CN114195394B - Glass composition, microcrystalline glass, and preparation method and application thereof - Google Patents
Glass composition, microcrystalline glass, and preparation method and application thereof Download PDFInfo
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- CN114195394B CN114195394B CN202111682724.5A CN202111682724A CN114195394B CN 114195394 B CN114195394 B CN 114195394B CN 202111682724 A CN202111682724 A CN 202111682724A CN 114195394 B CN114195394 B CN 114195394B
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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
- 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
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- 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
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- 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
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- 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
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- 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
- 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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- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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Abstract
The invention discloses a glass composition, microcrystalline glass, and a preparation method and application thereof, wherein the glass composition comprises the following components in percentage by mass: SiO 2 2 71.5～74.5％、Al 2 O 3 7.3～8.7％、P 2 O 5 1.7～3％、B 2 O 3 0.1～1％、Li 2 O10.2～12％、Na 2 0.4 to 1.5% of O and ZrO 2 3.1 to 5 percent. In the technical scheme of the invention, the component SiO in the glass composition 2 、Al 2 O 3 、P 2 O 5 、B 2 O 3 、Li 2 O、Na 2 O and ZrO 2 The specific gravity 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, and the microcrystalline glass with excellent strengthening performance is obtained.
Description
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.
Disclosure of Invention
The invention mainly aims to provide a glass composition, microcrystalline glass, and a preparation method and application thereof, and aims to solve the problems of large b value and high haze of the conventional microcrystalline glass.
In order to achieve the above object, the present invention provides a glass composition comprising, by mass:
SiO 2 ，71.5～74.5％；
Al 2 O 3 ，7.3～8.7％；
P 2 O 5 ，1.7～3％；
B 2 O 3 ，0.1～1％；
Li 2 O，10.2～12％；
Na 2 O，0.4～1.5％；
ZrO 2 ，3.1～5％。
alternatively, -1.1 ≦ W (SiO) 2 )-6×W(Al 2 O 3 )-2×W(Li 2 O)≤6.7。
Alternatively, 0.19 ≦ W (Li) 2 O)-W(Al 2 O 3 )]/[W(P 2 O 5 )+W(ZrO 2 )]≤0.98。
Alternatively, 0.06 ≦ [ W (ZrO) 2 )-3×W(B 2 O 3 )]/W(P 2 O 5 )≤1.57。
Optionally, the method comprises the following steps by mass percent:
SiO 2 ，72～74％；
Al 2 O 3 ，7.5～8.4％；
P 2 O 5 ，2～2.8％；
B 2 O 3 ，0.3～0.8％；
Li 2 O，10.5～11.8％；
Na 2 O，0.5～1.3％；
ZrO 2 ，3.4～4.7％。
alternatively, 0.6 ≦ W (SiO) 2 )-6×W(Al 2 O 3 )-2×W(Li 2 O)≤5.4；
0.28≤[W(Li 2 O)-W(Al 2 O 3 )]/[W(P 2 O 5 )+W(ZrO 2 )]≤0.8；
0.5≤[W(ZrO 2 )-3×W(B 2 O 3 )]/W(P 2 O 5 )≤1.36。
Optionally, the method comprises the following steps by mass percent:
SiO 2 ，72.5～73.5％；
Al 2 O 3 ，7.7～8％；
P 2 O 5 ，2.1～2.5％；
B 2 O 3 ，0.5～0.7％；
Li 2 O，11～11.5％；
Na 2 O，0.7～1.1％；
ZrO 2 ，3.8～4.4％。
alternatively, 2.5 ≦ W (SiO) 2 )-6×W(Al 2 O 3 )-2×W(Li 2 O)≤4.3；
0.43≤[W(Li 2 O)-W(Al 2 O 3 )]/[W(P 2 O 5 )+W(ZrO 2 )]≤0.64；
0.81≤[W(ZrO 2 )-3×W(B 2 O 3 )]/W(P 2 O 5 )≤1.16。
The invention also provides microcrystalline glass comprising the glass composition.
Optionally, the thickness of the microcrystalline glass is 0.3-1.5 mm.
The invention also provides a preparation method of the microcrystalline glass, which comprises the following steps:
s10, weighing the glass composition;
s20, mixing and melting the glass composition, then clarifying, homogenizing, forming, annealing, and finally cutting to obtain base glass;
and S30, carrying out heat treatment on the base glass to obtain the microcrystalline glass.
Optionally, step S30 includes:
heating the base glass to 510-540 ℃ from room temperature within 20-60 min, and carrying out first nucleation treatment, wherein the first nucleation treatment time is 3-8 h;
heating to 580-610 ℃ within 5-30 min, and carrying out secondary nucleation treatment, wherein the time of the secondary nucleation treatment is 3-8 h;
heating to 650-680 ℃ within 5-30 min, and carrying out crystallization treatment for 3-8 h;
cooling to room temperature to obtain the microcrystalline glass.
Optionally, after step S30, the method further includes:
s40, pretreating the microcrystalline glass, and then placing the pretreated microcrystalline glass into an ion exchange bath for salt bath to obtain chemically strengthened microcrystalline glass;
wherein the ion exchange bath comprises 20-40% of NaNO by mass 3 And 60-80% KNO 3 (ii) a And/or the presence of a gas in the atmosphere,
the salt bath strengthening temperature is 420-500 ℃; and/or the presence of a gas in the gas,
the salt bath strengthening time is 3-8 h.
Optionally, in step S20, the forming method includes float forming, overflow forming, calender 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 composition 2 、Al 2 O 3 、P 2 O 5 、B 2 O 3 、Li 2 O、Na 2 O and ZrO 2 The specific gravity 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, and the microcrystalline glass with excellent strengthening performance is 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.
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 obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection 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.
In view of the above, the invention provides a glass composition, and the microcrystalline glass prepared by the glass composition can effectively solve the problems that the existing transparent microcrystalline glass has a large b value and a high haze.
In an embodiment of the present invention, a glass composition is provided, which includes, by mass: SiO 2 2 ，71.5～74.5％；Al 2 O 3 ，7.3～8.7％；P 2 O 5 ，1.7～3％；B 2 O 3 ，0.1～1％；Li 2 O，10.2～12％；Na 2 O，0.4～1.5％；ZrO 2 ，3.1～5％。
Firstly, the molecular formula of the microcrystalline glass crystalline phase petalite expected by the invention is LiAlSi 4 O 10 Lithium disilicate having the molecular formula of Li 2 Si 2 O 5 . The mass percent of each component is calculated to be SiO in the glass composition 2 、Al 2 O 3 、P 2 O 5 、B 2 O 3 、Li 2 O、Na 2 O and ZrO 2 The sum of the masses of (a) is a reference.
Incorporation of SiO into the glass compositions of the present invention 2 SiO, a component constituting the glass skeleton 2 Can 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 Li 2 Si 2 O 5 And LiAlSi 4 O 10 The crystalline phase provides SiO 2 Source, in the glass microcrystallization process, of too high SiO 2 Promoting the occurrence of quartz and quartz solid solution in the glass micro crystallization process. Thus, taken together, SiO 2 The content is selected from 71.5 wt% to 74.5 wt%.
Incorporation of Al into the glass compositions of the invention 2 O 3 Belong to the network intermediate oxygenAnd (4) melting the mixture. 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, Al 2 O 3 The 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 (aluminum) 2 O 3 The 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 process 4 O 10 Excessive formation of LiAlSi even in the base glass 2 O 6 The crystal phase is generated, so that the glass transmittance is reduced. Therefore, taken together, Al 2 O 3 The content is selected from 7.3 wt% to 8.7 wt%.
Incorporation of P into the glass compositions of the present invention 2 O 5 ，P 2 O 5 More favouring the crystallization of lithium disilicate crystals. P 5+ The ions have large field intensity and strong oxygen-depriving capacity, and the phosphorus-oxygen network structure tends to be strong. Due to P 5+ The ionic field strength is greater than that of Si 4+ Ion, P 5+ 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. Li 2 O and P 2 O 5 Reaction to form Li 3 PO 4 Crystal phase, thereby inducing Li in the glass 2 O and SiO 2 Reaction to form Li 2 SiO 3 And finally form Li 2 Si 2 O 5 A crystalline phase; furthermore, P 2 O 5 It 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 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 is 2 O 5 The 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 formed 2 Si 2 O 5 A 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, P 2 O 5 The content is 1.7 wt% -3 wt%.
Incorporation of B into the glass compositions of the invention 2 O 3 ，B 2 O 3 Can improve the meltability of the glass and lower the melting point, and can help to improve the scratch resistance of the glass surface. In the present study, it was found that B 2 O 3 With dense [ BO ] in the microcrystalline glass structure 4 ]In a form effective in suppressing nucleation of lithium disilicate: (>580 ℃), the growth of petalite further causes the problem of high haze of the microcrystalline glass; on the other hand, the migration of alkali metal ions in the glass ceramics is limited, and the crystal structure of the glass ceramics is stabilized. Therefore, taken together, B 2 O 3 The content is 0.1 wt% -1 wt%.
Incorporation of Li into the glass composition of the present invention 2 O, 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 Li 2 Li in the process of promoting basic microcrystallization by O concentration 3 PO 4 Formation, 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, cracks on the surface of the crystallized glass are reduced, and the mechanical strength function of the microcrystalline glass is provided. But too high Li 2 The 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, Li 2 The content of O is 10.2 to 12 weight percent。
Incorporation of Na into the glass composition of the present invention 2 And 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, in general, Na 2 The content of O is 0.4 wt% -1.5 wt%.
Incorporation of ZrO into the glass compositions of the invention 2 . On the one hand, the potential energy of zirconium ions is large, the glass network structure can be enhanced, and ZrO is 2 The petalite crystal is more likely to be precipitated; on the other hand, ZrO 2 The 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 ZrO 2 Content results in ZrO in the glass 2 Unmelts exist, resulting in non-uniform devitrification of the glass. Thus, taken together, ZrO 2 The content is 3.1 wt% -5 wt%.
In the technical scheme of the invention, the component SiO in the glass composition 2 、Al 2 O 3 、P 2 O 5 、B 2 O 3 、Li 2 O、Na 2 O and ZrO 2 The specific gravity 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, and the microcrystalline glass with excellent strengthening performance is obtained.
The microcrystalline glass comprises the following components: -1.1. ltoreq. W (SiO) 2 )-6×W(Al 2 O 3 )-2×W(Li 2 O) is less than or equal to 6.7. Let A ═ W (SiO) 2 )-6×W(Al 2 O 3 )-2×W(Li 2 O), W represents the mass percentage of the component in the sum of all the components, and the value A is the molecular value of the mass percentage calculated by the formula. If the A value is lower, SiO 2 All enter the crystalline phase, relative to Al 2 O 3 Or Li 2 O is excessive; the petalite crystal phase is formed in a large proportion, and crystal grains are easy to grow up, so that the microcrystal proportion is semitransparent and even devitrified. If the A value is too high, Al 2 O 3 Or Li 2 All O enters a crystal phase, and the rest SiO 2 The 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. Therefore, the A value is controlled in the range, the microcrystalline proportion of the microcrystalline glass is prevented from being semitransparent and even devitrified, and the total crystalline phase content of the microcrystalline glass is effectively improved.
The microcrystalline glass comprises the following components: w (Li) of 0.19 ≤ 2 O)-W(Al 2 O 3 )]/[W(P 2 O 5 )+W(ZrO 2 )]Less than or equal to 0.98. Let B ═ W (Li) 2 O)-W(Al 2 O 3 )]/[W(P 2 O 5 )+W(ZrO 2 )]And W represents the mass percentage of the component to the sum of the masses of all the components. If the value of B is too low, the proportion of glass phase in the glass-ceramic increases, and the performance advantage of the glass-ceramic cannot be fully exerted. If the B value is too high, undesirable crystalline phases such as beta-quartz and the like are easily generated, the formation ratio of the petalite crystalline phase is high, and the crystal grains are easily grown, so that the ratio of the microcrystal is semitransparent and even devitrification is caused. 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.
The microcrystalline glass comprises the following components: w (ZrO) of 0.06 ≤ 2 )-3×W(B 2 O 3 )]/W(P 2 O 5 ) Less than or equal to 1.57. Let C ═ W (ZrO) 2 )-3×W(B 2 O 3 )]/W(P 2 O 5 ) And W represents the mass percentage of the component to the sum of the masses of all the components. 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. The liquid phase crystallization and the unstable decomposition are realized to cause the development of a phase interface, the activation energy or energy barrier of nucleation is reduced, and the nucleation temperature and the crystallization temperature are reduced. The two crystal phases compete for the silicon source and the lithium source, namely the crystal phase structure formed by the other crystal phase is destroyed to form the own crystal phase, the crystal phases of the formed petalite and the lithium disilicate are close in amount, the crystal sizes are uniform, and the crystal sizes are uniform<100nm, meets the basic requirement of optical visibility. Too high or too low C value leads to increase of single crystal phase and easy growth, decrease of visible light transmittance of microcrystal and increase of haze.
Further, it is preferable that the components of the glass composition satisfy the following conditions: SiO 2 2 ，72～74％；Al 2 O 3 ，7.5～8.4％；P 2 O 5 ，2～2.8％；B 2 O 3 ，0.3～0.8％；Li 2 O，10.5～11.8％；Na 2 O，0.5～1.3％；ZrO 2 And 3.4-4.7%. The properties of the glass-ceramic obtained from this glass composition are further optimized.
According to the component proportion of the glass composition, more preferably, the microcrystalline glass satisfies the following conditions: w (SiO) of 0.6. ltoreq. 2 )-6×W(Al 2 O 3 )-2×W(Li 2 O)≤5.4；0.28≤[W(Li 2 O)-W(Al 2 O 3 )]/[W(P 2 O 5 )+W(ZrO 2 )]≤0.8；0.5≤[W(ZrO 2 )-3×W(B 2 O 3 )]/W(P 2 O 5 )≤1.36。
Further, the components of the glass composition satisfy the following conditions: SiO 2 2 ，72.5～73.5％；Al 2 O 3 ，7.7～8％；P 2 O 5 ，2.1～2.5％；B 2 O 3 ，0.5～0.7％；Li 2 O，11～11.5％；Na 2 O，0.7～1.1％；ZrO 2 And 3.8-4.4%. The performance of the microcrystalline glass obtained by the glass composition is better.
According to the component proportion of the glass composition, more preferably, the microcrystalline glass satisfies the following conditions: w (SiO) of 2.5 ≤ 2 )-6×W(Al 2 O 3 )-2×W(Li 2 O)≤4.3；0.43≤[W(Li 2 O)-W(Al 2 O 3 )]/[W(P 2 O 5 )+W(ZrO 2 )]≤0.64；0.81≤[W(ZrO 2 )-3×W(B 2 O 3 )]/W(P 2 O 5 )≤1.16。
In an embodiment of the present invention, a glass-ceramic including the glass composition described above is also provided. The glass ceramics include all technical features of the glass composition, so that all technical effects brought by the glass composition are achieved, and detailed description is omitted here.
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:
s10, weighing the glass composition.
And S20, mixing and melting the glass composition, then clarifying, homogenizing, forming, 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 S30, carrying out heat treatment on the base glass to obtain the microcrystalline glass.
Specifically, step S30 includes: heating the base glass to 510-540 ℃ from room temperature within 20-60 min, and carrying out primary nucleation treatment, wherein the primary nucleation treatment time is 3-8 h; heating to 580-610 ℃ within 5-30 min, and carrying out secondary nucleation treatment, wherein the time of the secondary nucleation treatment is 3-8 h; heating to 650-680 ℃ within 5-30 min, and carrying out crystallization treatment for 3-8 h; cooling to room temperature to obtain the microcrystalline glass.
Further, as shown in fig. 2, after the step S30, the method further includes:
and S40, pretreating the microcrystalline glass, and then placing the pretreated microcrystalline glass into an ion exchange bath for salt bath to obtain the chemically strengthened microcrystalline glass. Wherein the ion exchange bath comprises 20-40% of NaNO by mass 3 And 60-80% KNO 3 (ii) a The salt bath strengthening temperature is 420-500 ℃; the salt bath has strong strengthThe chemical time is 3-8 h.
Because the content of the crystals in the microcrystalline glass is high, the structural difference exists between the glass phase and the crystalline phase, and a structural cavity is formed; such as by containing>40wt％NaNO 3 Molten salt, albeit Na, for a short time during ion exchange + /Li + Deeper ion depths can be achieved, but Na + Easily agglomerate in the cavity of the microcrystalline phase and the glass phase, and hardly form compressive stress. Na in the glass phase + /Li + When the exchange is too fast, the difference between the glass phase and the crystallite phase becomes larger, and the b value tends to increase.
The adoption of the strengthening system can slow down Na in a crystal phase + /Li + Exchange speed is favorable for reducing Na in the cavity of microcrystalline phase and glass phase + Agglomeration, effectively forming compressive stress; the glass phase and the exchange speed can be reduced, the difference between the glass phase and the crystal phase is reduced, and the b value of the glass is further reduced.
In step S40, the preprocessing specifically includes: and (3) insulating the microcrystalline glass for 5-20 min at 300-330 ℃. 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 comprises the microcrystalline glass, the specific characteristics of the microcrystalline glass refer to the above embodiments, and the electronic display terminal adopts all technical solutions of all the above embodiments, so that the electronic display terminal at least has all beneficial effects brought by the technical solutions of the above embodiments, and further description is omitted here. 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 2 71.5％、Al 2 O 3 8.7％、P 2 O 5 3％、B 2 O 3 0.1％、Li 2 O10.2％、Na 2 O1.5% and ZrO 2 5％，A＝-1.1，B＝0.19，C＝1.57。
(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 510 ℃ from room temperature within 20min, and carrying out first nucleation treatment, wherein the first nucleation treatment time is 3 h; raising the temperature to 580 ℃ within 5min, and carrying out secondary nucleation treatment, wherein the time of the secondary nucleation treatment is 3 h; heating to 650 ℃ within 30min, and carrying out crystallization treatment for 3 h; cooling to room temperature to obtain the microcrystalline glass.
(4) Pretreating the microcrystalline glass, and then placing the pretreated microcrystalline glass into an ion exchange bath for salt bath to obtain the chemically strengthened microcrystalline glass, wherein the ion exchange bath comprises 20 mass percent of NaNO 3 And 80% of KNO 3 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 15 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 compositions of comparative examples 1 to 7 shown in table 3 were weighed to obtain raw materials, and the microcrystalline glasses of comparative examples 1 to 7 and the chemically strengthened microcrystalline glasses were prepared by 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 examples 1 and 9, and the specific process parameters for the preparation were shown in table 4.
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 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 15, the performance of the crystallized glass and the chemically strengthened crystallized glass obtained in comparative examples 1 to 7, and the performance of the crystallized glass obtained according to the process parameters in table 4 were respectively tested according to the test methods and the test equipment 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 8 glass composition components and glass properties
Table 2 examples 9 to 15 glass composition components and glass properties
Table 3 comparative examples 1 to 7 glass composition components and glass Properties
TABLE 4 Process parameters and Properties for the preparation of glass-ceramics with the glass compositions of examples 1 and 9
Wherein, the time in the first nucleation treatment, the second 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.
As can be seen from the results of the performance tests of the glasses of examples shown in tables 1, 2 and 4, examples 1 to 15 according to the present invention were used to obtain lithium disilicate Li in microcrystalline glass 2 Si 2 O 5 30 to 45 percent of petalite LiAlSi 4 O 10 30-45 percent of the total crystalline phase, 60-90 percent of the microcrystalline glass, uniform crystal size and average crystal size<100 nm. Transmittance of 0.7mm microcrystalline glass at wavelength of 560nm>Haze 91%)<0.17, b value<0.5; height of falling resistance>200cm。
As can be seen from Table 3, comparative examples 1, B 2 O 3 0% and 1.58% of C. 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 a small crystal size>100 nm; and has low transmittance, excessive b value and high haze.
Comparative examples 2, B 2 O 3 1.1%, but C-0.22. 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 a small crystal size>100 nm; the transmittance is low, the b value is overlarge, and the haze is large; the drop resistance is poor.
Comparative example 3, Al 2 O 3 9.5%, a-4.8, and B0.08. 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 a small crystal size>100 nm; the transmittance is low, the b value is overlarge, and the haze is large; the drop resistance is poor.
Comparative example 4, SiO 2 74.7%, a 12.1. The glass composition of the invention is not satisfied, and the content of microcrystalline phase in the heat-treated microcrystalline glass is low; poor anti-falling performance。
Comparative example 5, Li 2 O is 13% and B is 1.08. 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 a small crystal size>100 nm; and has low transmittance, excessive b value and high haze.
Comparative example 6, Al 2 O 3 9%, and B-0.06. The glass composition of the invention is not satisfied, and the content of microcrystalline phase in the heat-treated microcrystalline glass is low; the drop resistance is poor.
Comparative example 7, although the glass component is within the requirements of the present invention, C ═ 1.91, which does not meet the requirements of the glass composition of the present invention, the content of the microcrystalline phase in the heat-treated microcrystalline glass is small, the crystal size is >100 nm; and has low transmittance, excessive b value and high haze.
Compared with the b value and the haze of the microcrystalline glass in the comparative example, the b value of the microcrystalline glass in the embodiment of the invention is obviously reduced, and the haze is obviously reduced, which shows that the embodiment of the invention can effectively solve the problems that the currently prepared transparent microcrystalline glass has a larger b value and a higher haze, and the obtained microcrystalline glass 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 (12)
1. A glass composition, wherein the glass composition is formed from SiO 2 、Al 2 O 3 、P 2 O 5 、B 2 O 3 、Li 2 O、Na 2 O、ZrO 2 The composition comprises the following components in percentage by mass:
SiO 2 ，71.5～74.5％；
Al 2 O 3 ，7.3～8.7％；
P 2 O 5 ，1.7～3％；
B 2 O 3 ，0.1～1％；
Li 2 O，10.2～12％；
Na 2 O，0.4～1.5％；
ZrO 2 ，3.1～5％；
wherein each component also satisfies 0.6 ≤ W (SiO) 2 )-6×W(Al 2 O 3 )-2×W(Li 2 O)≤5.4；0.19≤[W(Li 2 O)-W(Al 2 O 3 )]/[W(P 2 O 5 )+W(ZrO 2 )]≤0.98；0.06≤[W(ZrO 2 )-3×W(B 2 O 3 )]/W(P 2 O 5 )≤1.57。
2. The glass composition according to claim 1, wherein the glass composition comprises the following components in percentage by mass:
SiO 2 ，72～74％；
Al 2 O 3 ，7.5～8.4％；
P 2 O 5 ，2～2.8％；
B 2 O 3 ，0.3～0.8％；
Li 2 O，10.5～11.8％；
Na 2 O，0.5～1.3％；
ZrO 2 ，3.4～4.7％。
3. the glass composition according to claim 2,
0.28≤[W(Li 2 O)-W(Al 2 O 3 )]/[W(P 2 O 5 )+W(ZrO 2 )]≤0.8；
0.5≤[W(ZrO 2 )-3×W(B2O3)]/W(P 2 O 5 )≤1.36。
4. the glass composition according to claim 1, wherein the glass composition comprises the following components in percentage by mass:
SiO 2 ，72.5～73.5％；
Al 2 O 3 ，7.7～8％；
P 2 O 5 ，2.1～2.5％；
B 2 O 3 ，0.5～0.7％；
Li 2 O，11～11.5％；
Na 2 O，0.7～1.1％；
ZrO 2 ，3.8～4.4％。
5. the glass composition according to claim 4,
2.5≤W(SiO 2 )-6×W(Al 2 O 3 )-2×W(Li 2 O)≤4.3；
0.43≤[W(Li 2 O)-W(Al 2 O 3 )]/[W(P 2 O 5 )+W(ZrO 2 )]≤0.64；
0.81≤[W(ZrO 2 )-3×W(B 2 O 3 )]/W(P 2 O 5 )≤1.16。
6. a glass-ceramic comprising the glass composition according to any one of claims 1 to 5.
7. The glass-ceramic according to claim 6, wherein the thickness of the glass-ceramic is 0.3 to 1.5 mm.
8. The preparation method of the microcrystalline glass is characterized by comprising the following steps of:
s10, weighing the glass composition as defined in any one of claims 1 to 5:
s20, mixing and melting the glass composition, then clarifying, homogenizing, forming, annealing, and finally cutting to obtain base glass;
and S30, carrying out heat treatment on the base glass to obtain the microcrystalline glass.
9. The method for producing a crystallized glass according to claim 8, wherein step S30 includes:
heating the base glass to 510-540 ℃ from room temperature within 20-60 min, and carrying out first nucleation treatment, wherein the first nucleation treatment time is 3-8 h;
heating to 580-610 ℃ within 5-30 min, and carrying out secondary nucleation treatment, wherein the time of the secondary nucleation treatment is 3-8 h;
heating to 650-680 ℃ within 5-30 min, and carrying out crystallization treatment for 3-8 h;
cooling to room temperature to obtain the microcrystalline glass.
10. The method for producing a glass ceramic according to claim 8, further comprising, after step S30:
s40, pretreating the microcrystalline glass, and then placing the pretreated microcrystalline glass into an ion exchange bath for salt bath to obtain chemically strengthened microcrystalline glass;
wherein the ion exchange bath comprises 20-40% of NaNO by mass 3 And 60-80% KNO 3 (ii) a And/or the presence of a gas in the gas,
the salt bath strengthening temperature is 420-500 ℃: and/or the presence of a gas in the gas,
the salt bath strengthening time is 3-8 h.
11. The method for producing glass ceramic according to claim 8, wherein in step S20, the forming method includes float forming, overflow forming, calender forming, or slot draw forming.
12. An electronic display terminal, characterized by comprising the crystallized glass according to claim 6 or 7.
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