CN114195392A - Glass composition, microcrystalline glass, and preparation method and application thereof - Google Patents

Glass composition, microcrystalline glass, and preparation method and application thereof Download PDF

Info

Publication number
CN114195392A
CN114195392A CN202111681556.8A CN202111681556A CN114195392A CN 114195392 A CN114195392 A CN 114195392A CN 202111681556 A CN202111681556 A CN 202111681556A CN 114195392 A CN114195392 A CN 114195392A
Authority
CN
China
Prior art keywords
glass
microcrystalline
sio
zro
ceramic
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.)
Pending
Application number
CN202111681556.8A
Other languages
Chinese (zh)
Inventor
徐兴军
陶武刚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen New Kibing Technology Co ltd
Original Assignee
Shenzhen New Kibing Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shenzhen New Kibing Technology Co ltd filed Critical Shenzhen New Kibing Technology Co ltd
Publication of CN114195392A publication Critical patent/CN114195392A/en
Priority to PCT/CN2022/139075 priority Critical patent/WO2023125015A1/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • C03C10/0027—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 containing SiO2, Al2O3, Li2O as main constituents
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C03B17/06—Forming glass sheets
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00—Shaping glass in contact with the surface of a liquid
    • C03B18/02—Forming sheets
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses a glass composition, microcrystalline glass, a preparation method and an application thereof, wherein the glass composition comprises the following components in percentage by mass: SiO 2272～74.3％、Al2O37～8.5％、P2O51.8～3％、Li2O10.2～12.5％、Na20.5 to 2% of O and ZrO23.5 to 4.7 percent. In the technical scheme of the invention, the component SiO in the glass composition2、Al2O3、P2O5、Li2O、Na2O and ZrO2The specific proportion combination is adopted, and the crystallization process and the strengthening process of the microcrystalline glass are combined, so that the b value and the haze can be obviously reduced, the crystal content can not be excessively reduced after the chemical strengthening, and the interlocking structure of a double crystal phase can not be excessively destroyed, and the microcrystalline glass with excellent strengthening performance can be obtained.

Description

Glass composition, microcrystalline glass, and preparation method and application thereof
Technical Field
The invention relates to the technical field of glass manufacturing, and particularly relates to a glass composition, microcrystalline glass, and a preparation method and application thereof.
Background
With the development of display technology, glass is often used in the protection of display devices. Cover plate glass for protecting electronic products in the market generally belongs to high-alumina silicate glass, and high alumina is beneficial to improving the stress strength and the depth of a stress layer after ion exchange, but the anti-falling performance of the glass is poor. Studies have shown that 70% of electronic product damage is caused by inadvertent dropping.
The glass is prepared by introducing nucleating agent into the glass formulation or adjusting the oxide proportion in the formulation to form one or more crystalline phases in the subsequent heat treatment process, which is called as microcrystalline glass. The glass has high permeability and high strength of ceramic, and can improve the average hardness, fracture toughness and other performances of the glass. The microcrystalline phase in the microcrystalline glass can block the expansion path of the microcrack, and is beneficial to the integral improvement of the performances of scratch resistance, impact resistance, falling resistance and the like of the glass.
The properties of the glass-ceramic depend on the ratio of the crystal phase to the glass phase, the size of the crystal grains, and the like. In the process of preparing the microcrystalline glass, due to factors such as agglomeration of glass components, interface morphology of crystalline phases, appearance of crystalline grains and the like, the currently prepared transparent microcrystalline glass has a large b value and a high haze, and macroscopically shows that transmitted light turns yellow, so that the transmittance and the service performance of the microcrystalline glass are influenced. During the chemical strengthening process of the microcrystalline glass, the lithium in the crystalline phase participates in the chemical strengthening ion exchange, so that the crystal content in the microcrystalline glass is reduced, and meanwhile, the interlocking structure of the double crystalline phases is damaged, so that the optimal performance of the microcrystalline glass cannot be exerted.
Disclosure of Invention
The invention mainly aims to provide a glass composition, a microcrystalline glass, a preparation method and application thereof, and aims to provide a glass composition which can be used for preparing the microcrystalline glass capable of reducing the b value and the haze, not reducing the crystal content excessively after chemical strengthening and not destroying the interlocking structure of a double crystal phase excessively.
In order to achieve the purpose, the invention provides a glass composition which comprises the following components in percentage by mass:
SiO272～74.3％、Al2O37～8.5％、P2O51.8～3％、Li2O10.2～12.5％、Na20.5 to 2% of O and ZrO23.5～4.7％。
Alternatively, 2.9 ≦ W (SiO)2)-6×W(Al2O3)-2×W(Li2O)≤5.2；
0.26≤[W(Li2O)-W(Al2O3)]/[W(P2O5)+W(ZrO2)]≤0.85；
1.17≤W(ZrO2)/W(P2O5)≤2.61；
2.5≤[W(SiO2)-6×W(Al2O3)-2×W(Li2O)]/W(Na2O)≤5.8。
Optionally, the composition comprises the following components in percentage by mass:
SiO272.8～73.9％、Al2O37.4～8％、P2O52.1～2.6％、Li2O10.7～11.7％、Na20.9 to 1.4% of O and ZrO23.9～4.4％。
Alternatively, 4.5 ≦ W (SiO)2)-6×W(Al2O3)-2×W(Li2O)≤5.2；
0.42≤[W(Li2O)-W(Al2O3)]/[W(P2O5)+W(ZrO2)]≤0.66；
1.5≤W(ZrO2)/W(P2O5)≤2.1；
3.57≤[W(SiO2)-6×W(Al2O3)-2×W(Li2O)]/W(Na2O)≤5。
The invention also provides a microcrystalline glass which comprises the glass composition, wherein the microcrystalline glass contains crystalline phase Li2Si2O5And a crystal phase LiAlSi4O10。
Alternatively, 0.91 ≦ W (Li)2Si2O5)/W(LiAlSi4O10)≤1.06。
Alternatively, 0.97 ≦ W (Li)2Si2O5)/W(LiAlSi4O10)≤1.03。
Alternatively, 10.44 ≦ M ≦ 12.54;
wherein M is 1.3 × [ W (Li)2Si2O5)/W(LiAlSi4O10)]×{0.86×[W(SiO2)-6×W(Al2O3)-2×W(Li2O)]+1.83×[(W(Li2O)-W(Al2O3))/(W(P2O5)+W(ZrO2))]+1.67×[W(ZrO2)/W(P2O5)]+0.25×[(W(SiO2)-6×W(Al2O3)-2×W(Li2O))/W(Na2O)]}。
Alternatively, 11.85 ≦ M ≦ 12.54.
The invention also provides a preparation method of the microcrystalline glass, which comprises the following steps:
weighing the glass composition as described above;
mixing and melting the glass composition, then clarifying, homogenizing, forming, annealing, and finally cutting to obtain base glass;
and carrying out heat treatment on the base glass to obtain the microcrystalline glass.
Optionally, the step of performing heat treatment on the base glass to obtain the glass ceramics comprises:
heating the base glass to 530-570 ℃ from room temperature within 20-60 min, and carrying out nucleation treatment for more than 3 h;
heating to 680-720 ℃ within 5-30 min, and carrying out crystallization treatment for more than 3 h;
and cooling to room temperature to obtain the microcrystalline glass.
Optionally, after the step of performing heat treatment on the base glass to obtain the glass-ceramic, the method further includes:
providing an ion exchange bath, wherein the ion exchange bath comprises 20-40% of NaNO by mass3And 60-80% KNO3；
And (3) pretreating the microcrystalline glass, and then putting the pretreated microcrystalline glass into the ion exchange bath for salt bath to obtain chemically strengthened microcrystalline glass, wherein the salt bath strengthening temperature is 420-500 ℃, and the salt bath strengthening time is 3-8 h.
Optionally, in the step of mixing the glass composition, melting, then clarifying, homogenizing, shaping, annealing, and finally cutting to obtain the base glass, the shaping method comprises float forming, overflow forming, calendaring forming or slot draw forming.
The invention also provides an electronic display terminal which comprises the microcrystalline glass.
In the technical scheme of the invention, the component SiO in the glass composition2、Al2O3、P2O5、Li2O、Na2O and ZrO2The specific proportion combination is adopted, and the crystallization process and the strengthening process of the microcrystalline glass are combined, so that the b value and the haze can be obviously reduced, the crystal content can not be excessively reduced after the chemical strengthening, and the interlocking structure of a double crystal phase can not be excessively destroyed, and the microcrystalline glass with excellent strengthening performance can be obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic flow chart of an embodiment of a method for preparing microcrystalline glass according to the present invention;
fig. 2 is a schematic flow chart of another embodiment of the method for preparing microcrystalline glass according to the present invention;
FIG. 3 is a linear relationship between M and the fracture toughness KIC of the glass-ceramic in the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments.
It should be noted that those whose specific conditions are not specified in the examples were performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
With the development of display technology, glass is often used in the protection of display devices. Cover plate glass for protecting electronic products in the market generally belongs to high-alumina silicate glass, and high alumina is beneficial to improving the stress strength and the depth of a stress layer after ion exchange, but the anti-falling performance of the glass is poor. Studies have shown that 70% of electronic product damage is caused by inadvertent dropping.
The glass is prepared by introducing nucleating agent into the glass formulation or adjusting the oxide proportion in the formulation to form one or more crystalline phases in the subsequent heat treatment process, which is called as microcrystalline glass. The glass has high permeability and high strength of ceramic, and can improve the average hardness, fracture toughness and other performances of the glass. The microcrystalline phase in the microcrystalline glass can block the expansion path of the microcrack, and is beneficial to the integral improvement of the performances of scratch resistance, impact resistance, falling resistance and the like of the glass.
The properties of the glass-ceramic depend on the ratio of the crystal phase to the glass phase, the size of the crystal grains, and the like. In the process of preparing the microcrystalline glass, due to factors such as agglomeration of glass components, interface morphology of crystalline phases, appearance of crystalline grains and the like, the currently prepared transparent microcrystalline glass has a large b value and a high haze, and macroscopically shows that transmitted light turns yellow, so that the transmittance and the service performance of the microcrystalline glass are influenced. During the chemical strengthening process of the microcrystalline glass, the lithium in the crystalline phase participates in the chemical strengthening ion exchange, so that the crystal content in the microcrystalline glass is reduced, and meanwhile, the interlocking structure of the double crystalline phases is damaged, so that the optimal performance of the microcrystalline glass cannot be exerted.
In view of the above, the present invention provides a glass composition, and a glass ceramic prepared from the glass composition can effectively solve the problems of large b value, high haze, and reduced crystal content and damaged interlocking structure of a dual crystal phase in a chemical strengthening process.
The glass composition comprises the following components in percentage by mass: SiO 2272～74.3％、Al2O37～8.5％、P2O51.8～3％、Li2O10.2～12.5％、Na20.5 to 2% of O and ZrO23.5～4.7％。
Firstly, the molecular formula of the microcrystalline glass crystalline phase petalite expected by the invention is LiAlSi4O10Lithium disilicate having the molecular formula of Li2Si2O5. The mass percent of each component is calculated to be SiO in the glass composition2、Al2O3、P2O5、Li2O、Na2O and ZrO2The sum of the masses of (a) is a reference.
Incorporation of SiO into the glass compositions of the present invention2SiO, a component constituting the glass skeleton2Can be used as a main body of a glass network structure, and endows base glass and microcrystalline glass with better chemical stability, mechanical property and forming property. During the glass microcrystallization process, to form Li2Si2O5And LiAlSi4O10The crystalline phase provides SiO2Source, in the glass microcrystallization process, of too high SiO2Promoting the occurrence of quartz and quartz solid solution in the glass micro crystallization process. Thus, taken together, SiO2The content is 72 wt% -74.3 wt%.
Incorporation of Al into the glass compositions of the invention2O3Belonging to the network intermediate oxide. The non-bridging oxygen and Al form an aluminum-oxygen tetrahedron, the volume of which is larger than that of a silicon-oxygen tetrahedron, larger gaps are generated in a glass structure, ion exchange is facilitated, the chemical strengthening effect is better, and the mechanical property of the glass is improved. However, Al2O3The glass belongs to an extremely refractory oxide, and the high-temperature viscosity of the glass can be rapidly improved, so that the clarification and homogenization difficulty of the glass is increased, and the concentration of bubble defects in the glass is greatly increased; al (Al)2O3The content is too high, so that the glass microcrystallization temperature can be obviously improved, the crystallization capacity of the basic glass is inhibited, and lithium disilicate is difficult to form; glass LiAlSi for promoting crystallization process4O10Excessive formation of LiAlSi even in the base glass2O6The crystal phase is generated, so that the glass transmittance is reduced. Therefore, taken together, Al2O3The content is selected from 7 wt% to 8.5 wt%.
Incorporation of P into the glass compositions of the present invention2O5，P2O5More favouring the crystallization of lithium disilicate crystals. P5+The ions have large field intensity and strong oxygen-depriving capacity, and the phosphorus-oxygen network structure tends to be strong. ByIn P5+The ionic field strength is greater than that of Si4+Ion, P5+The ions are easy to be separated from the network by combining with alkali metal ions to form crystal nuclei, thereby promoting the phase separation of the basic glass, reducing the nucleation activation energy and being beneficial to the crystallization of the glass. Li2O and P2O5Reaction to form Li3PO4Crystal phase, thereby inducing Li in the glass2O and SiO2Reaction to form Li2SiO3And finally form Li2Si2O5A crystalline phase; furthermore, P2O5It is prepared from [ PO ]4]The tetrahedrons are connected into a network, so that the glass network structure is in a loose state, and the network gaps are enlarged, thereby being beneficial to Na in the glass+K in ions and molten salts+Ions are diffused mutually, and the strengthening of the ions plays a promoting role in the glass strengthening process and plays an important role in obtaining a higher compressive stress layer. But P is2O5The content is too high, which promotes the precipitation of lithium metasilicate in the crystallization process, so that the glass phase is too little and sufficient Li cannot be formed2Si2O5A crystalline phase and promotes the precipitation of a quartz phase, and it is difficult to obtain a crystallized glass having high transmittance. Thus, taken together, P2O5The content is 1.8 wt% -3 wt%.
Incorporation of Li into the glass composition of the present invention2O, which is a network exo-oxide, lowers the viscosity of the glass and promotes melting and fining of the glass. Li+Is the main exchange ion in the chemical strengthening treatment process. Li+Small ion radius, containing Li+The ion exchange speed of the glass is higher, so that the glass can obtain a thicker strengthening layer in a short time. Li+Ions and Na in the melt+Ion exchange and velocity ratio Na+And K+The exchange speed of the ions is high. High Li2Li in the process of promoting basic microcrystallization by O concentration3PO4Formation, which is beneficial to forming a lithium disilicate crystal phase and a petalite crystal phase in the crystallization process; in order to achieve a microcrystallized glass with a high depth of ion strengthening, sufficient Li must be present in the glass+In the chemical strengthening process with Na+Mutual strengthening occurs to reduce the crystallized glassThe cracks on the surface provide the mechanical strength function of the microcrystalline glass. But too high Li2The viscosity of the O glass is too low to obtain a chemically stable glass composition, and also results in too low a compressive stress value during ion strengthening and increased raw material costs. Therefore, taken together, Li2The content of O is 10.2 wt% -12.5 wt%.
Incorporation of Na into the glass composition of the present invention2And O, the viscosity of the base glass can be obviously reduced, the melting and clarification of the base glass are promoted, and the crystallization temperature of the glass is reduced. Promoting the crystallized glass to be capable of being mixed with K in the potassium nitrate molten salt+Strengthening by ions to generate high compressive stress on the surface of the glass to improve the strength of the glass, and the glass must have sufficient Na+Are present. Therefore, taken together, Na2The content of O is 0.5 wt% -2 wt%.
Incorporation of ZrO into the glass compositions of the invention2. On the one hand, the potential energy of zirconium ions is large, the glass network structure can be enhanced, and ZrO is2The petalite crystal is more likely to be precipitated; on the other hand, ZrO2The method is beneficial to reducing the size of crystal grains in the crystallization process, thereby improving the transmittance of the glass and rapidly improving the chemical stability of the glass. And secondly, the fracture toughness and the bending strength of the glass are improved, the crystal phase of the zirconia is transformed, stress induction can be generated, and the fracture toughness after crystallization is improved. Too high ZrO2Content results in ZrO in the glass2Unmelts exist, resulting in non-uniform devitrification of the glass. Thus, taken together, ZrO2The content is 3.5 wt% -4.7 wt%.
In the technical scheme of the invention, the component SiO in the glass composition2、Al2O3、P2O5、Li2O、Na2O and ZrO2The specific proportion combination is adopted, and the crystallization process and the strengthening process of the microcrystalline glass are combined, so that the b value and the haze can be obviously reduced, the crystal content can not be excessively reduced after the chemical strengthening, and the interlocking structure of a double crystal phase can not be excessively destroyed, and the microcrystalline glass with excellent strengthening performance can be obtained.
The components of the glass composition meet the following conditions: 2.9≤W(SiO2)-6×W(Al2O3)-2×W(Li2o) is less than or equal to 5.2. Let A ═ W (SiO)2)-6×W(Al2O3)-2×W(Li2O), W represents the mass percent of the component accounting for the sum of the masses of all the oxide components, and the value A is the molecular value of the mass percent calculated by the formula. If the A value is lower, SiO2All enter the crystalline phase, relative to Al2O3Or Li2O is excessive; if the A value is too high, Al2O3Or Li2All O enters a crystal phase, and the rest SiO2The glass exists in a network skeleton structure in a glass phase, and the total content of the crystalline phase of the glass ceramics is low. Thus, by controlling the A value within the above range, Al is avoided2O3Or Li2And the content of O is excessive, so that the total crystalline phase content of the glass ceramics is effectively improved. Preferably, 4.5. ltoreq. W (SiO)2)-6×W(Al2O3)-2×W(Li2O)≤5.2。
The components of the glass composition meet the following conditions: w (Li) of 0.26 ≤ and2O)-W(Al2O3)]/[W(P2O5)+W(ZrO2)]less than or equal to 0.85. Let B ═ W (Li)2O)-W(Al2O3)]/[W(P2O5)+W(ZrO2)]And W represents the mass percentage of the component to the sum of the masses of all the oxide components. If the B value is too low, undesirable crystal phases such as beta-quartz and the like are easily generated, the formation proportion of the petalite crystal phase is high, and crystal grains are easily grown, so that the proportion of the microcrystal is semitransparent and even devitrification is caused. If the value of B is too high, the glass phase proportion in the glass-ceramic is increased, and the performance advantage of the glass-ceramic cannot be fully exerted. Therefore, by controlling the B value within the range, the performance advantages of the microcrystalline glass are fully exerted, and the microcrystalline proportion of the microcrystalline glass is prevented from being semitransparent and even devitrified. Preferably, 0.42 ≦ W (Li)2O)-W(Al2O3)]/[W(P2O5)+W(ZrO2)]≤0.66。
The components of the glass composition meet the following conditions: w (ZrO) of 1.17. ltoreq.2)/W(P2O5) Less than or equal to 2.61. Inscription of C-W (ZrO)2)/W(P2O5) W represents the mass of the component based on the sum of the masses of all the oxide componentsPercentage (D). By controlling the C value within the above range, the liquid-liquid surface activation energy is reduced to cause phase separation, and nucleation and crystallization can be performed at a lower temperature. Further realizing the development of phase interface caused by liquid phase crystallization and unstable decomposition, reducing the activation energy or energy barrier of nucleation, and reducing the nucleation temperature and the crystallization temperature. The two crystal phases compete for the silicon source and the lithium source, namely, the crystal phase structure formed by the opposite crystal phase is destroyed to form the own crystal phase, and the crystal phase amounts of the formed petalite and the lithium disilicate are close (W (Li)2Si2O5)/W(LiAlSi4O10) 0.91 to 1.06, described in detail below), uniform crystal size and uniform crystal size<100nm, meets the basic requirement of optical visibility. The C value is too high or too low, so that a single crystal phase is increased and is easy to grow, the visible light transmittance of the microcrystal is reduced, and the haze is increased. Preferably, 1.5. ltoreq. W (ZrO)2)/W(P2O5)≤2.1。
The components of the glass composition meet the following conditions: 2.5 ≤ [ W (SiO)2)-6×W(Al2O3)-2×W(Li2O)]/W(Na2O) is less than or equal to 5.8. Let D ═ W (SiO)2)-6×W(Al2O3)-2×W(Li2O)]/W(Na2O), W represents the mass percentage of the component to the sum of the masses of all the oxide components. By controlling the value of D within the above range, it is helpful to stabilize the crystal structure of the glass, especially to inhibit the migration of lithium ions during the strengthening process. Further maintaining the interlocking structure formed by the microcrystalline glass petalite and the lithium disilicate and improving the performance of the microcrystalline glass. The value D is too high, and the chemical strengthening ions of the microcrystalline glass are difficult to exchange; the D value is too low to maintain the interlocking structure formed by the microcrystalline glass petalite and the lithium disilicate, and the microcrystalline structure is damaged in the chemical strengthening process. Preferably, 3.57 ≦ [ W (SiO)2)-6×W(Al2O3)-2×W(Li2O)]/W(Na2O)≤5。
Further, it is preferable that the components of the glass composition satisfy the following conditions: SiO 2272.8～73.9％、Al2O37.4～8％、P2O52.1～2.6％、Li2O10.7～11.7％、Na20.9 to 1.4% of O and ZrO23.9～4.4 percent. The properties of the glass-ceramic obtained from this glass composition are further optimized.
In an embodiment of the present invention, a glass-ceramic is also provided, which includes the glass composition as described above, and the glass-ceramic includes the crystalline phase Li2Si2O5And a crystal phase LiAlSi4O10The microcrystalline glass includes all technical features of the glass composition, and therefore, all technical effects brought by the glass composition are provided, which is not repeated herein.
The microcrystalline glass also needs to meet the following requirements: w (Li) of 0.91 ≤2Si2O5)/W(LiAlSi4O10) Less than or equal to 1.06. Let E ═ W (Li)2Si2O5)/W(LiAlSi4O10) And W represents the mass percentage of the crystalline phase in the glass ceramics. By controlling the E value in the range, the crystalline phase amounts of the formed petalite and the lithium disilicate are ensured to be close, and the performance of the glass ceramics is further improved. Further preferably 0.97. ltoreq. W (Li)2Si2O5)/W(LiAlSi4O10)≤1.03。
The microcrystalline glass also needs to meet the following requirements: m is more than or equal to 10.44 and less than or equal to 12.54; wherein M is 1.3 × [ W (Li)2Si2O5)/W(LiAlSi4O10)]×{0.86×[W(SiO2)-6×W(Al2O3)-2×W(Li2O)]+1.83×[(W(Li2O)-W(Al2O3))/(W(P2O5)+W(ZrO2))]+1.67×[W(ZrO2)/W(P2O5)]+0.25×[(W(SiO2)-6×W(Al2O3)-2×W(Li2O))/W(Na2O)]}. That is, when M is 1.3 × E × (0.86 × a +1.83 × B +1.67 × C +0.25 × D), it was found that M has a linear relationship with the fracture toughness KIC of the glass-ceramic, and as shown in fig. 3, the value of M is controlled within the above range according to the linear relationship, which contributes to improvement of the fracture toughness of the glass-ceramic. Further preferably, 11.85. ltoreq. M.ltoreq.12.54.
Furthermore, the thickness of the microcrystalline glass is 0.3-1.5 mm. As the thickness of the glass ceramics is thinner, the weight of the glass ceramics can be reduced.
In addition, the invention also provides a preparation method of the microcrystalline glass, which is used for preparing the microcrystalline glass and comprises the following steps as shown in fig. 1:
step S10, weighing the glass composition as described above.
And step S20, mixing and melting the glass composition, then clarifying, homogenizing, molding, annealing, and finally cutting to obtain the base glass.
Specifically, in step S20, the forming method includes float forming, overflow forming, calender forming or slot draw forming. Other processes such as clarification, homogenization, annealing and cutting are conventional procedures in the technical field of glass, and are not described herein any more, and after the processes, the thickness of the obtained basic glass is 0.3-1.5 mm.
And step S30, carrying out heat treatment on the base glass to obtain the microcrystalline glass.
Specifically, step S30 includes: heating the base glass to 530-570 ℃ from room temperature within 20-60 min, and carrying out nucleation treatment for more than 3 h; heating to 680-720 ℃ within 5-30 min, and carrying out crystallization treatment for more than 3 h; and cooling to room temperature to obtain the microcrystalline glass.
Further, after step S30, as shown in fig. 2, the method further includes:
step S40, providing an ion exchange bath, wherein the ion exchange bath comprises 20-40% of NaNO by mass3And 60-80% KNO3。
And S50, pretreating the microcrystalline glass, and then placing the pretreated microcrystalline glass into the ion exchange bath for salt bath to obtain chemically strengthened microcrystalline glass, wherein the salt bath strengthening temperature is 420-500 ℃, and the salt bath strengthening time is 3-8 hours.
In step S40, the preprocessing specifically includes: and (3) insulating the microcrystalline glass at 300-330 ℃ for 5-20 min. The above-mentioned pretreatment is a conventional means in the glass technology field and will not be described in detail here.
The invention further provides an electronic display terminal, which includes the microcrystalline glass, and the specific features of the microcrystalline glass refer to the above embodiments. The microcrystalline glass is used as protective glass or a protective component of an electronic display terminal, or the microcrystalline glass is used as protective glass of an intelligent terminal, or the microcrystalline glass is used as protective glass of a solar battery.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
(1) Weighing a glass composition, wherein the glass composition comprises the following components in percentage by mass: SiO 2272％、Al2O37％、P2O53％、Li2O12.5％、Na2O2% and ZrO23.5％。
(2) And mixing and melting the glass composition, then clarifying, homogenizing, forming, annealing, and finally cutting to obtain the base glass.
(3) Heating the base glass to 530 ℃ from room temperature within 20min, and carrying out nucleation treatment, wherein the nucleation treatment time is 3 h; heating to 680 ℃ within 30min, and carrying out crystallization treatment for 3 h; cooling to room temperature to obtain the microcrystalline glass.
(4) Providing an ion exchange bath comprising, by mass percent, 40% NaNO3And 60% of KNO3And after the microcrystalline glass is pretreated, putting the pretreated microcrystalline glass into the ion exchange bath for salt bath to obtain chemically strengthened microcrystalline glass, wherein the salt bath strengthening temperature is 420 ℃, and the salt bath strengthening time is 3 hours.
The glass-ceramics and the chemically strengthened glass-ceramics of other examples 2 to 14 were prepared by weighing the raw materials in the glass composition component ratios of the respective examples shown in tables 1 and 2 and by referring to the preparation method of example 1.
The glass ceramics and the chemically strengthened glass ceramics of comparative examples 1 to 5 were respectively prepared by weighing the raw materials in the glass composition component ratios of comparative examples 1 to 5 shown in table 3 and referring to the preparation method of example 1.
Microcrystalline glass was prepared by carrying out the steps (1) to (3) of the preparation method in example 1 using the glass compositions of example 8 and example 14, and the specific process parameters for the preparation were shown in table 4.
The glass compositions of example 8 and example 14 were subjected to steps (1) to (4) of the production method of example 1 to produce a chemically strengthened glass ceramic, and specific process parameters of step (4) in the production were shown in table 5, and the remaining steps (1) to (3) were kept the same as in example 1.
Test examples
The test method and test equipment are as follows:
the main crystal phase test was performed using an X-ray diffraction analyzer.
And observing the appearance and the appearance of the crystal by using a scanning electron microscope.
And testing the b value of the color by using a Datacolor650 ultrahigh-precision desktop spectrophotometry color measuring instrument.
Reference standard ISO 13468-1: 1996 visible light transmittance test.
The haze of the glass was measured by the ASTM D1003-92 test.
The glass fracture toughness KIC was determined in MPa m according to ASTM E-18201/2。
The complete machine abrasive paper dropping performance is measured by a mobile phone controlled drop test machine, and the specific test conditions are as follows: 180-mesh sand paper, 195g total weight, 60cm base height, 5cm increment, 1 time per height until breaking.
The performance of the crystallized glass and the chemically strengthened crystallized glass obtained in examples 1 to 14, the crystallized glass and the chemically strengthened crystallized glass obtained in comparative examples 1 to 5, the crystallized glass obtained according to the process parameters of table 4, and the chemically strengthened crystallized glass obtained according to the process parameters of table 5 were respectively tested according to the test methods and the test apparatuses of the test examples, and filled in the corresponding tables, respectively.
It should be understood that the above test mode and test equipment are common modes for evaluating the relevant performance of glass in the industry, and are only one means for characterizing or evaluating the technical scheme and technical effect of the present invention, and other test modes and test equipment can be adopted without affecting the final result.
Table 1 examples 1 to 7 glass composition components and glass properties
Figure BDA0003452887500000111
Table 2 examples 8 to 14 glass composition components and glass properties
Figure BDA0003452887500000112
Figure BDA0003452887500000121
Table 3 comparative examples 1 to 5 glass composition components and glass Properties
Figure BDA0003452887500000122
TABLE 4 Process parameters and Properties for the preparation of glass-ceramics with the glass compositions of examples 8 and 14
Figure BDA0003452887500000131
Wherein, the time in the nucleation treatment and the crystallization treatment represents the time of temperature rise, the temperature represents the temperature rise target temperature, and the time represents the treatment time.
TABLE 5 Process parameters and Properties for the preparation of chemically strengthened glass ceramics with the glass compositions of examples 8 and 14
Figure BDA0003452887500000132
As can be seen from the results of the performance tests of the crystallized glasses of the examples shown in tables 1, 2, 4 and 5, the crystallized phases of lithium disilicate Li in the crystallized glasses obtained after the heat treatment in examples 1 to 14 according to the present invention2Si2O5>30% of crystalline phase petalite LiAlSi4O10>30 percent; total crystalline phase in glass ceramics>68 percent. The microcrystalline glass has a transmittance of 0.7mm>Haze 91%)<0.17, b value<0.4. The average crystal size of the microcrystalline glass crystal grains is<100 nm. The microcrystalline glass has fracture toughness KIC>1.1MPa·m1/2Height of falling resistance>200cm。
As can be seen from Table 3, comparative example 1, SiO271.5%, a 0.5, and D0.42. Heat-treated glass ceramics, Li, not meeting the requirements of the glass composition of the invention2Si2O5/LiAlSi4O100.81, crystal size>100 nm; low transmittance, excessive b value and high haze; the mechanical properties after chemical strengthening are poor.
Comparative example 2, a equals 8 and D equals 6.67. Not meeting the requirements of the glass composition of the present invention, the heat-treated glass-ceramics have a small content of microcrystalline phase and Li2Si2O5/LiAlSi4O10When the chemical strengthening rate is 0.6, the mechanical properties are poor after the chemical strengthening.
Comparative example 3, Li2O is 10% and B is 0.2. Not meeting the requirements of the glass composition of the present invention, the heat-treated glass-ceramics have a small content of microcrystalline phase and Li2Si2O5/LiAlSi4O100.74, crystal size>100 nm; low transmittance, excessive b value and high haze; the mechanical properties after chemical strengthening are poor.
Comparative example 4, P2O51.7%, a 2.1, C2.82, and D2.33. Not meeting the requirements of the glass composition of the present invention, the heat-treated glass-ceramics have a small content of microcrystalline phase and Li2Si2O5/LiAlSi4O100.55, crystal size>100 nm; the transmittance is low, the b value is overlarge, and the haze is large; the mechanical properties after chemical strengthening are poor.
Comparative example 5, P2O53.8%, a 2.7, C0.97, and D2.45. Not meeting the requirements of the glass composition of the present invention, the heat-treated glass-ceramics have a small content of microcrystalline phase and Li2Si2O5/LiAlSi4O101.7, crystal size>100 nm; the transmittance is low, the b value is overlarge, and the haze is large; the mechanical properties after chemical strengthening are poor.
Compared with the chemically strengthened microcrystalline glass in the comparative example, the fracture toughness KIC value (0.43-0.72 MPa-m) of the chemically strengthened microcrystalline glass1/2) The fracture toughness KIC value (1.012-1.78 MPa.m) of the chemically strengthened microcrystalline glass in the embodiment of the invention1/2) Furthermore, the situation that the content of crystals is reduced and the interlocking structure of a double crystal phase is damaged in the chemical strengthening process of the microcrystalline glass provided by the embodiment of the invention is obviously improved; compared with the high b value and the high haze of the microcrystalline glass in the comparative example, the b value and the haze of the microcrystalline glass in the example of the invention are obviously lower, which shows that the microcrystalline glass in the example of the invention realizes the reduction of the b value and the haze. Finally, the obtained chemically strengthened glass ceramics has excellent strengthening performance.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.

Claims (14)

1. The glass composition is characterized by comprising the following components in percentage by mass:
SiO272～74.3％、Al2O37～8.5％、P2O51.8～3％、Li2O10.2～12.5％、Na20.5 to 2% of O and ZrO23.5～4.7％。
2. The glass composition according to claim 1, wherein 2.9. ltoreq. W (SiO)2)-6×W(Al2O3)-2×W(Li2O)≤5.2；
0.26≤[W(Li2O)-W(Al2O3)]/[W(P2O5)+W(ZrO2)]≤0.85；
1.17≤W(ZrO2)/W(P2O5)≤2.61；
2.5≤[W(SiO2)-6×W(Al2O3)-2×W(Li2O)]/W(Na2O)≤5.8。
3. The glass composition according to claim 1, comprising the following components in mass percent:
SiO272.8～73.9％、Al2O37.4～8％、P2O52.1～2.6％、Li2O10.7～11.7％、Na20.9 to 1.4% of O and ZrO23.9～4.4％。
4. The glass composition according to claim 2, wherein 4.5. ltoreq. W (SiO)2)-6×W(Al2O3)-2×W(Li2O)≤5.2；
0.42≤[W(Li2O)-W(Al2O3)]/[W(P2O5)+W(ZrO2)]≤0.66；
1.5≤W(ZrO2)/W(P2O5)≤2.1；
3.57≤[W(SiO2)-6×W(Al2O3)-2×W(Li2O)]/W(Na2O)≤5。
5. A glass-ceramic comprising the glass composition according to any one of claims 1 to 4, wherein the glass-ceramic contains a crystalline phase Li2Si2O5And a crystal phase LiAlSi4O10。
6. The microcrystalline glass according to claim 5, characterised in that 0.91. ltoreq. W (Li)2Si2O5)/W(LiAlSi4O10)≤1.06。
7. The glass-ceramic according to claim 6, wherein 0.97. ltoreq. W (Li)2Si2O5)/W(LiAlSi4O10)≤1.03。
8. The microcrystalline glass according to claim 6, wherein 10.44. ltoreq. M.ltoreq.12.54;
wherein M is 1.3 × [ W (Li)2Si2O5)/W(LiAlSi4O10)]×{0.86×[W(SiO2)-6×W(Al2O3)-2×W(Li2O)]+1.83×[(W(Li2O)-W(Al2O3))/(W(P2O5)+W(ZrO2))]+1.67×[W(ZrO2)/W(P2O5)]+0.25×[(W(SiO2)-6×W(Al2O3)-2×W(Li2O))/W(Na2O)]}。
9. The glass-ceramic according to claim 8, wherein M is 11.85. ltoreq. M.ltoreq.12.54.
10. The preparation method of the microcrystalline glass is characterized by comprising the following steps of:
weighing the glass composition according to any one of claims 1 to 4;
mixing and melting the glass composition, then clarifying, homogenizing, forming, annealing, and finally cutting to obtain base glass;
and carrying out heat treatment on the base glass to obtain the microcrystalline glass.
11. The method for producing a glass-ceramic according to claim 10, wherein the step of heat-treating the base glass to obtain a glass-ceramic comprises:
heating the base glass to 530-570 ℃ from room temperature within 20-60 min, and carrying out nucleation treatment for more than 3 h;
heating to 680-720 ℃ within 5-30 min, and carrying out crystallization treatment for more than 3 h;
and cooling to room temperature to obtain the microcrystalline glass.
12. The method for producing a glass ceramic according to claim 10, wherein the step of heat-treating the base glass to obtain a glass ceramic further comprises:
providing an ion exchange bath, wherein the ion exchange bath comprises 20-40% of NaNO by mass3And 60-80% KNO3；
And (3) pretreating the microcrystalline glass, and then putting the pretreated microcrystalline glass into the ion exchange bath for salt bath to obtain chemically strengthened microcrystalline glass, wherein the salt bath strengthening temperature is 420-500 ℃, and the salt bath strengthening time is 3-8 h.
13. The method for preparing glass-ceramic according to claim 10, wherein the step of mixing the glass composition, melting, clarifying, homogenizing, shaping, annealing, and finally cutting to obtain the base glass comprises float forming, overflow forming, calendaring or slot draw forming.
14. An electronic display terminal, characterized by comprising the crystallized glass of any one of claims 5 to 9.
CN202111681556.8A 2021-12-24 2021-12-31 Glass composition, microcrystalline glass, and preparation method and application thereof Pending CN114195392A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2022/139075 WO2023125015A1 (en) 2021-12-24 2022-12-14 Glass composition, microcrystalline glass, preparation method therefor and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2021116088597 2021-12-24
CN202111608859 2021-12-24

Publications (1)

Publication Number Publication Date
CN114195392A true CN114195392A (en) 2022-03-18

Family

ID=80657955

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111681556.8A Pending CN114195392A (en) 2021-12-24 2021-12-31 Glass composition, microcrystalline glass, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114195392A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115490428A (en) * 2022-09-16 2022-12-20 四川虹科创新科技有限公司 Transparent glass ceramics with ultrahigh drop strength and preparation method thereof
CN115716709A (en) * 2022-11-22 2023-02-28 湖南旗滨微晶新材料有限公司 Microcrystalline glass, preparation method thereof and microcrystalline glass product
CN115745400A (en) * 2022-11-22 2023-03-07 湖南旗滨微晶新材料有限公司 Glass composition, reinforced microcrystalline glass, preparation method of reinforced microcrystalline glass and microcrystalline glass product
WO2023125015A1 (en) * 2021-12-24 2023-07-06 深圳市新旗滨科技有限公司 Glass composition, microcrystalline glass, preparation method therefor and use thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6284340B1 (en) * 1999-09-29 2001-09-04 Ngk Insulators, Ltd. Crystallized glass, magnetic disc substrate and magnetic disc
TW202106645A (en) * 2019-05-29 2021-02-16 美商康寧公司 Colored glass-ceramics having petalite and lithium silicate structures
CN113195424A (en) * 2018-07-16 2021-07-30 康宁股份有限公司 Glass-ceramic articles with improved properties and methods of making the same
CN113248152A (en) * 2021-05-21 2021-08-13 常熟佳合显示科技有限公司 Three-dimensional glass ceramics and preparation method thereof
CN113387586A (en) * 2021-08-06 2021-09-14 成都光明光电股份有限公司 Glass ceramics, glass ceramics product and manufacturing method thereof
CN113402172A (en) * 2021-08-06 2021-09-17 成都光明光电有限责任公司 Glass-ceramic and glass-ceramic article

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6284340B1 (en) * 1999-09-29 2001-09-04 Ngk Insulators, Ltd. Crystallized glass, magnetic disc substrate and magnetic disc
CN113195424A (en) * 2018-07-16 2021-07-30 康宁股份有限公司 Glass-ceramic articles with improved properties and methods of making the same
TW202106645A (en) * 2019-05-29 2021-02-16 美商康寧公司 Colored glass-ceramics having petalite and lithium silicate structures
CN113248152A (en) * 2021-05-21 2021-08-13 常熟佳合显示科技有限公司 Three-dimensional glass ceramics and preparation method thereof
CN113387586A (en) * 2021-08-06 2021-09-14 成都光明光电股份有限公司 Glass ceramics, glass ceramics product and manufacturing method thereof
CN113402172A (en) * 2021-08-06 2021-09-17 成都光明光电有限责任公司 Glass-ceramic and glass-ceramic article

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023125015A1 (en) * 2021-12-24 2023-07-06 深圳市新旗滨科技有限公司 Glass composition, microcrystalline glass, preparation method therefor and use thereof
CN115490428A (en) * 2022-09-16 2022-12-20 四川虹科创新科技有限公司 Transparent glass ceramics with ultrahigh drop strength and preparation method thereof
CN115716709A (en) * 2022-11-22 2023-02-28 湖南旗滨微晶新材料有限公司 Microcrystalline glass, preparation method thereof and microcrystalline glass product
CN115745400A (en) * 2022-11-22 2023-03-07 湖南旗滨微晶新材料有限公司 Glass composition, reinforced microcrystalline glass, preparation method of reinforced microcrystalline glass and microcrystalline glass product
CN115716709B (en) * 2022-11-22 2024-03-12 湖南旗滨新材料有限公司 Microcrystalline glass, preparation method thereof and microcrystalline glass product
WO2024109498A1 (en) * 2022-11-22 2024-05-30 湖南旗滨新材料有限公司 Glass ceramics, preparation method therefor, and glass ceramics article
WO2024109499A1 (en) * 2022-11-22 2024-05-30 湖南旗滨新材料有限公司 Glass composition, strengthened glass ceramics and preparation method therefor, and glass-ceramic product

Similar Documents

Publication Publication Date Title
CN110104954B (en) Low-temperature crystallized ion-exchangeable glass ceramic
CN114195393B (en) Glass composition, microcrystalline glass, and preparation method and application thereof
CN114195392A (en) Glass composition, microcrystalline glass, and preparation method and application thereof
CN114195394B (en) Glass composition, microcrystalline glass, and preparation method and application thereof
TW202016039A (en) Microcrystalline glass, microcrystalline glass product, and manufacturing method therefor
CN110143759B (en) High-strength transparent glass-ceramic
JP2022550970A (en) Lithium zirconium aluminosilicate glass, tempered glass, manufacturing method thereof and display parts
CN108863050A (en) Lithium alumina silicate glass and preparation method thereof
CN110627365B (en) Transparent strengthened glass ceramic and preparation method thereof
WO2020082328A1 (en) Microcrystalline glass product and microcrystalline glass for electronic equipment cover plate
CN115286251B (en) Tempered glass, microcrystalline glass and preparation method and application thereof
CN110028240B (en) Aluminosilicate glass and preparation method thereof
CN109694187B (en) Lithium-containing glass with low softening point
CN114605074A (en) Microcrystalline glass and preparation method thereof
CN110577364A (en) Lithium-aluminum silicate nanocrystalline glass ceramic and preparation method thereof
CN115849719A (en) Black microcrystalline glass, 3D black microcrystalline glass and covering piece
WO2024109495A1 (en) 3d microcrystalline glass, preparation method therefor, and pre-crystallized microcrystalline glass
WO2024109498A1 (en) Glass ceramics, preparation method therefor, and glass ceramics article
WO2024109499A1 (en) Glass composition, strengthened glass ceramics and preparation method therefor, and glass-ceramic product
CN115893851A (en) Microcrystalline glass and preparation method thereof
CN113831021B (en) Microcrystalline glass and preparation method thereof, glass protection layer, glass cover plate and electronic device
CN115490423A (en) Aluminosilicate glass and preparation method thereof
WO2022141274A1 (en) Glass, tempered glass and preparation method therefor, and electronic product
CN116023025B (en) Aluminoborosilicate glass for ion exchange, preparation method and application thereof
CN115745410B (en) Glass ceramic and preparation method and application 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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20220318