CN112939472B - Microcrystalline glass and preparation method and application thereof - Google Patents
Microcrystalline glass and preparation method and application thereof Download PDFInfo
- Publication number
- CN112939472B CN112939472B CN201911268661.1A CN201911268661A CN112939472B CN 112939472 B CN112939472 B CN 112939472B CN 201911268661 A CN201911268661 A CN 201911268661A CN 112939472 B CN112939472 B CN 112939472B
- Authority
- CN
- China
- Prior art keywords
- glass
- weight
- microcrystalline
- ceramic
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- C03C10/0009—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 silica as main constituent
-
- 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
- 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
-
- 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
Abstract
The invention relates to the field of glass, and particularly discloses microcrystalline glass and a preparation method and application thereof. The microcrystalline glass comprises the following components by taking the total weight of the microcrystalline glass as a reference: 52-65% by weight of SiO212-27% by weight of Al2O35-19% by weight of Na2O, 0-3.5% by weight of K2O, 2-7 wt% MgO, 3-10 wt% Li2O, 0.5-5 wt% ZrO20-4.5% by weight of TiO2(ii) a The crystallized glass comprises a crystallized portion having a spherical crystal phase comprising lithium disilicate, beta-quartz, a beta-quartz solid solution, Mg and a glass phase portion, and the degree of crystallization is 10 to 25% by weight2TiO4And lithium metasilicate. The microcrystalline glass has high light transmittance, high strength, excellent impact resistance and excellent drop resistance, and is particularly suitable for being used as display device protective glass.
Description
Technical Field
The invention relates to the field of glass, in particular to microcrystalline glass and a preparation method and application thereof.
Background
With the development of communication technology, the thinning, large screen and portability of mobile terminal equipment rapidly become the mainstream of the market, and with the increasing popularization of 5G and wireless charging technology, the rear cover glass of mobile communication equipment (such as mobile phones, smart watches and the like) becomes a necessary trend, which puts higher requirements on the front and rear cover glass materials for protecting display devices. How to lighten, thin and enlarge the screen of the glass and improve the mechanical strength of the glass, thereby ensuring that the screen of the mobile communication equipment can not be broken when the mobile communication equipment collides with and collides with foreign objects or falls from a high place (more than 100 cm) to a rough surface (such as cement ground, gravel, asphalt roads and the like) in the using process, and becoming the key point of research and development of various large original factories and cover plate factories.
The protective glass of the display device adopted in the market at present is usually medium-high alumina glass or lithium-aluminum-silicon glass, after primary strengthening or secondary chemical strengthening, the surface Compressive Stress (CS) can reach 600-700MPa, the depth of stress layer (DOL) can reach 60-80 μm, and the protective glass has better mechanical properties, but the glass is taken as a brittle material, a plurality of Griffith cracks exist in the glass, the breaking of the glass is the result of crack propagation, although the surface compressive stress layer after chemical strengthening can play a certain role in blocking the cracks, the crack propagation resistance is limited (the glass is ineffective when the surface compressive stress layer depth exceeds the compressive stress layer depth). Therefore, after the screen is assembled and applied to mobile terminal equipment, the impact resistance and the drop resistance of the whole machine to sharp objects are not enough, and particularly when the screen falls from a higher position to a rough surface, the screen breakage rate is greatly increased when the drop height exceeds 100 cm.
The microcrystalline glass is a functional material which contains a large amount of microcrystalline phases and glass phases and has excellent mechanical properties, is obtained by controlling the crystallization process of basic glass with a specific composition, and crystal grains in the microcrystalline glass can cause the bending and passivation of crack tips, increase the fracture energy, slow down and even prevent cracks from passing through the crystal phases and possible interfaces to form a hindered fracture path in the glass, thereby improving the crack propagation resistance and the scratch resistance. But the shock resistance and the drop resistance of the pure glass ceramics are still not strong enough, and the glass ceramics need to be further enhanced by a chemical strengthening method, so that the shock resistance and the drop resistance are improved. In addition, most kinds of crystals in the microcrystalline glass easily cause the reduction of the light transmittance of the glass, the increase of the haze and even devitrification, so that the application of the microcrystalline glass as a protective material of mobile terminal equipment is limited.
CN107207332A discloses a method for strengthening microcrystalline glass, which realizes chemical strengthening by divalent ion exchange, and although the surface compressive stress level can be improved to some extent by strengthening with the chemical strengthening method, the surface compressive stress of the obtained microcrystalline glass is not more than 230Mpa at most, and the depth of the compressive stress layer is not more than 10 μm at most.
CN105859143A discloses a microcrystalline glass which precipitates Li2SiO5And beta-spodumene and other crystalline phases, the breaking strength of the obtained glass ceramics is improved to a certain extent, but the light transmittance of the glass ceramics is only up to 70% at most, and the application requirements of the mobile terminal cannot be met.
Therefore, the microcrystalline glass with high light transmittance, high strength, excellent impact resistance and excellent drop resistance is urgently needed to be developed so as to meet the performance requirements of front and rear cover plate materials of the intelligent mobile terminal.
Disclosure of Invention
The invention aims to solve the problems of insufficient impact resistance and drop resistance of sharp objects, light transmittance reduction, haze increase and the like of display device protective glass in the prior art, and provides microcrystalline glass and a preparation method and application thereof.
To achieve the above object, a first aspect of the present invention provides a method for manufacturing a semiconductor deviceThe microcrystalline glass comprises the following components by taking the total weight of the microcrystalline glass as a reference: 52-65% by weight of SiO212-27% by weight of Al2O35-19% by weight of Na2O, 0-3.5% by weight of K2O, 2-7 wt% MgO, 3-10 wt% Li2O, 0.5-5 wt% ZrO20-4.5% by weight of TiO2；
Wherein the crystallized glass comprises a microcrystalline portion having a spherical crystal phase containing lithium disilicate, β -quartz, a β -quartz solid solution, Mg, and a glass phase portion, and the crystallized glass has a crystallinity of 10 to 25% by weight2TiO4And lithium metasilicate.
Preferably, the size of the spherical crystalline phase is not more than 1 μm, preferably 0.4-0.9 μm.
Preferably, the microcrystalline glass comprises, based on the total weight of the microcrystalline glass:
55-60% by weight of SiO2，
15.5-23.5 wt.% of Al2O3，
7-13% by weight of Na2O，
0.5-2.5% by weight of K2O，
2.5-4.5% by weight of MgO,
3.5-6.5 wt.% Li2O，
1.2-4% by weight of ZrO2，
0.5-3.5 wt% TiO2。
Preferably, the microcrystalline glass further comprises 0.1-2 wt% of a fining agent component; more preferably, the clarifier composition comprises SO4 2-、NO3 -、F-And Cl-At least one of (1).
Preferably, SiO2、Al2O3、Li2Sum of the weight contents of O and SiO2+Al2O3+Li2O is 80-90 wt%.
Preferably, ZrO2、TiO2ZrO in a total amount by weight2+TiO2Is 2-6 wt%.
Preferably, Al2O3/Na2The weight ratio of O is 2-4.
Preferably, Al2O3/(Na2O+Li2O) in a weight ratio of 1.2-2, wherein Na is2O+Li2O is Na2O、Li2Sum of the weight contents of O.
Preferably, the microcrystalline glass has a transmittance of 86% or more in a wavelength range of 380-780 nm.
Preferably, the haze of the microcrystalline glass in the wavelength range of 380-780nm is less than 0.5%.
Preferably, the surface compressive stress of the glass-ceramic is at least greater than 800 MPa.
Preferably, the depth of layer of compressive stress of the glass-ceramic is 90 μm or more, preferably more than 95 μm.
Preferably, the compressive stress of the microcrystalline glass at a distance of 50 μm from the surface is greater than 80MPa, preferably 90MPa or greater, and more preferably greater than 100 MPa.
Preferably, the complete machine sand paper falling height of the microcrystalline glass is more than 160 cm.
Preferably, the microcrystalline glass has a Vickers hardness of 630kgf/mm2The four-point bending strength is 650MPa or more.
Preferably, the impact strength of the glass ceramics is more than 0.3J.
In a second aspect, the present invention provides a method for producing a glass-ceramic, including:
(1) carrying out microcrystallization treatment on the basic glass substrate; and
(2) carrying out secondary chemical strengthening treatment on the base glass matrix subjected to the microcrystallization treatment;
wherein the microcrystallization process comprises a step of nucleating a base glass substrate at a first temperature and then crystallizing the base glass substrate at a second temperature, both the first temperature and the second temperature being lower than a softening point temperature of the base glass substrate, and the second temperature being higher than the first temperature; and is
Wherein the base glass substrate comprises, based on the total weight of the base glass substrate: 52-65% by weight of SiO212-27% by weight of Al2O35-19% by weight of Na2O, 0-3.5% by weight of K2O, 2-7 wt% MgO, 3-10 wt% Li2O, 0.5-5 wt% ZrO20-4.5% by weight of TiO2；
Preferably, the first temperature is 550-640 ℃, and the nucleation time is 2-7 h; the second temperature is 640-750 ℃, and the crystallization time is 0.2-4 h.
Preferably, the base glass substrate comprises:
55-60% by weight of SiO2，
15.5-23.5 wt.% of Al2O3，
7-13% by weight of Na2O，
0.5-2.5% by weight of K2O，
2.5-4.5% by weight of MgO,
3.5-6.5 wt.% Li2O，
1.2-4% by weight of ZrO2，
0.5-3.5 wt% TiO2。
Preferably, the microcrystalline glass further comprises 0.1-2 wt% of a fining agent component; preferably, the clarifier composition comprises SO4 2-、NO3 -、F-And Cl-At least one of (1).
Preferably, the base glass substrate is produced by any one of a float process, an overflow process and a down-draw process.
Preferably, the base glass substrate is a glass substrate, preferably a glass substrate having a thickness of 0.33 to 1 mm.
Preferably, the secondary chemical strengthening treatment comprises: placing the base glass substrate after micro crystallization treatment into 100% NaNO3Carrying out a first ion exchange in the molten salt at a first strengthening temperature, and adding 100% KNO after the first ion exchange3Molten saltAt a second strengthening temperature, the first strengthening temperature being higher than the second strengthening temperature.
Preferably, the conditions of the first ion exchange include: the first strengthening temperature is 400-470 ℃, preferably 410-460 ℃, and the duration is 1-4h, preferably 2-3 h.
Preferably, the conditions of the second ion exchange include: the second strengthening temperature is 400-450 ℃, preferably 410-440 ℃, and the duration is 0.5-3h, preferably 1-2.5 h.
The third aspect of the invention provides an application of the microcrystalline glass provided by the invention in the manufacture of display screen protective glass and rear cover protective glass of an intelligent mobile terminal.
On one hand, the microcrystalline glass solves the problem that the impact resistance and the drop resistance of the existing high-alumina glass or lithium aluminosilicate glass are generally weaker even after primary strengthening or secondary chemical strengthening; on the other hand, the problems that the light transmittance is reduced and the performance is not improved after chemical strengthening are solved when the intrinsic strength of the common glass ceramics is improved. The microcrystalline glass provided by the invention has the characteristics of high transparency and super strong performance, and specifically has the following excellent performance characteristics: the light transmittance is more than 86% in the wave band range of 380-780nm, and the haze is less than 0.5%; the surface compressive stress is at least more than 800MPa, preferably more than 900 MPa; the depth of the compressive stress layer is more than 90 μm, even more than 95 μm, and more preferably more than 110 μm; a compressive stress at 50 μm from the surface of greater than 80MPa, preferably greater than 90MPa, more preferably greater than 100 MPa; the whole sand paper has a falling height of over 160cm and a Vickers hardness of 630kgf/mm2The four-point bending strength reaches more than 650Mpa, and the impact strength is more than 0.3J.
Drawings
FIG. 1 is a graph showing the transmittance of a glass ceramic A1 obtained in example 1 of the present invention;
FIG. 2 is an XRD pattern of a microcrystalline glass A1 obtained in example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a glass ceramic, including, based on the total weight of the glass ceramic: 52-65% by weight of SiO212-27% by weight of Al2O35-19% by weight of Na2O, 0-3.5% by weight of K2O, 2-7 wt% MgO, 3-10 wt% Li2O, 0.5-5 wt% ZrO20-4.5% by weight of TiO2；
Wherein the crystallized glass comprises a microcrystalline portion having a spherical crystal phase containing lithium disilicate, β -quartz, a β -quartz solid solution, Mg, and a glass phase portion, and the crystallized glass has a crystallinity of 10 to 25% by weight2TiO4And lithium metasilicate.
According to the present invention, in order to further improve the light transmittance of the glass-ceramic, the size of the spherical crystalline phase should be not more than 1 μm, preferably 0.4 to 0.9 μm.
Herein, the crystalline phase in the glass-ceramic can be measured by XRD, and the crystallinity is normalized by the peak intensity value of each diffraction peak in the XRD pattern. The crystal phase size was determined by SEM scanning electron microscopy.
Preferably, the microcrystalline glass comprises, based on the total weight of the microcrystalline glass:
55-60% by weight of SiO2，
15.5-23.5 wt.% of Al2O3，
7-13% by weight of Na2O，
0.5-2.5% by weight of K2O，
2.5-4.5% by weight of MgO,
3.5-6.5 wt.% Li2O，
1.2-4% by weight of ZrO2，
0.5-3.5 wt% TiO2。
Preferably, the glass ceramic further comprises 0.1-2 wt% of a clarifier component. Preferably, the clarifier composition comprises SO4 2-、NO3 -、F-And Cl-At least one of (1).
In order to better understand the design of the material prescription composition of the present invention, the following further explains the relevant compositions:
SiO2is the main component forming silica tetrahedron and connected to form glass network structure, and is the basic skeleton of glass. Microcrystalline glass, SiO according to the invention2The content of (b) is 52 to 65% by weight, preferably 55 to 60% by weight, and may be, for example, 55% by weight, 55.5% by weight, 56% by weight, 56.5% by weight, 57% by weight, 57.5% by weight, 58% by weight, 58.5% by weight, 59% by weight, 59.5% by weight, 59.8% by weight, or any one of the ranges of any two of the above values. When SiO is present2When the content of (b) is more than 65% by weight, the difference between the thermal expansion coefficients of the crystal phase and the glass phase is large, and the crystallite size of the glass ceramics is not easy to control, and the size of the precipitated crystal is large, so that it is difficult to obtain transparent glass ceramics; if SiO2When the content of (b) is less than 52% by weight, the resulting glass-ceramic has poor hardness and poor devitrification resistance.
Al2O3Is a component of the glass network structure and is also a basic component of the β -quartz solid solution crystal phase, which is effective in improving the heat resistance and ion exchange properties of the glass and helps stabilize the base glass matrix to form a desired crystal phase. Microcrystalline glass according to the invention, Al2O3The content of (b) is in the range of 12 to 27 wt%, preferably 15.5 to 23.5 wt%, and may be, for example, 16 wt%, 16.5 wt%, 17 wt%, 17.5 wt%, 18 wt%, 18.5 wt%, 19 wt%, 19.5 wt%, 20 wt%, 20.5 wt%, 21 wt%, 21.5 wt%, 22 wt%, 22.5 wt%, or 23 wt%, and any of the ranges consisting of any two of the above numerical valuesOne value. When Al is present2O3The content of (B) is higher than 12 wt%, so that the formed alundum tetrahedron and silicon-oxygen tetrahedron are interpenetrated to form a network structure, and the microcrystalline glass with better transparency can be obtained. But when Al2O3When the content exceeds 27% by weight, glass is liable to be frosted or even devitrified, and further, high-temperature viscosity is increased, and the difficulty in melting is increased, which is disadvantageous in production.
Li2O is an important composition for forming LAS-based glass ceramics, and can improve the meltability and moldability of the glass. Furthermore, Li+The existence of the glass is beneficial to secondary chemical strengthening, so that the surface of the glass has compressive stress and the strength is improved. However, Li2The content of O is not so high that when it exceeds 10% by weight, the control of crystal precipitation is not good, the crystallization is easy, and the glass stability is deteriorated. And tends to precipitate unwanted crystalline beta-spodumene, resulting in devitrification of the glass. Therefore, in the glass ceramics of the present invention, Li2The content of O is in the range of 3 to 10% by weight, preferably 3.5 to 6.5% by weight, and may be, for example, 4%, 4.5%, 5%, 5.5%, 6% or 6.2% by weight, and any one value in the range of any two of the above values.
Na2O is a good co-solvent in the glass component and is an important element for ion exchange in chemical tempering. When Na is present2The content of O is more than 19% by weight, which lowers the chemical stability of the glass, and the content is at least 5% by weight or more to maintain the melting temperature of the glass at a proper level and to provide the glass with considerable ion exchange characteristics. In the microcrystalline glass of the present invention, Na2The content of O is in the range of 5 to 19% by weight, preferably 7 to 13% by weight, and may be, for example, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5% or 12.8% by weight, and any one of the ranges of any two of the above numerical values.
K2O can reduce the high temperature viscosity of the glass, thereby improving the solubility and formability of the glass and reducing the incidence of cracking. Adding a small amount of one partThe surface can prevent the base glass from crystallizing during molding, and on the other hand can promote the formation of quartz crystals and quartz solid solutions during crystallization. If K2The content of O is more than 3.5 percent, which can promote the glass to separate out the undesirable crystal phases such as potassium feldspar and the like, and influence the strength and the optical performance of the glass. In the microcrystalline glass of the present invention, K2The content of O is in the range of 0 to 3.5% by weight, preferably 0.5 to 2.5% by weight, and may be, for example, 0.7%, 1%, 1.5%, 1.8%, 2% or 2.2% by weight, and any one of the ranges of any two of the above values.
MgO can improve the meltability, strain point and Young's modulus of glass, but too high MgO content increases the surface tension of glass, makes it difficult to exchange alkali metal ions with glass, and decreases the ion exchange rate, so that the content is not more than 7% by weight. In the glass ceramic according to the present invention, the content of MgO is in the range of 2 to 7% by weight, preferably 2.5 to 4.5% by weight, and may be, for example, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, or 4.2% by weight, and any one of the ranges of any two of the above numerical values.
TiO2Is a good composite crystal nucleus agent which is beneficial to the formation and growth of crystal nucleus, but TiO2Should not be too high, not only because of Ti4+Valence electrons transition between different energy levels causing selective absorption of visible light, resulting in a yellow colored glass and an undesirable rutile phase during devitrification. Therefore, in the glass ceramics according to the present invention, TiO2The content of (b) is in the range of 0 to 4.5% by weight, preferably 0.5 to 3.5% by weight, and may be, for example, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.5%, 3%, 3.2% by weight, or any one of the ranges of any two of the above values.
ZrO2Not only is a good composite nucleating agent, but also contributes to the improvement of chemical durability and hardness of the glass, if ZrO2Too high content of (A) reduces devitrification resistance of the glass, and also deteriorates meltability and causes the glass to have a problemIn the tendency to devitrification, molding becomes difficult. Thus, in the microcrystalline glass of the present invention, ZrO2The content of (b) is in the range of 0.5 to 5% by weight, preferably 1.2 to 4% by weight, and may be, for example, 1.4%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 3%, 3.5% or 3.8% by weight, and any one of the ranges consisting of any two of the above numerical values.
According to the present invention, in a preferred embodiment, the glass ceramics comprises, based on the total weight of the glass ceramics:
55-60% by weight of SiO2，
15.5-23.5 wt.% of Al2O3，
7-13% by weight of Na2O，
0.5-2.5% by weight of K2O，
2.5-4.5% by weight of MgO,
3.5-6.5 wt.% Li2O，
1.2-4% by weight of ZrO2，
0.5-3.5 wt% TiO2，
0.1-2 wt% of a clarifier component;
wherein the clarifier component comprises SO4 2-、NO3 -、F-And Cl-At least one of (1).
According to the present invention, in order to further obtain a desired crystal phase, thereby further improving the hardness and light transmittance of the glass ceramics, preferably, SiO2、Al2O3、Li2Sum of the weight contents of O and SiO2+Al2O3+Li2O is 80-90 wt%.
According to the present invention, in order to further improve the low-temperature melting property and the preferable formability of the glass, it is preferable that Al is present2O3/Na2The ratio of the O content by weight is 2-4.
According to the invention, in order to further improve the toughening effect, the bending resistance and the impact resistance of the microcrystalline glass are further improvedPerformance and drop resistance, preferably, Al2O3/(Na2O+Li2O) in a weight ratio of 1.2-2, wherein Na2O+Li2O is Na2O、Li2Sum of the weight contents of O.
According to the present invention, in order to further obtain uniform fine crystal grains and obtain a colorless transparent glass ceramics, preferably, ZrO2、TiO2ZrO in a total amount by weight2+TiO2Is 2-6 wt%.
According to the invention, in a particularly preferred embodiment, the glass ceramic comprises, based on the total weight of the glass ceramic:
55-60% by weight of SiO2，
15.5-23.5 wt.% of Al2O3，
7-13% by weight of Na2O，
0.5-2.5% by weight of K2O，
2.5-4.5% by weight of MgO,
3.5-6.5 wt.% Li2O，
1.2-4% by weight of ZrO2，
0.5-3.5 wt% TiO2，
0.1-2 wt% of a clarifier component;
the clarifier component comprises SO4 2-、NO3 -、F-And Cl-At least one of; and is
Wherein, SiO2+Al2O3+Li2The content of O is 80-90 wt%,
Al2O3/Na2the weight ratio of O is 2-4,
Al2O3/(Na2O+Li2o) weight ratio of 1.2-2,
ZrO2、TiO2ZrO in a total amount by weight2+TiO2Is 2-6 wt%.
Preferably, the microcrystalline glass has a transmittance of more than 86% in the wavelength range of 380-780 nm.
Preferably, the haze of the microcrystalline glass provided by the invention in the wavelength range of 380-780nm is less than 0.5%.
Preferably, the surface compressive stress of the microcrystalline glass is at least more than 800MPa, preferably more than 900 MPa; the depth of the compressive stress layer is more than 90 μm, even more than 95 μm, and more preferably more than 110 μm.
Preferably, the compressive stress of the microcrystalline glass of the present invention at a distance of 50 μm from the surface is greater than 80MPa, preferably 90MPa or greater, and more preferably greater than 100 MPa.
Preferably, the complete machine sand paper of the microcrystalline glass has a falling height of more than 160 cm.
Preferably, the microcrystalline glass of the present invention has a Vickers hardness of 630kgf/mm2The four-point bending strength is 650MPa or more.
Preferably, the impact strength of the microcrystalline glass is more than 0.3J.
Herein, the transmission of the glass-ceramic is determined by using a spectrophotometer according to standard ISO 13468-1: 1996.
The haze of the glass-ceramic is measured by using a haze meter with reference to the standard ISO14782: 1999.
The surface compressive stress value, the depth of layer of compressive stress and the compressive stress at 50 μm from the surface of the glass-ceramic are measured by using a surface stress meter, as described in GB/T18144-2008.
The impact strength of the microcrystalline glass is measured by a ball drop tester, specifically, a glass sample to be measured is placed on a jig, so that a 32g steel ball falls from a specified height, and the maximum ball drop height of the impact which can be borne by the glass sample to be measured without fragmentation is measured. Specifically, the test was carried out starting from a height of 30mm, the centre point falling 3 times, each time rising 10mm, until the glass broke. And calculating the impact resistance by using the potential energy formula Ep-mgh.
The complete machine abrasive paper dropping performance of the microcrystalline glass is measured by a mobile phone controlled dropping tester, and the specific test conditions are as follows: 180-mesh sand paper, 170g total weight, 60cm base height, 10cm increment, 1 time per height until breaking.
The hardness of the glass-ceramic is measured by using a Vickers hardness tester according to the standard GB/T16534-2009.
The four-point bending strength of the glass-ceramic was measured by using a universal tester with reference to the standard JC/T676-.
In a second aspect, the present invention provides a method for producing a glass-ceramic, including:
(1) carrying out microcrystallization treatment on the basic glass substrate; and
(2) carrying out secondary chemical strengthening treatment on the base glass matrix subjected to the microcrystallization treatment;
wherein the microcrystallization process includes a step of nucleating a base glass substrate at a first temperature and then crystallizing the base glass substrate at a second temperature, both the first temperature and the second temperature being lower than a softening point temperature of the base glass substrate, and the second temperature being higher than the first temperature.
Wherein the base glass matrix comprises, based on the total weight of the base glass matrix: 52-65% by weight of SiO212-27% by weight of Al2O35-19% by weight of Na2O, 0-3.5% by weight of K2O, 2-7 wt% MgO, 3-10 wt% Li2O, 0.5-5 wt% ZrO20-4.5% by weight of TiO2。
Preferably, the glass-ceramic comprises:
55-60% by weight of SiO2，
15.5-23.5 wt.% of Al2O3，
7-13% by weight of Na2O，
0.5-2.5% by weight of K2O，
2.5-4.5% by weight of MgO,
3.5-6.5 wt.% Li2O，
1.2-4% by weight of ZrO2，
0.5-3.5 wt% TiO2。
Preferably, the glass ceramics further contains 0.1-2% by weight of a clarifier component. Preferably, the clarifier composition comprises SO4 2-、NO3 -、F-And Cl-At least one of (1).
The basic glass matrix prepared by adopting the composition is particularly suitable for the microcrystallization treatment and the strengthening treatment in the later period.
Preferably, the base glass substrate is produced by any one of a float process, an overflow process and a down-draw process.
Preferably, the base glass substrate is a glass substrate, preferably a glass substrate having a thickness of 0.33 to 1 mm.
In order to keep the base glass body dimensionally stable, the base glass body (e.g. a glass substrate) is preferably placed directly on the carrier plate for the microcrystallization. Preferably, the carrier plate is graphite, more preferably while using nitrogen as a shielding gas.
In order to further ensure the maximum nucleation efficiency and the desired crystal size, the first temperature is preferably 550-640 ℃, more preferably 560-620 ℃, and the nucleation time is preferably 2-7h, more preferably 4-6 h.
In order to further ensure the precipitation of the ideal crystal size, the second temperature is preferably 640-750 ℃, more preferably 650-720 ℃, and the crystallization time is 0.2-4h, more preferably 0.5-2 h.
In a preferred embodiment, the microcrystallization process comprises nucleating the base glass substrate at 550-640 ℃ for 2-7h followed by crystallizing at 640-750 ℃ for 0.2-4 h.
In the present invention, the nucleation temperature, the nucleation time, the crystallization temperature, and the crystallization time are collectively referred to as a heat treatment schedule, and the heat treatment schedule can be determined as follows: the transition temperature (Tg) and the temperature at which the devitrification rate is maximum (Tp) of a base glass substrate (e.g., a base glass substrate) are measured by a differential scanning calorimeter (DSC404F 3). A small part of basic glass substrate (such as a basic glass substrate) is ground and then sieved by a 200-mesh sieve, 10mg of the ground basic glass substrate is weighed and placed in a platinum crucible for testing, and the temperature is raised from room temperature at a rate of 10K/min until the test is finished. The base glass is in a high internal energy metastable state, and can emit heat in the process of transforming into crystals, so that the Tg point and the Tp point of the base glass are analyzed, and the temperatures of a nucleation step and a crystallization step are further determined.
Preferably, the secondary chemical strengthening treatment comprises: placing the base glass substrate after micro crystallization treatment into 100% NaNO3Carrying out a first ion exchange in the molten salt at a first strengthening temperature, and adding 100% KNO after the first ion exchange3A second ion exchange in the molten salt is performed at a second strengthening temperature, the first strengthening temperature being higher than the second strengthening temperature.
Preferably, the conditions of the first ion exchange include: the first strengthening temperature is 400-470 ℃, preferably 410-460 ℃, and the duration is 1-4h, preferably 2-3 h.
Preferably, the conditions of the second ion exchange include: the second strengthening temperature is 400-450 ℃, preferably 410-440 ℃, and the duration is 0.5-3h, preferably 1-2.5 h.
In a preferred embodiment, the secondary chemical strengthening treatment comprises: (a) placing the microcrystallized basic glass substrate into 100% NaNO at 400-470 deg.C3Carrying out first ion exchange in molten salt for 1-4 h; and (b) subjecting the resulting mixture to 100% KNO at 400-3And carrying out secondary ion exchange in molten salt for 0.5-3 h.
After the secondary chemical strengthening, the surface compressive stress of the microcrystalline glass is more than 800MPa, preferably more than 900 MPa; the depth of the stress layer is 90 μm or more, preferably 95 μm or more, and more preferably more than 110 μm; a compressive stress at 50 μm from the surface of greater than 80MPa, preferably greater than 90MPa, more preferably greater than 100 MPa; a Vickers hardness of 630kgf/mm2The above; the four-point bending strength is more than 650 MPa; the impact strength is more than 0.3J; the whole sand paper falls to a height of over 160 cm.
In one embodiment of the present invention, the strengthening treatment may be selectively performed or not performed after the microcrystallization treatment, depending on the application environment and the purpose of use of the glass.
According to the invention, the invention is adoptedThe crystalline phase of the microcrystalline glass prepared by the microcrystallization step comprises lithium disilicate, beta-quartz solid solution and Mg2TiO4And lithium metasilicate crystal, the crystallization degree is 10-25 wt%, the crystal size is less than 1 μm, preferably 0.4-0.9 μm, and the obtained glass ceramics has better strength, light transmittance and lower haze. For example, the microcrystalline glass obtained by the invention has the light transmittance of more than 86% in the wavelength range of 380nm-780nm and the haze of less than 0.5%.
Herein, the crystalline phase of the microcrystalline glass is obtained by comparing an XRD pattern with a Jade index card. In the glass-ceramic according to the present invention, the crystals are present in a spherical form. The spherical crystals are very beneficial to improving the bending resistance and mechanical property of the glass, and the existence of a certain content of spherical crystal phases can bend and passivate the tips of cracks, increase the breaking work and relieve and prevent the cracks from penetrating through the interfaces of the crystal phases and the glass phases.
Herein, the devitrification degree of the microcrystalline glass is obtained by normalizing each diffraction peak intensity value in the XRD pattern.
The light transmittance is an important index for determining the optical performance of the microcrystalline glass. When light passes through the glass-ceramic, there is a relationship of T + R + Q equal to 1 between the transmittance (T), reflectance (R), and absorptance (Q) according to the principle of conservation of energy. Because the microcrystalline glass has low crystallization degree, thin thickness and colorless and transparent state, the light absorption rate Q can be ignored. The transmittance is therefore related only to the reflectance, which in turn is related to the refractive index according to Fresnel's equation (1) which is:
in the formula (1), n is a refractive index.
The refractive indexes of the crystalline phase and the glass phase in the glass ceramics are approximately equal. For example, the glass ceramics have a refractive index of 1.54 and a reflectance of 4.52%. For a single layer of glass having two surfaces, the total reflectance was 8.9% and the transmittance was 91.1%.
Haze is another important indicator for determining the optical properties of the glass-ceramic. Haze is the ratio of the scattered luminous flux to the transmitted luminous flux. From the light scattering angle, the light scattering intensity distribution of the glass ceramics conforms to Rayleigh law, and the Rayleigh-Gans model describes the light scattering intensity:
in formula (2), σ — the light scattering intensity of the sample; n-degree of crystallization; v-volume of crystals in μm3(ii) a K-constant, K ═ 2 pi/λ; d-crystal diameter in μm; n is the difference in refractive index between the glassy and crystalline phases.
On the one hand, to some extent, the size, volume and degree of crystallization of crystals in the glass-ceramic depend on the conditions of nucleation and crystallization processes, and the light scattering intensity is related to the difference between the refractive indices of the glass phase and the crystalline phase. The glass phase and the crystalline phase in the glass ceramics have approximately equal refractive indexes, so the glass ceramics have low scattering strength and small haze. On the other hand, it is generally accepted that the forward scattering is promoted by crystal particles close to the wavelength of light, and the crystallite size in the glass-ceramic according to the invention is smaller than 1 μm, preferably 0.4-0.9 μm, and is close to the wavelength range of visible light, so that the scattering intensity is low and the haze is small.
In this context, the relevant test items may all adopt the test means commonly used in the art, and specifically may be as follows:
the transmission of the glass-ceramic is determined by using a spectrophotometer according to standard ISO 13468-1: 1996 measurement;
the haze of the glass-ceramic is measured by using a haze meter with reference to the standard ISO14782: 1999;
the surface compressive stress value, the depth of layer of compressive stress and the compressive stress at 50 μm from the surface of the glass-ceramic are measured by using a surface stress meter according to the method described in the standard GB/T18144-2008;
the impact strength of the microcrystalline glass is measured by a ball drop tester, specifically, a glass sample to be measured is placed on a jig, so that a 32g steel ball falls from a specified height, and the maximum ball drop height of the impact which can be borne by the glass sample to be measured without fragmentation is measured. Specifically, the test was carried out starting from a height of 30mm, the centre point falling 3 times, each time rising 10mm, until the glass broke. Calculating the impact resistance by using a potential energy formula Ep-mgh;
the complete machine abrasive paper dropping performance of the microcrystalline glass is measured by a mobile phone controlled dropping tester, and the specific test conditions are as follows: 180-mesh sand paper, 170g of the total weight, 60cm of base height, increasing by 10cm, and 1 time per height until the sand paper is crushed;
the hardness of the glass ceramics is measured by using a Vickers hardness tester according to the standard GB/T16534-;
the four-point bending strength of the crystallized glass was measured by using a universal tester with reference to the standard JC/T676- "1997 (test conditions: upper/lower span 20/40cm, pressing speed 10mm/min, rod diameter 6 mm).
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.
The third aspect of the present invention provides an application of the glass ceramics according to the first aspect of the present invention and/or the glass ceramics prepared by the method according to the second aspect of the present invention in the manufacture of display screen protection glass and rear cover protection glass of an intelligent mobile terminal.
Herein, the smart mobile terminal includes, but is not limited to, a mobile phone, a tablet computer, a notebook computer, and the like.
The microcrystalline glass provided by the invention is particularly suitable for being used as display device protective glass due to high light transmittance, high strength, excellent impact resistance and excellent drop resistance.
The present invention will be described in detail below by way of examples.
It should be understood that the specific embodiments described herein are merely illustrative and explanatory of the invention and are not restrictive thereof.
In some embodiments, the base glass substrate used to make the microcrystalline glass of the present invention is made by a float process.
In other embodiments, the base glass substrate used to make the glass-ceramic of the present invention is made by an overflow process.
Examples 1 to 10
A base glass substrate prepared using the float process, the base glass substrate having a composition as shown in table 1 and a thickness of 0.7 mm.
TABLE 1
Cutting, grinding, polishing and other procedures are carried out on the obtained basic glass substrate to obtain a sheet with the specification of 140mm multiplied by 70mm multiplied by 0.7mm, and then microcrystallization treatment is carried out, wherein in the whole microcrystallization treatment process, a graphite carrier is adopted as a glass carrier, and nitrogen is filled as a protective gas. The nucleation temperature, nucleation time, crystallization temperature and crystallization time are collectively referred to as a heat treatment schedule, and specific heat treatment schedules are as described in table 2 below.
TABLE 2
Placing the microcrystallized base glass substrate on a stainless steel sample holder using molten NaNO3And melting KNO3After the secondary chemical strengthening treatment (conditions shown in Table 3), glass ceramics A1-A10 were obtained.
TABLE 3
The obtained glass ceramics A1-A10 were subjected to the following performance tests:
comparing the X-ray spectrum with Jade index card by using an X-ray diffraction analysis device, as shown in FIG. 2, the crystalline phase of the glass ceramics obtained in example 1 is β -Quartz solid solution, beta-quartz. The crystal phases precipitated in other examples precipitated lithium disilicate crystal phases (JCPDS #23-1203, Jade index card JCPDS #30-0766), Mg and Mg in addition to the β -quartz solid solution and β -quartz crystal phases2TiO4Crystalline phase (Jade index card JCPDS #25-1157), and the like.
And (5) determining the crystal morphology and the crystal size by using a scanning electron microscope. And etching the sample of the microcrystalline glass A1-A10 in HF acid, spraying gold on the surface of the microcrystalline glass, and performing surface scanning under a scanning electron microscope to determine the crystal form and the size of the microcrystalline glass.
The surface compressive stress value, the stress layer depth and the compressive stress at 50 mu m from the surface of the glass ceramics A1-A10 are tested by using FSM-6000 and SLP-2000 surface stress instruments according to the standard GB-T18144-2008.
The transmittance of the resulting glass-ceramic at a wavelength of 550nm (as shown in FIG. 1) is determined using a spectrophotometer, with reference to ISO13468, and the haze is determined using a haze meter, with reference to ISO14782: 1999.
The hardness of the glass ceramics was measured using a Vickers hardness tester, reference standard GB/T16534-2009.
The impact strength of the microcrystalline glass A1-A10 was tested by a falling ball tester. Specifically, a microcrystalline glass sample was placed on a jig, a 32g steel ball was dropped from a predetermined height, and the maximum ball drop height of the impact that the sample could withstand without being broken was measured. Specifically, the test was carried out starting from a height of 30mm, the centre point falling 3 times, each time rising 10mm, until the glass broke. And calculating the impact resistance by using the potential energy formula Ep-mgh.
The four-point bending strength test is carried out on the microcrystalline glass sample by using a universal tester according to a standard JC/T676-: the up/down span is 20/40cm, the pressing speed is 10mm/min, and the rod diameter is 6 mm.
And testing the complete machine abrasive paper dropping performance by adopting a mobile phone controlled dropping tester with the model number of GP-2112. The specific test conditions were: 180 grit sandpaper, 170g total weight, 60cm base height, in 10cm increments, each height tested 1 time until broken.
The test results are shown in table 4.
TABLE 4
Examples 11 to 20
A base glass substrate having a composition as shown in Table 5 and a thickness of 0.5mm was prepared by the overflow process.
TABLE 5
The base glass was subjected to cutting, grinding, polishing, and the like to obtain a sheet having a size of 140mm × 70mm × 0.5 mm. And then carrying out microcrystallization treatment, wherein in the whole microcrystallization treatment process, the glass carrier adopts a graphite carrier, and nitrogen serving as a protective gas is filled in the graphite carrier. The nucleation temperature, nucleation time, crystallization temperature and crystallization time are collectively referred to as a heat treatment schedule, and specific heat treatment schedules are as described in table 6 below.
TABLE 6
The secondary chemical strengthening treatment was carried out by the method described in example 1 under the specific conditions shown in table 7, to finally obtain glass ceramics a11-a 20.
TABLE 7
The glass ceramics a11-a20 were subjected to the relevant performance tests in accordance with the method described in example 1, and the test results are shown in table 8.
TABLE 8
Comparative examples 1 to 15
Comparative examples 1 to 3 general lithium aluminosilicate glass (manufactured by the float process) having a composition as shown in table 9 and a thickness of 0.7mm was used as a base glass substrate, and the microcrystallization treatment was performed as described in example 1 under specific conditions as shown in table 9 without performing secondary chemical strengthening treatment.
Comparative examples 4 to 6 using general lithium aluminosilicate glass (manufactured by the float process) as a base glass substrate having a composition as shown in table 9 and a thickness of 0.7mm, chemical strengthening treatment was performed without microcrystallization treatment according to the method described in example 1, and specific conditions are shown in table 9.
Comparative examples 7 to 9 general lithium aluminosilicate glasses (manufactured by the overflow process) were used as base glass substrates having compositions as shown in table 9 and thicknesses of 0.5mm, and subjected to microcrystallization treatment as described in example 11 under conditions shown in table 9, followed by chemical strengthening treatment (not the chemical strengthening method of the present invention).
Comparative examples 10 to 12 general lithium aluminosilicate glasses (manufactured by the overflow process) were used as base glass substrates, the compositions of which are shown in table 9, and the thicknesses of which were 0.5mm, and after the microcrystallization treatment, secondary chemical strengthening treatment was performed, and the microcrystallization treatment was performed by the method not described in the present invention, and the chemical strengthening treatment was performed by the method described in example 11, under the conditions shown in table 9.
Comparative examples 13 to 15 using conventional lithium aluminosilicate glass (manufactured by the float process) as a base glass substrate having a composition as shown in table 9 and a thickness of 0.7mm, the microcrystallization treatment and the secondary chemical strengthening treatment were carried out as described in example 11 under the specific treatment conditions as shown in table 9.
Comparative glasses D1-D15 were finally prepared according to the compositions and process conditions shown in Table 9. The performance test was carried out as described in example 1, and the test results are shown in Table 10.
By comprehensively comparing the data in tables 4, 8 and 10, it can be found that:
according to the invention, the microcrystalline glass prepared by micro crystallization treatment and secondary chemical strengthening treatment has the light transmittance of over 86 percent, the falling performance of the whole machine of over 160cm, and also has excellent mechanical properties such as impact resistance, surface Vickers hardness, bending resistance (four-point bending strength) and the like.
Compared glass obtained by adopting the basic glass matrix composed of the glass and the microcrystallization treatment process of the invention without secondary chemical strengthening treatment has the advantages of less than 0.25J of impact strength, less than 70cm of complete machine drop performance and far lower performance than the microcrystalline glass of the invention.
After the existing lithium-aluminum-silicon glass is used and subjected to secondary chemical strengthening, the falling performance of the whole machine is less than 120cm and far lower than 160cm of the microcrystalline glass.
By adopting the basic glass substrate composed of the glass and the microcrystallization treatment process, but the secondary chemical strengthening process is different from the microcrystallization treatment process, the final prepared comparative glass has the whole machine falling performance of less than 120cm and far lower than 160cm of the microcrystalline glass.
By adopting the basic glass substrate composed of the glass and the secondary chemical strengthening treatment process, but the microcrystallization treatment process is different from the secondary chemical strengthening treatment process, the finally prepared comparative glass has the advantages that the whole machine dropping performance is less than 125cm, the light transmittance is less than 85 percent, and the performance of the glass is far less than that of the microcrystalline glass.
The base glass substrate with the composition different from that of the microcrystalline glass provided by the invention is adopted, but the microcrystalline treatment process and the secondary chemical strengthening treatment process are adopted, so that the contrast glass is finally obtained, the whole machine dropping performance of the contrast glass is less than 125cm, the light transmittance is less than 85%, and the performance of the contrast glass is far less than that of the microcrystalline glass provided by the invention.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (25)
1. A glass ceramic comprising, based on the total weight of the glass ceramic: 52-59.8% by weight of SiO212-27% by weight of Al2O35-19% by weight of Na2O, 0-3.5% by weight of K2O, 2.5-4.5 wt% MgO, 3-10 wt% Li2O, 0.5-5 wt% ZrO20-4.5% by weight of TiO2；
Wherein, Al2O3/Na2The weight ratio of O is 2-4;
Al2O3/（Na2O+Li2o) in a weight ratio of 1.2-2, wherein Na is2O+Li2O is Na2O、Li2Sum of the weight contents of O;
wherein the crystallized glass comprises a microcrystalline portion having a spherical crystal phase containing lithium disilicate, β -quartz, a β -quartz solid solution, Mg, and a glass phase portion, and the crystallized glass has a crystallinity of 10 to 25% by weight2TiO4And lithium metasilicate.
2. The glass-ceramic according to claim 1, characterized in that the size of the spherical crystalline phase is not more than 1 μm.
3. Glass-ceramic according to claim 2, characterized in that the size of the spherical crystalline phase is 0.4-0.9 μm.
4. The glass-ceramic according to any one of claims 1 to 3, characterized in that the glass-ceramic comprises, based on the total weight of the glass-ceramic:
55-59.8% by weight of SiO2，
15.5-23.5 wt.% of Al2O3，
7-13% by weight of Na2O，
0.5-2.5% by weight of K2O，
2.5-4.5% by weight of MgO,
3.5-6.5 wt.% Li2O，
1.2-4% by weight of ZrO2，
0.5-3.5 wt% TiO2；
And/or the glass ceramics also comprises 0.1-2 wt% of a clarifier component.
5. The microcrystalline glass according to claim 4, characterised in that the refining agent component comprises SO4 2-、NO3 -、F-And Cl-At least one of (1).
6. The glass-ceramic according to any one of claims 1 to 3 or 5, wherein SiO is SiO2、Al2O3、Li2Sum of the weight contents of O and SiO2+Al2O3+Li2O is 80-90 wt%;
and/or, ZrO2、TiO2ZrO in a total amount by weight2+TiO2Is 2-6 wt%.
7. Microcrystalline glass according to claim 4, characterised in that SiO2、Al2O3、Li2Sum of the weight contents of O and SiO2+Al2O3+Li2O is 80-90 wt%;
and/or, ZrO2、TiO2ZrO in a total amount by weight2+TiO2Is 2-6 wt%.
8. The glass-ceramic according to any one of claims 1 to 3, 5 and 7, wherein the glass-ceramic has a transmittance of 86% or more in a wavelength range of 380-780 nm;
and/or the haze of the microcrystalline glass in the wavelength range of 380-780nm is less than 0.5 percent;
and/or the surface compressive stress of the microcrystalline glass is at least more than 800 MPa;
and/or the depth of the compressive stress layer of the microcrystalline glass is more than 90 mu m;
and/or the compressive stress of the microcrystalline glass at a position 50 [ mu ] m away from the surface is more than 80 MPa;
and/or the whole machine sand paper falling height of the microcrystalline glass is more than 160 cm;
and/or the Vickers hardness of the microcrystalline glass is 630kgf/mm2The four-point bending strength is above 650 MPa;
and/or the impact strength of the microcrystalline glass is more than 0.3J.
9. The glass-ceramic according to claim 8, wherein the depth of layer of compressive stress of the glass-ceramic is greater than 95 μm;
and/or the compressive stress of the microcrystalline glass at a position 50 [ mu ] m away from the surface is more than 90 MPa.
10. The glass-ceramic according to claim 9, characterized in that the depth of layer of compressive stress of the glass-ceramic is greater than 110 μm;
and/or the compressive stress of the microcrystalline glass at a position 50 [ mu ] m away from the surface is more than 100 MPa.
11. The glass-ceramic according to claim 4, wherein the glass-ceramic has a transmittance of 86% or more in a wavelength range of 380-780 nm;
and/or the haze of the microcrystalline glass in the wavelength range of 380-780nm is less than 0.5 percent;
and/or the surface compressive stress of the microcrystalline glass is at least more than 800 MPa;
and/or the depth of the compressive stress layer of the microcrystalline glass is more than 90 mu m;
and/or the compressive stress of the microcrystalline glass at a position 50 [ mu ] m away from the surface is more than 80 MPa;
and/or the whole machine sand paper falling height of the microcrystalline glass is more than 160 cm;
and/or the Vickers hardness of the microcrystalline glass is 630kgf/mm2The four-point bending strength is above 650 MPa;
and/or the impact strength of the microcrystalline glass is more than 0.3J.
12. The glass-ceramic according to claim 6, wherein the glass-ceramic has a transmittance of 86% or more in a wavelength range of 380-780 nm;
and/or the haze of the microcrystalline glass in the wavelength range of 380-780nm is less than 0.5 percent;
and/or the surface compressive stress of the microcrystalline glass is at least more than 800 MPa;
and/or the depth of the compressive stress layer of the microcrystalline glass is more than 90 mu m;
and/or the compressive stress of the microcrystalline glass at a position 50 [ mu ] m away from the surface is more than 80 MPa;
and/or the whole machine sand paper falling height of the microcrystalline glass is more than 160 cm;
and/or the Vickers hardness of the microcrystalline glass is 630kgf/mm2The four-point bending strength is above 650 MPa;
and/or the impact strength of the microcrystalline glass is more than 0.3J.
13. The glass-ceramic according to claim 11 or 12, characterized in that the depth of layer of compressive stress of the glass-ceramic is greater than 95 μ ι η;
and/or the compressive stress of the microcrystalline glass at a position 50 [ mu ] m away from the surface is more than 90 MPa.
14. The glass-ceramic according to claim 13, characterized in that the depth of layer of compressive stress of the glass-ceramic is greater than 110 μm;
and/or the compressive stress of the microcrystalline glass at a position 50 [ mu ] m away from the surface is more than 100 MPa.
15. A method for producing a glass-ceramic, comprising:
(1) carrying out microcrystallization treatment on the basic glass substrate; and
(2) carrying out secondary chemical strengthening treatment on the base glass matrix subjected to the microcrystallization treatment;
wherein the microcrystallization process comprises a step of nucleating a base glass substrate at a first temperature and then crystallizing the base glass substrate at a second temperature, both the first temperature and the second temperature being lower than a softening point temperature of the base glass substrate, and the second temperature being higher than the first temperature; and is
Wherein the base glass matrix comprises, based on the total weight of the base glass matrix: 52-59.8% by weight of SiO212-27% by weight of Al2O35-19% by weight of Na2O, 0-3.5% by weight of K2O, 2.5-4.5 wt% MgO, 3-10 wt% Li2O, 0.5-5 wt% ZrO20-4.5% by weight of TiO2；
Wherein, Al2O3/Na2The weight ratio of O is 2-4;
Al2O3/（Na2O+Li2o) in a weight ratio of 1.2-2, wherein Na is2O+Li2O is Na2O、Li2Sum of the weight contents of O.
16. The method as claimed in claim 15, wherein the first temperature is 550-640 ℃, and the nucleation time is 2-7 h; the second temperature is 640-750 ℃, and the crystallization time is 0.2-4 h.
17. The method of claim 15 or 16, wherein the base glass substrate comprises:
55-59.8% by weight of SiO2，
15.5-23.5 wt.% of Al2O3，
7-13% by weight of Na2O，
0.5-2.5% by weight of K2O，
2.5-4.5% by weight of MgO,
3.5-6.5 wt.% Li2O，
1.2-4% by weight of ZrO2，
0.5-3.5 wt% TiO2；
And/or the glass ceramics also comprises 0.1-2 wt% of a clarifier component; and/or the base glass substrate is prepared by any one process of a float process, an overflow process and a pull-down process;
and/or the base glass substrate is a glass substrate.
18. The method of claim 17, wherein the fining agent component comprises SO4 2-、NO3 -、F-And Cl-At least one of;
and/or the base glass substrate is a glass substrate with the thickness of 0.33-1 mm.
19. The method according to any one of claims 15-16, 18, wherein the secondary chemical strengthening treatment comprises: placing the base glass substrate after micro crystallization treatment into 100% NaNO3Carrying out a first ion exchange in the molten salt at a first strengthening temperature, and adding 100% KNO after the first ion exchange3A second ion exchange in the molten salt is performed at a second strengthening temperature, the first strengthening temperature being higher than the second strengthening temperature.
20. The method of claim 19, wherein the conditions of the first ion exchange comprise: the first strengthening temperature is 400-470 ℃, and the duration time is 1-4 h;
and/or, the conditions of the second ion exchange include: the second strengthening temperature is 400-450 ℃, and the duration is 0.5-3 h.
21. The method of claim 20, wherein the conditions of the first ion exchange comprise: the first strengthening temperature is 410-460 ℃, and the duration time is 2-3 h;
and/or, the conditions of the second ion exchange include: the second strengthening temperature is 410-440 ℃, and the duration is 1-2.5 h.
22. The method of claim 17, wherein the secondary chemical strengthening treatment comprises: placing the base glass substrate after micro crystallization treatment into 100% NaNO3Carrying out a first ion exchange in the molten salt at a first strengthening temperature, and adding 100% KNO after the first ion exchange3A second ion exchange in the molten salt is performed at a second strengthening temperature, the first strengthening temperature being higher than the second strengthening temperature.
23. The method of claim 22, wherein the conditions of the first ion exchange comprise: the first strengthening temperature is 400-470 ℃, and the duration time is 1-4 h;
and/or, the conditions of the second ion exchange include: the second strengthening temperature is 400-450 ℃, and the duration is 0.5-3 h.
24. The method of claim 23, wherein the conditions of the first ion exchange comprise: the first strengthening temperature is 410-460 ℃, and the duration time is 2-3 h;
and/or, the conditions of the second ion exchange include: the second strengthening temperature is 410-440 ℃, and the duration is 1-2.5 h.
25. Use of the glass ceramic according to any one of claims 1 to 14 and/or the glass ceramic produced by the method according to any one of claims 15 to 24 in the manufacture of display screen protection glass and rear cover protection glass of intelligent mobile terminals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911268661.1A CN112939472B (en) | 2019-12-11 | 2019-12-11 | Microcrystalline glass and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911268661.1A CN112939472B (en) | 2019-12-11 | 2019-12-11 | Microcrystalline glass and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112939472A CN112939472A (en) | 2021-06-11 |
| CN112939472B true CN112939472B (en) | 2022-04-26 |
Family
ID=76234109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911268661.1A Active CN112939472B (en) | 2019-12-11 | 2019-12-11 | Microcrystalline glass and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112939472B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594406A (en) * | 2021-07-08 | 2023-01-13 | 荣耀终端有限公司（Cn） | Chemically strengthened glass ceramics and preparation method and application thereof |
| CN113880412B (en) * | 2021-10-25 | 2023-04-28 | 清远南玻节能新材料有限公司 | Microcrystalline glass and preparation method thereof, glass protection layer, glass cover plate and electronic device |
| CN116199416A (en) * | 2021-11-30 | 2023-06-02 | 深圳市微思腾新材料科技有限公司 | Preparation method of high-strength glass |
| CN114477792A (en) * | 2022-02-25 | 2022-05-13 | Oppo广东移动通信有限公司 | Method for strengthening microcrystalline glass, cover plate, and electronic device |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101437769A (en) * | 2006-03-31 | 2009-05-20 | 欧罗克拉公司 | Beta-spodumene glass-ceramic materials and process for making the same |
| CN102690059A (en) * | 2011-03-23 | 2012-09-26 | 肖特玻璃科技(苏州)有限公司 | Aluminosilicate glass for chemical tempering and glass ceramics |
| CN104108883A (en) * | 2014-08-11 | 2014-10-22 | 中国地质大学（北京） | High-strength lithium disilicate glass ceramic and preparation method thereof |
| EP3228602A1 (en) * | 2016-04-06 | 2017-10-11 | Hass Co., Ltd. | Nano lithium disilicate glass-ceramic and its method for preparing |
| CN107840578A (en) * | 2017-12-01 | 2018-03-27 | 成都光明光电股份有限公司 | Devitrified glass and its substrate |
| CN107902909A (en) * | 2017-12-01 | 2018-04-13 | 成都光明光电股份有限公司 | Devitrified glass and its substrate |
| CN108069611A (en) * | 2016-11-16 | 2018-05-25 | 中国科学院过程工程研究所 | The lithium metasilicate devitrified glass of high permeability and lithium bisilicate devitrified glass, preparation method and use |
| GB201905559D0 (en) * | 2018-04-18 | 2019-06-05 | Alzahrani Ali Saleh A | Composition and method |
| CN109867447A (en) * | 2017-12-01 | 2019-06-11 | 成都光明光电股份有限公司 | Devitrified glass and its substrate |
| CN110002744A (en) * | 2019-04-30 | 2019-07-12 | 四川旭虹光电科技有限公司 | A kind of high impact properties glass and preparation method thereof |
| CN110482866A (en) * | 2019-08-21 | 2019-11-22 | 成都光明光电股份有限公司 | Crystallized glass article, devitrified glass and its manufacturing method |
| CN110510879A (en) * | 2019-08-21 | 2019-11-29 | 成都光明光电股份有限公司 | Crystallized glass article, devitrified glass and its manufacturing method |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2263234C3 (en) * | 1972-12-23 | 1975-07-10 | Jenaer Glaswerk Schott & Gen., 6500 Mainz | Process for the production of high-strength glass objects which are resistant to temperature changes by surface crystallization using ion exchange within the glass |
| JPS6153131A (en) * | 1984-08-23 | 1986-03-17 | Nippon Electric Glass Co Ltd | Crystallized glass and its production |
| JP2002154840A (en) * | 2000-11-16 | 2002-05-28 | Nippon Electric Glass Co Ltd | Li2O-Al2O3-SiO2 CRYSTALLIZED GLASS |
| JP4647256B2 (en) * | 2003-07-28 | 2011-03-09 | 株式会社オハラ | Glass ceramics |
| JP4430001B2 (en) * | 2005-11-01 | 2010-03-10 | 湖州大享玻璃制品有限公司 | Li2O-Al2O3-SiO2-MgO-K2O-F-based crystalline glass and crystallized glass, and method for producing the crystalline glass and crystallized glass |
| CN109694186A (en) * | 2019-01-25 | 2019-04-30 | 四川旭虹光电科技有限公司 | A kind of chemically reinforced glass plate and preparation method thereof |
-
2019
- 2019-12-11 CN CN201911268661.1A patent/CN112939472B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101437769A (en) * | 2006-03-31 | 2009-05-20 | 欧罗克拉公司 | Beta-spodumene glass-ceramic materials and process for making the same |
| CN102690059A (en) * | 2011-03-23 | 2012-09-26 | 肖特玻璃科技(苏州)有限公司 | Aluminosilicate glass for chemical tempering and glass ceramics |
| CN104108883A (en) * | 2014-08-11 | 2014-10-22 | 中国地质大学（北京） | High-strength lithium disilicate glass ceramic and preparation method thereof |
| EP3228602A1 (en) * | 2016-04-06 | 2017-10-11 | Hass Co., Ltd. | Nano lithium disilicate glass-ceramic and its method for preparing |
| CN108069611A (en) * | 2016-11-16 | 2018-05-25 | 中国科学院过程工程研究所 | The lithium metasilicate devitrified glass of high permeability and lithium bisilicate devitrified glass, preparation method and use |
| CN107840578A (en) * | 2017-12-01 | 2018-03-27 | 成都光明光电股份有限公司 | Devitrified glass and its substrate |
| CN107902909A (en) * | 2017-12-01 | 2018-04-13 | 成都光明光电股份有限公司 | Devitrified glass and its substrate |
| CN109867447A (en) * | 2017-12-01 | 2019-06-11 | 成都光明光电股份有限公司 | Devitrified glass and its substrate |
| GB201905559D0 (en) * | 2018-04-18 | 2019-06-05 | Alzahrani Ali Saleh A | Composition and method |
| CN110002744A (en) * | 2019-04-30 | 2019-07-12 | 四川旭虹光电科技有限公司 | A kind of high impact properties glass and preparation method thereof |
| CN110482866A (en) * | 2019-08-21 | 2019-11-22 | 成都光明光电股份有限公司 | Crystallized glass article, devitrified glass and its manufacturing method |
| CN110510879A (en) * | 2019-08-21 | 2019-11-29 | 成都光明光电股份有限公司 | Crystallized glass article, devitrified glass and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112939472A (en) | 2021-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112939472B (en) | Microcrystalline glass and preparation method and application thereof | |
| JP7184073B2 (en) | glass for chemical strengthening | |
| CN110128010B (en) | Transparent glass-ceramic articles, glass-ceramic precursor glasses and methods of forming the same | |
| JP5392391B2 (en) | Tempered glass substrate and manufacturing method thereof | |
| TWI650294B (en) | Anti-fracture glass ceramic article and method for manufacturing same | |
| CN103588392A (en) | Tempered glass and glass | |
| WO2019230889A1 (en) | Tempered glass and glass for tempering | |
| CN114956577A (en) | High-strength transparent microcrystalline glass and preparation method thereof | |
| CN113929308A (en) | Microcrystalline glass with ultrahigh bifurcation threshold | |
| WO2014002932A1 (en) | Glass substrate for organic el device and manufacturing method therefor | |
| WO2019003565A1 (en) | Crystallized glass substrate | |
| JP2021181388A (en) | Crystallized glass | |
| JP2024011959A (en) | Inorganic composition article | |
| JP2024011923A (en) | Inorganic composition article |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |