108516681B - Microcrystalline glass calendering preparation process applied to 5G communication mobile terminal - Google Patents
Microcrystalline glass calendering preparation process applied to 5G communication mobile terminal Download PDFInfo
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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
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B13/00—Rolling molten glass, i.e. where the molten glass is shaped by rolling
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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- 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
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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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
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Abstract
A microcrystalline glass rolling preparation process applied to a 5G communication mobile terminal belongs to the technical field of microcrystalline glass and comprises the following steps: A. preparing raw materials: preparing 45-75 parts of quartz sand, 10-25 parts of aluminum oxide, 14.5-39.6 parts of sodium carbonate, 2.3-9.2 parts of potassium nitrate, 0-12.5 parts of lithium carbonate, 0-20 parts of magnesium oxide, 0-8 parts of titanium oxide, 0-20 parts of zirconium oxide, 0-10 parts of zinc oxide, 0-9 parts of ammonium dihydrogen phosphate, 0-3 parts of antimony oxide, 0-3 parts of europium oxide and 0-5 parts of ferric oxide by weight parts, and mixing to obtain a batch mixture; B. melting glass; C. rolling and forming; D. annealing, nucleating and crystallizing the glass, and chemically enhancing to obtain the glass ceramics applied to the 5G communication mobile terminal. The microcrystalline glass prepared by the preparation process has excellent optical property and mechanical property, and can be used for electronic terminal display protection screens and rear cover protection shells.
Description
Technical Field
The invention belongs to the technical field of microcrystalline glass, and particularly relates to a preparation process of microcrystalline glass for a 5G communication mobile terminal by a rolling method.
Background
Chemically strengthened glass is often used as a screen protection material in the field of communication mobile terminal electronic equipment. However, the conventional chemically strengthened glass has good scratch and scratch resistance, but still cannot resist the impact caused by equipment falling. Furthermore, with the development of 5G signals, the metal material generally used for the rear cover of the mobile terminal is also restricted to a certain extent.
The microcrystalline glass is used as one of glass materials, has higher mechanical properties than amorphous glass through composition design and controlled crystallization, simultaneously enhances the drop impact resistance by adopting reasonable chemical strengthening, and has great prospect in the application of front and back protective materials of communication mobile terminal equipment.
At present, the continuous forming process of the microcrystalline glass mainly comprises a float method and a rolling method. Both methods have certain limitations in the production of different types of glass. It is known that float glass has two surfaces in contact with air and in contact with molten tin, which differ in chemical composition, and this difference is not apparent in appearance, but has little effect on communication mobile terminal glass substrates requiring chemical strengthening. The influence is shown in that the stress layers on the two surfaces are not uniformly distributed after ion exchange, and finally the strengthening effect is greatly reduced. While conventional calendering methods have advantages in producing thicker glass sheets, they have compositional and processing problems in making ultra-thin glass.
The patent No. CN103073186A utilizes a calendering method to prepare the iron tailing calendered microcrystal cast stone plate, thereby realizing the utilization of the tailing, and the thickness of the formed plate is 5mm-30 mm. The white fluorine-free rolled microcrystalline glass mentioned in patent No. CN103588394A is formed to have a thickness of 18mm to 20 mm. Both aims at producing thicker decorative plates, and does not relate to the production process of ultrathin glass ceramics for 5G mobile terminals. The thickness of the plate produced by the process seriously exceeds the standard, and the energy consumption is large no matter the cutting machine thins, the chemical thinnings and the grinding thinnings.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a multiple rolling forming process for microcrystalline glass for a 5G communication mobile terminal, so as to solve the problems of poor strengthening effect caused by different stress layer structures due to component deviation of the upper surface and the lower surface of chemically strengthened glass and thinning of glass by a rolling method.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a microcrystalline glass rolling preparation process applied to a 5G communication mobile terminal comprises the following steps:
A. preparing raw materials: according to parts by weight, 45-75 parts of quartz sand, 10-25 parts of aluminum oxide, 14.5-39.6 parts of sodium carbonate, 2.3-9.2 parts of potassium nitrate, 0-12.5 parts of lithium carbonate, 0-20 parts of magnesium oxide, 0-8 parts of titanium oxide, 0-20 parts of zirconium oxide, 0-10 parts of zinc oxide, 0-9 parts of ammonium dihydrogen phosphate, 0-3 parts of antimony oxide, 0-3 parts of europium oxide and 0-5 parts of ferric oxide are mixed to obtain a batch mixture;
B. melting: heating the batch to 1550-;
C. rolling and forming: cooling the glass liquid to 1250-;
D. annealing, nucleating and crystallizing: and cooling the rolled glass belt to 700-600 ℃, annealing, performing online nucleation and crystallization at 950-600 ℃ for 3-10 hours to obtain the original plate microcrystalline glass, polishing the original plate microcrystalline glass, and performing chemical enhancement to obtain the microcrystalline glass applied to the 5G mobile terminal.
Control of (MgO + ZnO)/Al in microcrystalline glass composition2O3The mass ratio of (A) to (B) is 0.3-0.88.
In the step A, 0-3 parts of yttrium oxide, 0-3 parts of cerium oxide, 0-3 parts of rubidium oxide, 0-5 parts of gallium oxide, 0-2 parts of manganese oxide and 0-3 parts of nickel oxide are also included.
The invention has the beneficial effects that:
the forming method of rolling and polishing is adopted, so that the stress layer structures caused by the inconsistent components of the upper surface and the lower surface of the microcrystalline glass are prevented from being different, the method has the advantages of good strengthening effect and good economic benefit compared with the float production, and the glass with the thickness of 2-3mm is obtained by rolling.
The glass is thinned by combining the matching of a material prescription design with a continuous rolling method, cutting is not needed in the aspect of thickness processing after rolling forming, the requirements of thickness and smooth surface can be met only in the polishing process, the process is simple, and the economic benefit is good.
The microcrystalline glass prepared by the rolling process has excellent optical performance and mechanical performance after being chemically strengthened, the visible light transmittance of 1mm of a formed glass plate after grinding and polishing can reach 91%, the surface stress reaches above 850MPa after crystallization and chemical strengthening, the stress depth can reach above 35 mu m and even above 60 mu m, the Vickers hardness can reach above 7.3GPa and even above 7.5GPa, the four-point bending strength reaches above 600MPa and even above 650MPa, compared with the float forming method, the Vickers hardness and the four-point bending strength are improved, and the microcrystalline glass can be used for an electronic terminal display protection screen and a rear cover protection shell.
The rolling preparation process of the microcrystalline glass for the 5G communication mobile terminal is suitable for a rolling process and obtaining high-strength microcrystalline meeting performance requirements, and simultaneously, in order to meet the subsequent chemical strengthening process, the design of a long-material glass component is completed through a large number of experiments, wherein the glass component comprises (MgO + ZnO)/Al2O3The mass ratio of (A) to (B) is controlled to be between 0.3 and 0.88.
TiO for glass2And ZrO2At the same time as a nucleating agent, and the total amount is 4-12%, preferably 6-10%, and TiO2In an amount greater than ZrO2And [ TiO ]2/R2O]The mole ratio is controlled between 0.2-0.45, preferably 0.25-0.4, mainly controlling the coloring caused by high titanium content in the glass.
The raw materials of the invention are compounded as follows:
if the content of the silica sand is less than 45 parts, the phase of the glass produced tends to be separated and the chemical stability is poor. On the other hand, if SiO2If the content is too high, more than 75 parts of the composition will result in too high a melting temperature and difficulty in melting, and further affect the forming processes such as float process, rolling, lattice process, and drawing-down process in the later stage.
Alumina is a very important network former, but its coordination structure is closely related to the free oxygen concentration in the glass network. When the microcrystalline glass is introduced together with magnesium oxide, zinc oxide and europium oxide, the aluminum oxide can promote the precipitation of expected crystalline phases and improve the mechanical property and the magnetic property of the microcrystalline glass. The content of the alumina is more than 10 parts, and the strength and the chemical stability of the microcrystalline glass can be improved. However, since the content of alumina is too high, the melting temperature is too high, the melting is difficult, and the subsequent forming processes such as float process, rolling, lattice process, and drawing are affected, the amount of alumina to be incorporated needs to be controlled to 25 parts or less.
The addition of sodium carbonate can reduce the polymerization degree of the glass network structure, reduce the glass melting temperature and improve the glass melting performance. When the titanium dioxide is added together with titanium oxide, the coordination condition of Ti ions can be effectively regulated and controlled. When lithium carbonate is added into the glass raw material at the same time, the lithium carbonate exchanges with potassium ions in molten salt in the chemical enhancement process of the glass ceramics, and the appropriate surface compressive stress value and diffusion depth can be obtained. Therefore, the amount of the addition thereof is controlled to 14.5 parts or more. However, too much sodium carbonate causes deterioration of chemical stability of the glass and influences the formation of the intended main crystal phase during the crystallization, so that the addition amount thereof needs to be controlled to 39.6 or less.
The addition of potassium nitrate can reduce the melting temperature of the glass, improve the melting quality and improve the optical performance of the glass. In addition, under the condition that lithium carbonate and sodium carbonate are added together, the potassium nitrate is added, so that the ion exchange depth is improved, and the mechanical property and the optical property of the chemically-enhanced microcrystalline glass are improved. Therefore, the addition amount of potassium nitrate must be controlled to 2.3-9.2.
The lithium carbonate is added into the glass raw material, so that the glass melting temperature can be greatly reduced, the melting quality is improved, and the glass forming is improved. Under the condition that ammonium carbonate and potassium nitrate are introduced together, the deep ion exchange depth is favorably formed. However, too high a content thereof may affect the chemical stability of the glass and exert a series of influences on the forming process. Therefore, the adding amount of the additive needs to be controlled between 0 and 12.5 parts. When the lithium carbonate is added in an amount of more than 6 parts, the ion exchange depth can be increased to more than 60 μm, while if it is not introduced, the ion exchange depth will be less than 60 μm.
The addition of magnesium oxide into the glass raw material can improve the melting of the glass, and when zinc oxide, aluminum oxide and europium oxide are added together, the content of magnesium oxide can control the crystallization process of the microcrystalline glass and adjust the microstructure of the microcrystalline glass. However, too high a content can have a negative effect, leading to uncontrolled devitrification of the glass melt. Therefore, the amount of the addition is controlled to be 0 to 41 parts.
Zinc oxide is one of the constituents of the crystallized phase of the glass ceramics. The zinc oxide is added into the glass raw material, so that the melting of the glass can be improved, and the optical performance of the glass can be improved. However, too high a content adversely affects the melting and forming of the glass, and tends to cause phase separation between the melt and the glass. Therefore, the addition amount is controlled to be 0 to 10 parts.
Titanium oxide is one of the optional components as a nucleating agent. On one hand, the addition of the titanium oxide effectively promotes the precipitation of crystal nuclei in the nucleation process, and on the other hand, the addition of the titanium oxide easily causes the phase change of the melt, so that the uncontrollable crystallization of the melt is caused, and the forming of the glass is influenced. Therefore, the amount of titanium oxide to be added is controlled to 0 to 8.
Zirconia is one of the optional components as a crystal nucleus agent. The zirconia is added into the glass raw material, so that the crystal nucleus can be effectively promoted, the effect of refining crystal grains can be achieved, and the precipitation of nano-scale crystals in the microcrystalline glass is promoted. In addition, the zirconium oxide is beneficial to improving the chemical stability of the glass and improving the visible light transmittance. Therefore, the zirconia content is preferably 2 parts or more. Under the condition of adding ammonium dihydrogen phosphate together, the solubility of zirconium oxide in glass melt can be improved, the glass forming performance is improved, and the strength of crystallized glass ceramics is improved. However, the upper limit of the amount of zirconia added is 20 parts because it causes difficulty in melting and the glass melt is liable to devitrify to affect the forming process.
Europium oxide is used as a network outer body, and the melting effect of the glass can be obviously improved by adding the europium oxide into the raw materials, so that the forming is facilitated. More importantly, in the presence of lithium carbonate, sodium carbonate, magnesium oxide and zinc oxide, europium oxide is added to perform synergistic action with the 4 components, so that the functions of supporting each other are realized, the paramagnetism of the glass ceramics is improved, the magnetic loss is reduced, and the mechanical property of the glass ceramics is improved, and the adding amount of the europium oxide is required to be controlled to be less than 3 parts.
The addition of ammonium dihydrogen phosphate to the raw materials is beneficial to improving the melting of the glass. And under the condition that the zirconia is added together, the solubility of the zirconia in the glass melt can be improved, and the introduction amount of the zirconia can be increased. However, when the amount of ammonium dihydrogen phosphate added is too large, phase separation tends to occur and devitrification of the glass tends to occur, so that the amount to be added is controlled to 0 to 9 parts.
Antimony oxide is used as an important clarifying agent of glass, the addition of the antimony oxide is favorable for reducing the formation of gas defects in a glass melt, reducing the number of bubbles in the melt and improving the clarifying effect, and the antimony oxide is very important for preparing microcrystalline glass which meets the requirements of a mobile terminal, and the addition amount of the antimony oxide needs to be controlled to be 0-3 parts.
The iron oxide is an important component of the microcrystalline glass rear cover, and the europium oxide, the aluminum oxide, the magnesium oxide and the zinc oxide are added together, so that the glass rear cover can obtain an expected color, the magnetic performance of the glass can be further improved, and the magnetic loss of the microcrystalline glass is reduced. However, since the amount of iron oxide added is too high to cause difficulty in melting, the amount thereof needs to be controlled to 0 to 5 parts.
In order to further reduce the glass melting temperature, improve the melting quality and improve the glass forming performance, thereby obtaining uniform and flawless mother glass and forming a proper crystal phase in the crystallization process to obtain corresponding magnetic properties, yttrium oxide, cerium oxide, rubidium oxide and gallium oxide can be preferably introduced into the composition.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Detailed description of the preferred embodiments
Example 1
A rolling method preparation process of microcrystalline glass for a 5G communication mobile terminal comprises the following steps:
A. firstly, accurately weighing raw materials according to a material prescription, forcibly and uniformly mixing the raw materials, and then putting the raw materials into a feeding pool at regular time and quantity. The material formula is as follows: 50 parts of quartz sand, 10.5 parts of aluminum oxide, 15 parts of sodium carbonate, 2.5 parts of potassium nitrate, 2 parts of lithium carbonate, 9.5 parts of magnesium oxide, 3 parts of titanium oxide, 2.5 parts of zirconium oxide, 4 parts of zinc oxide, 0.5 part of rubidium oxide, 0.25 part of gallium oxide and 0.25 part of europium oxide.
B. And heating the batch in the melting tank to 1525 ℃ for melting, clarifying, stirring and homogenizing to obtain the defect-free glass liquid with excellent quality.
C. Cooling the clarified and homogenized molten glass to 1200 ℃, performing calendering and forming, feeding the molten glass into a first calendering roller at 950 ℃, feeding the molten glass into a second calendering roller at 852 ℃, and discharging the molten glass from the second calendering roller at 765 ℃.
D. And (3) cooling the glass belt to 630 ℃, then annealing in an annealing kiln, nucleating at 680 ℃ for 2 hours, and crystallizing at 800 ℃ for 2 hours to obtain the original plate microcrystalline glass.
E. And soaking the original plate glass ceramics in potassium nitrate molten salt at 450 ℃ for 6 hours to obtain the glass ceramics for the 5G communication mobile terminal. .
The performance of the high-strength glass ceramics is prepared, and the glass forming thickness is as follows: 2mm, the thickness is 1mm after grinding and polishing, and the visible light transmittance is 91%. After crystallization and chemical strengthening, the surface stress is 910Mpa, the stress depth is 73 μm, the Vickers hardness reaches 8GPa, and the bending strength reaches 730 MPa.
Example 2
A. Firstly, accurately weighing raw materials according to a material prescription, forcibly and uniformly mixing the raw materials, and then putting the raw materials into a feeding pool at regular time and quantity. The material formula is as follows: 50 parts of quartz sand, 15.5 parts of alumina, 26.3 parts of sodium carbonate, 4.6 parts of potassium nitrate, 13.3 parts of magnesium oxide and 4.45 parts of ammonium dihydrogen phosphate.
B. And heating the batch in the melting tank to 1500 ℃ for melting, clarifying, stirring and homogenizing to obtain the defect-free glass liquid with excellent quality.
C. Cooling the clarified and homogenized molten glass to 1250 ℃, then performing calendering and forming, feeding the molten glass into a first calendering roller at 1000 ℃, and feeding the molten glass into a second calendering roller at 900 ℃. The temperature of the exit calender rolls was 750 ℃.
D. And (3) cooling the glass belt to 650 ℃, then annealing in an annealing kiln, nucleating at 680 ℃ for 2 hours, and crystallizing at 800 ℃ for 2 hours to obtain the original plate microcrystalline glass.
E. And soaking the original plate glass ceramics in potassium nitrate molten salt at 450 ℃ for 3 hours to obtain the glass ceramics for the 5G communication mobile terminal.
The performance of the high-strength glass ceramics is prepared, and the glass forming thickness is as follows: 3mm, the thickness is 1mm after grinding and polishing, and the visible light transmittance is 91%. After crystallization and chemical strengthening, the surface stress is 900Mpa, the stress depth is 35 mu m, the Vickers hardness is 7.8GPa, and the bending strength is 670 MPa.
Example 3
A. Firstly, accurately weighing raw materials according to a material prescription, forcibly and uniformly mixing the raw materials, and then putting the raw materials into a feeding pool at regular time and quantity. The material formula is as follows: 48.2 parts of quartz sand, 20.6 parts of aluminum oxide, 24.5 parts of sodium carbonate, 2.3 parts of potassium nitrate, 10.6 parts of lithium carbonate, 7.5 parts of magnesium oxide, 2 parts of zirconium oxide, 1.55 parts of ammonium dihydrogen phosphate, 1 part of antimony oxide and 1 part of rubidium oxide.
B. And heating the batch in the melting tank to 1550 ℃ for melting, clarifying, stirring and homogenizing to obtain the defect-free glass liquid with excellent quality.
C. Cooling the clarified and homogenized molten glass to 1235 ℃, performing calendering and forming, feeding the molten glass into a first calendering roller at 1050 ℃, and feeding the molten glass into a second calendering roller at 902 ℃. The temperature of the exit calender rolls was 800 ℃.
D. And (3) cooling the glass belt to 600 ℃, then annealing in an annealing kiln, nucleating for 3 hours at 650 ℃, and crystallizing for 1 hour at 800 ℃ to obtain the original plate microcrystalline glass.
E. The raw plate glass ceramics are soaked in sodium-potassium mixed molten salt at 400 ℃ for 6 hours, washed and then soaked in potassium nitrate molten salt at 450 ℃ for 2 hours to obtain the glass ceramics for the 5G communication mobile terminal.
The formula of the sodium-potassium mixed molten salt comprises the following components: 90 parts of sodium nitrate and 10 parts of potassium nitrate.
The performance of the high-strength glass ceramics is prepared, and the glass forming thickness is as follows: 2.5mm, the thickness is 1mm after grinding and polishing, and the visible light transmittance is 91%. After crystallization and chemical strengthening, the surface stress is 900Mpa, the stress depth is 115 mu m, the Vickers hardness is 7.7GPa, and the bending strength is 620MPa
Example 4
A. Firstly, accurately weighing raw materials according to a material prescription, forcibly and uniformly mixing the raw materials, and then putting the raw materials into a feeding pool at regular time and quantity. The material formula is as follows: 75 parts of quartz sand, 10 parts of aluminum oxide, 20 parts of sodium carbonate, 4.6 parts of potassium nitrate, 12.5 parts of lithium carbonate, 2 parts of magnesium oxide, 4 parts of titanium oxide, 1 part of zinc oxide, 1.03 parts of ammonium dihydrogen phosphate and 1 part of europium oxide.
B. And heating the batch in the melting tank to 1550 ℃ for melting, clarifying, stirring and homogenizing to obtain the defect-free glass liquid with excellent quality.
C. Cooling the clarified and homogenized molten glass to 1225 ℃, performing calendering and forming, feeding the molten glass into a first calendering roller at 950 ℃, and feeding the molten glass into a second calendering roller at 852 ℃. The temperature of the exit calender roll was 765 ℃.
D. And (3) cooling the glass belt to 700 ℃, then annealing in an annealing kiln, nucleating for 4 hours at 750 ℃, and crystallizing for 1 hour at 950 ℃ to obtain the original plate microcrystalline glass.
E. The glass ceramics of the original plate are soaked in potassium nitrate molten salt at 430 ℃ for 4 hours to obtain the glass ceramics for the 5G communication mobile terminal.
The performance of the high-strength glass ceramics is prepared, and the glass forming thickness is as follows: 2.8mm, the thickness is 1mm after grinding and polishing, the surface stress is 920Mpa, the stress depth is 78 mu m, the Vickers hardness is 8.5GPa, and the bending strength is 750MPa after crystallization and chemical strengthening.
Example 5
A. Firstly, accurately weighing raw materials according to a material prescription, forcibly and uniformly mixing the raw materials, and then putting the raw materials into a feeding pool at regular time and quantity. The material formula is as follows: 45 parts of quartz sand, 12 parts of aluminum oxide, 18.1 parts of sodium carbonate, 3.4 parts of potassium nitrate, 8.6 parts of lithium carbonate, 2.5 parts of magnesium oxide, 5 parts of titanium oxide, 10 parts of zirconium oxide, 2 parts of zinc oxide, 1.03 parts of ammonium dihydrogen phosphate, 3 parts of europium oxide and 1 part of yttrium oxide.
B. And heating the batch in the melting tank to 1530 ℃ for melting, clarifying, stirring and homogenizing to obtain the defect-free glass liquid with excellent quality.
C. Cooling the clarified and homogenized glass liquid to 1200 ℃, performing calendering and forming, feeding the glass liquid into a first calendering roller at 1000 ℃, and feeding the glass liquid into a second calendering roller at 8895 ℃. The temperature of the exit calender rolls was 800 ℃.
D. And (3) cooling the glass belt to 700 ℃, then annealing in an annealing kiln, nucleating for 4 hours at 750 ℃, and crystallizing for 1 hour at 950 ℃ to obtain the original plate microcrystalline glass.
E. The raw plate microcrystalline glass is soaked in sodium-potassium mixed molten salt at 400 ℃ for 6 hours, washed and then soaked in potassium nitrate molten salt at 460 ℃ for 2 hours to obtain the microcrystalline glass for the 5G communication mobile terminal.
The formula of the sodium-potassium mixed molten salt comprises the following components: 85 parts of sodium nitrate and 15 parts of potassium nitrate.
The performance of the high-strength glass ceramics is prepared, and the glass forming thickness is as follows: 2.88mm, the thickness is 1mm after grinding and polishing, and the visible light transmittance is 91%. After crystallization and chemical strengthening, the surface stress is 998Mpa, the stress depth is 79 mu m, the Vickers hardness is 8.3GPa, and the bending strength is 750 MPa.
Example 6
A. Firstly, accurately weighing raw materials according to a material prescription, forcibly and uniformly mixing the raw materials, and then putting the raw materials into a feeding pool at regular time and quantity. The material formula is as follows: 45 parts of quartz sand, 10 parts of aluminum oxide, 14.5 parts of sodium carbonate, 6.9 parts of potassium nitrate, 6.9 parts of lithium carbonate, 4 parts of magnesium oxide, 1 part of titanium oxide, 15 parts of zirconium oxide, 0.5 part of zinc oxide, 9 parts of ammonium dihydrogen phosphate, 1 part of cerium oxide and 1 part of europium oxide.
B. And heating the batch in the melting tank to 1510 ℃ for melting, clarifying, stirring and homogenizing to obtain the defect-free glass liquid with excellent quality.
C. Cooling the clarified and homogenized glass liquid to 1245 ℃, performing calendering and forming, feeding the glass liquid into a first calendering roller at 1050 ℃, and feeding the glass liquid into a second calendering roller at 860 ℃. The temperature of the exit calender rolls was 778 ℃.
D. And (3) cooling the glass belt to 650 ℃, then annealing in an annealing kiln, nucleating for 3 hours at 750 ℃, and crystallizing for 4 hours at 850 ℃ to obtain the original plate microcrystalline glass.
E. The raw plate glass ceramics are soaked in sodium-potassium mixed molten salt at 400 ℃ for 5 hours, washed and soaked in potassium nitrate molten salt at 450 ℃ for 4 hours to obtain the glass ceramics for the 5G communication mobile terminal.
The formula of the sodium-potassium mixed molten salt comprises the following components: 95 parts of sodium nitrate and 5 parts of potassium nitrate.
The performance of the high-strength glass ceramics is prepared, and the glass forming thickness is as follows: 2.7mm, the thickness is 1mm after grinding and polishing, and the visible light transmittance is 91%. After crystallization and chemical strengthening, the surface stress is 910MPa, the stress depth is 100 μm, the Vickers hardness is 9GPa, and the bending strength is 745 MPa.
Example 7
A. Firstly, accurately weighing raw materials according to a material prescription, forcibly and uniformly mixing the raw materials, and then putting the raw materials into a feeding pool at regular time and quantity. The material formula is as follows: 47.8 parts of quartz sand, 18 parts of alumina, 21.7 parts of sodium carbonate, 2.3 parts of potassium nitrate, 12.5 parts of lithium carbonate, 10 parts of magnesium oxide, 2 parts of titanium oxide, 2 parts of zirconium oxide, 1 part of zinc oxide, 0.55 part of ammonium dihydrogen phosphate, 0.4 part of europium oxide and 1 part of gallium oxide.
B. And heating the batch in the melting tank to 1500 ℃ for melting, clarifying, stirring and homogenizing to obtain the defect-free glass liquid with excellent quality.
C. Cooling the clarified and homogenized molten glass to 1200 ℃, performing calendering and forming, feeding the molten glass into a first calendering roller at 980 ℃, and feeding the molten glass into a second calendering roller at 875 ℃. The temperature of the discharged calendering rolls was 766 ℃.
D. And (3) cooling the glass belt to 600 ℃, then annealing in an annealing kiln, nucleating for 4 hours at 680 ℃, and crystallizing for 1 hour at 900 ℃ to obtain the original plate microcrystalline glass.
E. The mother plate glass ceramics are soaked in sodium-potassium mixed molten salt at 400 ℃ for 4 hours, washed and then soaked in potassium nitrate molten salt at 425 ℃ for 0.5 hour, and the glass ceramics for the 5G communication mobile terminal are obtained.
The formula of the sodium-potassium mixed molten salt comprises the following components: 90 parts of sodium nitrate and 10 parts of potassium nitrate.
The performance of the high-strength glass ceramics is prepared, and the glass forming thickness is as follows: 2.77mm and a visible light transmittance of 91 percent. After crystallization and chemical strengthening, the surface stress is 900Mpa, the stress depth is 88 mu m, the Vickers hardness is 8.6GPa, and the bending strength is 800 MPa.
Example 8
A. Firstly, accurately weighing raw materials according to a material prescription, forcibly and uniformly mixing the raw materials, and then putting the raw materials into a feeding pool at regular time and quantity. The material formula is as follows: 45 parts of quartz sand, 10 parts of aluminum oxide, 14.5 parts of sodium carbonate, 8 parts of potassium nitrate, 1 part of magnesium oxide, 2 parts of titanium oxide, 15 parts of zirconium oxide, 3.1 parts of ammonium dihydrogen phosphate, 2 parts of antimony oxide, 2.5 parts of europium oxide, 5 parts of iron oxide, 1 part of cerium oxide, 1 part of manganese oxide and 1 part of nickel oxide.
B. And heating the batch in the melting tank to 1500 ℃ for melting, clarifying, stirring and homogenizing to obtain the defect-free glass liquid with excellent quality.
C. Cooling the clarified and homogenized molten glass to 1240 ℃, then carrying out calendaring formation, entering a first calendaring roller at 1050 ℃, and entering a second calendaring roller at 900 ℃. The temperature of the exit calender rolls was 800 ℃.
D. And (3) cooling the glass belt to 600 ℃, then annealing in an annealing kiln, nucleating for 4 hours at 680 ℃, and crystallizing for 1 hour at 900 ℃ to obtain the original plate microcrystalline glass.
E. And soaking the original plate glass ceramics in potassium nitrate molten salt at 430 ℃ for 4 hours to obtain the glass ceramics for the 5G communication mobile terminal.
The performance of the high-strength glass ceramics is prepared, and the glass forming thickness is as follows: 2.65mm, and the thickness is 1mm after grinding and polishing. After crystallization and chemical strengthening, the surface stress is 890MPa, the stress depth is 40 μm, the Vickers hardness is 7.5GPa, and the bending strength is 660 MPa.
Example 9
A. Firstly, accurately weighing raw materials according to a material prescription, forcibly and uniformly mixing the raw materials, and then putting the raw materials into a feeding pool at regular time and quantity. The material formula is as follows: 45 parts of quartz sand, 10 parts of aluminum oxide, 20 parts of sodium carbonate, 4.6 parts of potassium nitrate, 10 parts of lithium carbonate, 6 parts of magnesium oxide, 3.5 parts of titanium oxide, 3 parts of zirconium oxide, 2.5 parts of zinc oxide, 4.13 parts of ammonium dihydrogen phosphate, 3 parts of europium oxide, 2 parts of iron oxide, 1 part of yttrium oxide, 1.5 parts of cerium oxide, 3 parts of rubidium oxide, 1 part of gallium oxide, 2 parts of manganese oxide and 1 part of nickel oxide.
B. And heating the batch in the melting tank to 1535 ℃ for melting, clarifying, stirring and homogenizing to obtain the defect-free glass liquid with excellent quality.
C. Cooling the clarified and homogenized glass liquid to 1200 ℃, performing calendering and forming, feeding the glass liquid into a first calendering roller at the temperature of 985 ℃, and feeding the glass liquid into a second calendering roller at the temperature of 852 ℃. The temperature of the exit calender roll was 765 ℃.
D. And (3) cooling the glass belt to 600 ℃, then annealing in an annealing kiln, nucleating for 4 hours at 680 ℃, and crystallizing for 1 hour at 900 ℃ to obtain the original plate microcrystalline glass.
E. The raw plate glass ceramics are soaked in sodium-potassium mixed molten salt at 450 ℃ for 4 hours, washed and then soaked in potassium nitrate molten salt at 450 ℃ for 2 hours to obtain the glass ceramics for the 5G communication mobile terminal.
The formula of the sodium-potassium mixed molten salt comprises the following components: 99 parts of sodium nitrate and 1 part of potassium nitrate.
The performance of the high-strength glass ceramics is prepared, and the glass forming thickness is as follows: 2.55mm, the thickness is 1mm after grinding and polishing, the surface stress is 950Mpa, the stress depth is 130 μm, the Vickers hardness is 8GPa, and the bending strength is 710MPa after crystallization and chemical strengthening.
Example 10
A. Firstly, accurately weighing raw materials according to a material prescription, forcibly and uniformly mixing the raw materials, and then putting the raw materials into a feeding pool at regular time and quantity. The material formula is as follows: 52 parts of quartz sand, 25 parts of aluminum oxide, 23.5 parts of sodium carbonate, 6.9 parts of potassium nitrate, 3.1 parts of ammonium dihydrogen phosphate, 1 part of antimony oxide and 3 parts of nickel oxide.
B. And heating the batch in the melting tank to 1550 ℃ for melting, clarifying, stirring and homogenizing to obtain the defect-free glass liquid with excellent quality.
C. Cooling the clarified and homogenized glass liquid to 1235 ℃, performing calendering and forming, feeding the glass liquid into a first calendering roller at 955 ℃, and feeding the glass liquid into a second calendering roller at 860 ℃. The temperature of the exit calender rolls was 770 ℃.
D. And (3) cooling the glass belt to 650 ℃, then annealing in an annealing kiln, nucleating for 2.5 hours at 700 ℃, and crystallizing for 1 hour at 900 ℃ to obtain the original plate microcrystalline glass.
E. And soaking the original plate glass ceramics in the potassium nitrate molten salt at 435 ℃ for 3 hours to obtain the glass ceramics for the 5G communication mobile terminal.
The performance of the high-strength glass ceramics is prepared, and the glass forming thickness is as follows: 3mm, the thickness is 1mm after grinding and polishing, the surface stress is 885Mpa, the stress depth is 35 mu m, the Vickers hardness is 7.3GPa, and the bending strength is 600MPa after crystallization and chemical strengthening.
Example 11
A. Firstly, accurately weighing raw materials according to a material prescription, forcibly and uniformly mixing the raw materials, and then putting the raw materials into a feeding pool at regular time and quantity. The material formula is as follows: 50 parts of quartz sand, 10 parts of aluminum oxide, 23.6 parts of sodium carbonate, 4.6 parts of potassium nitrate, 8.6 parts of lithium carbonate, 7 parts of magnesium oxide, 8 parts of titanium oxide, 1 part of zinc oxide, 2.5 parts of zirconium oxide, 3.1 parts of ammonium dihydrogen phosphate, 1 part of antimony oxide and 1 part of europium oxide.
B. And heating the batch in the melting tank to 1550 ℃ for melting, clarifying, stirring and homogenizing to obtain the defect-free glass liquid with excellent quality.
C. Cooling the clarified and homogenized molten glass to 1200 ℃, performing calendering and forming, feeding the molten glass into a first calendering roller at 965 ℃, and feeding the molten glass into a second calendering roller at 875 ℃. The temperature of the exit calender rolls was 756 ℃.
D. And (3) cooling the glass belt to 650 ℃, then annealing in an annealing kiln, nucleating for 2.5 hours at 700 ℃, and crystallizing for 1 hour at 900 ℃ to obtain the original plate microcrystalline glass.
E. The raw plate glass ceramics are soaked in sodium-potassium mixed molten salt at 400 ℃ for 6 hours, washed and then soaked in potassium nitrate molten salt at 475 ℃ for 3 hours to obtain the glass ceramics for the 5G communication mobile terminal.
The formula of the sodium-potassium mixed molten salt comprises the following components: 99 parts of sodium nitrate and 1 part of potassium nitrate.
The performance of the high-strength glass ceramics is prepared, and the glass forming thickness is as follows: 2.68mm, the thickness is 1mm after grinding and polishing, and the visible light transmittance is 91%. After crystallization and chemical strengthening, the surface stress is 1065MPa, the stress depth is 150 μm, the Vickers hardness is 8.3GPa, and the bending strength is 733 MPa.
Second, test analysis
Taking example 5 as an example, the test performance was performed by the same operation as in example 5 except that sodium carbonate was not included as control 1, lithium carbonate was not included as control 2, magnesium oxide was not included as control 3, zinc oxide was not included as control 4, and europium oxide was not included as control 5, and the results are shown in the following table.
From the above table, it can be seen that when sodium carbonate, lithium carbonate, magnesium oxide, zinc oxide, and europium oxide coexist at the same time, the vickers hardness, the bending strength, the surface compressive stress value, and the stress depth value can be further improved based on the formulation and process of the present invention.
Claims (3)
1. A microcrystalline glass rolling preparation process applied to a 5G communication mobile terminal is characterized by comprising the following steps:
A. preparing raw materials: according to parts by weight, 45-75 parts of quartz sand, 10-25 parts of aluminum oxide, 14.5-39.6 parts of sodium carbonate, 2.3-9.2 parts of potassium nitrate, 6.9-12.5 parts of lithium carbonate, 2-20 parts of magnesium oxide, 0-8 parts of titanium oxide, 0-20 parts of zirconium oxide, 0.5-10 parts of zinc oxide, 0-9 parts of ammonium dihydrogen phosphate, 0-3 parts of antimony oxide, 1-3 parts of europium oxide and 0-5 parts of ferric oxide are mixed to obtain a batch mixture;
B. melting: heating the batch to 1550-;
C. rolling and forming: cooling the glass liquid to 1250-;
D. annealing, nucleating and crystallizing: cooling the rolled glass ribbon to 700-600 ℃ for annealing, then carrying out online nucleation and crystallization at 950-600 ℃ for 3-10 hours to obtain original plate microcrystalline glass, polishing the original plate microcrystalline glass, and carrying out chemical enhancement to obtain the microcrystalline glass applied to the 5G mobile terminal;
the prepared microcrystalline glass has the surface stress of more than 910MPa, the stress depth of more than 73 mu m, the Vickers hardness of more than 7.5GPa and the four-point bending strength of more than 650 MPa.
2. The microcrystalline glass rolling method applied to 5G communication mobile terminal according to claim 1The preparation process is characterized in that (MgO + ZnO)/Al in the composition of the microcrystalline glass is controlled2O3The mass ratio of (A) to (B) is 0.3-0.88.
3. The microcrystalline glass rolling method preparation process applied to the 5G communication mobile terminal, according to claim 1, is characterized in that step A further comprises 0-3 parts of yttrium oxide, 0-3 parts of cerium oxide, 0-3 parts of rubidium oxide, 0-5 parts of gallium oxide, 0-2 parts of manganese oxide and 0-3 parts of nickel oxide.
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