阅读说明：本技术 一种高硬度、高强度及高透明度微晶玻璃及其制法和应用 (High-hardness, high-strength and high-transparency microcrystalline glass and preparation method and application thereof ) 是由 赵天佑 赵国祥 赵成玉 吴非 于 2019-12-11 设计创作，主要内容包括：本发明涉及一种高硬度、高强度及高透明度微晶玻璃及其制法和应用,制备方法为：将混合料铸造成玻璃后进行晶化处理制得微晶玻璃,其中,混合料主要由Li<Sub>2</Sub>O、A<Sub>2</Sub>lO<Sub>3</Sub>、SiO<Sub>2</Sub>、CaO、SrO、ZnO、BaO、K<Sub>2</Sub>O、Na<Sub>2</Sub>O、ZrO<Sub>2</Sub>、Sb<Sub>2</Sub>O<Sub>3</Sub>和NaCl组成；制得的微晶玻璃主要由玻璃基体以及分散在其中呈树枝状分布的锂辉石晶体、呈颗粒状分布的尖晶石晶体和呈颗粒状分布的立方氧化锆晶体组成；可应用于制备高强度耐磨透明微晶玻璃釉,也可应用于制备手机面板。本发明的一种高硬度、高强度及高透明度微晶玻璃的制备方法,简单易行,极具推广价值；制得的微晶玻璃熔点较低,成型加工性能优异,应用前景广阔。(The invention relates to a high-hardness, high-strength and high-transparency glass ceramic and a preparation method and application thereof, wherein the preparation method comprises the following steps: casting the mixture into glass, and crystallizing to obtain microcrystalline glass, wherein the mixture mainly comprises Li 2 O、A 2 lO 3 、SiO 2 、CaO、SrO、ZnO、BaO、K 2 O、Na 2 O、ZrO 2 、Sb 2 O 3 And NaCl; the obtained microcrystalline glass mainlyThe glass consists of a glass matrix, and spodumene crystals, spinel crystals and cubic zirconium oxide crystals which are dispersed in the glass matrix and distributed in a dendritic manner; the preparation method can be applied to preparation of high-strength wear-resistant transparent glass-ceramic glaze and can also be applied to preparation of mobile phone panels. The preparation method of the microcrystalline glass with high hardness, high strength and high transparency is simple and easy to implement and has great popularization value; the prepared microcrystalline glass has the advantages of low melting point, excellent forming and processing properties and wide application prospect.)

1. High hardness, high strength and high transparencyThe preparation method of the microcrystalline glass is characterized by comprising the following steps: casting the mixture into glass, and then performing crystallization treatment to obtain the microcrystalline glass, wherein the mixture mainly comprises 1.0-3.2% of Li in percentage by weight₂O、0.5～3.5％Al₂O₃、50.0～65.0％SiO₂、0.2～4.5％CaO、1.0～6.0％SrO、1.0～9.1％ZnO、2.0～8.0％BaO、0.0～2.5％K₂O、3.0～9.7％Na₂O、4.0～15.0％ZrO₂、0.3～0.6％Sb₂O₃And 0.3-0.6% NaCl.

2. The method for preparing the microcrystalline glass with high hardness, high strength and high transparency according to claim 1, wherein the casting process comprises the following steps: and melting the mixture at 1600-1630 ℃ for 8-9 h, and then pouring or pressing for molding.

3. The method for preparing the microcrystalline glass with high hardness, high strength and high transparency according to claim 1, wherein the crystallization treatment is divided into two stages, the temperature of the first stage is 670-690 ℃, and the time is 3-5 h; the temperature of the second stage is 930-950 ℃, and the time is 2-3 h.

4. The method for preparing the microcrystalline glass with high hardness, high strength and high transparency according to claim 3, wherein the annealing treatment is performed after the crystallization treatment, and the annealing treatment temperature is 670-690 ℃ and the time is 3-5 h.

5. The high-hardness, high-strength and high-transparency glass ceramics prepared by the method for preparing the high-hardness, high-strength and high-transparency glass ceramics according to any one of claims 1 to 4, which is characterized in that: mainly comprises a glass matrix, and spodumene crystals, spinel crystals and cubic zirconium oxide crystals which are dispersed in the glass matrix and distributed in a dendritic form, and are distributed in a granular form.

6. High hardness, high strength steel according to claim 5The microcrystalline glass with high hardness, high strength and high transparency is characterized in that the melting point of the microcrystalline glass with high hardness, high strength and high transparency is 1590-1610 ℃; the density is 2.85 to 1.28g/cm³(ii) a The thermal expansion coefficient is 72.8 multiplied by 10 under the temperature condition of 0-50 DEG C^-7～71.8×10^-7/° c; the thermal expansion coefficient is 71.6 multiplied by 10 under the temperature condition of 10-700 DEG C^-7～74.1×10^-7/° c; the visible light transmittance is more than or equal to 92.0 percent when the thickness is 0.7 mm; the Vickers hardness HV of the plate glass is (821-898) + -20 kg/mm under a load of 100g²(ii) a The Mohs hardness is 6.5-7.0; the elastic modulus is (9.2 +/-0.1) multiplied by 10⁵kg/cm²。

7. The use of the high-hardness, high-strength and high-transparency crystallized glass according to claim 5 or 6, wherein: the microcrystalline glass with high hardness, high strength and high transparency is used for preparing the high-strength wear-resistant transparent microcrystalline glass glaze.

8. The application of claim 7, wherein the process flow is as follows: material preparation → mixing → melting → cooling → pressing into thin sheet molding → crushing → ball milling and screening, wherein the melting adopts an electric melting furnace or a total oxygen natural gas pool furnace, the cooling temperature is 1440-1480 ℃, and the mesh number after ball milling and screening is 60-100; the glazed wear resistance of a finished ceramic tile product made of the high-strength wear-resistant transparent microcrystalline glass glaze is 1500 revolutions, the finished ceramic tile product is classified into 4 grades, and the Mohs hardness is 5.4-5.7.

9. The use of the high-hardness, high-strength and high-transparency crystallized glass according to claim 5 or 6, wherein: the microcrystalline glass with high hardness, high strength and high transparency is used for preparing the mobile phone panel.

10. The application of claim 9, wherein the process flow comprises: material preparation → mixing → melting → cooling → overflow method forming or float forming → annealing treatment → heat treatment, wherein the melting adopts an electric melting furnace or a total oxygen natural gas tank furnace, the cooling temperature is 1420-1460 ℃, the annealing treatment temperature is 680 ℃, and the time is 1 h; the Mohs hardness of the mobile phone panel is 6.5-7.2, and the mobile phone panel is not broken after being impacted by a steel ball which is 150g in weight and freely falls from 750mm high altitude when the thickness is 0.6-0.7 mm.

Technical Field

The invention belongs to the technical field of microcrystalline glass, and relates to microcrystalline glass with high hardness, high strength and high transparency, and a preparation method and application thereof.

Background

The microcrystalline glass has a wide variety, glass products with different purposes can be produced by different component proportions and different processes, and most of the microcrystalline glass disclosed in the prior art is architectural decorative materials, biological materials, artware or small heating products and the like. The microcrystalline glass used for the product in the prior art generally has higher strength and hardness, and the problem that the wear-resistant glass glaze, the mobile phone panel and the like cannot be prepared by processing and forming due to higher melting point generally exists.

Therefore, the research on the high-hardness, high-strength and high-transparency glass ceramics capable of being processed and molded to prepare the wear-resistant glass glaze and the mobile phone panel and the preparation method thereof have very important significance.

Disclosure of Invention

The invention aims to solve the problem that the microcrystalline glass in the prior art cannot be processed and molded to prepare the wear-resistant glass glaze and the mobile phone panel due to high melting point, and provides the microcrystalline glass with low melting point, high hardness, high strength and high transparency, and the preparation method and the application thereof.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a preparation method of microcrystalline glass with high hardness, high strength and high transparency comprises the steps of casting a mixture into glass and then carrying out crystallization treatment to obtain the microcrystalline glass, wherein the mixture mainly comprises 1.0-3.2% of Li in percentage by weight₂O、0.5～3.5％Al₂O₃、50.0～65.0％SiO₂、0.2～4.5％CaO、1.0～6.0％SrO、1.0～9.1％ZnO、2.0～8.0％BaO、0.0～2.5％K₂O、3.0～9.7％Na₂O、4.0～15.0％ZrO₂、0.3～0.6％Sb₂O₃And 0.3-0.6% NaCl.

Li₂O、Al₂O₃And SiO₂Passing crystalThe chemical treatment can generate spodumene crystals and endow the microcrystalline glass with high strength characteristic; MgO, ZnO and Al₂O₃And SiO₂The crystallization treatment can generate spinel crystal, ZrO₂Cubic zirconia crystals can be generated through crystallization treatment, and high hardness is endowed to the microcrystalline glass; k₂O and Na₂The introduction of O ensures that the melting point of the microcrystalline glass is lower and the forming performance is better; the introduction of CaO plays a role in adjusting the material property length; the introduction of SrO and BaO improves the transparency and the refractive index of the glass; sb₂O₃And NaCl are introduced to clarify the glass-ceramic.

It is particularly important to note that Li is currently also present₂O、Al₂O₃And SiO₂Of the microcrystalline glass₂Is generally not more than 3% by weight, since ZrO₂The invention forms eutectic in the melting process by reasonably designing the components and the content thereof, thereby avoiding introducing a large amount of ZrO₂Due to the introduction of a large amount of ZrO₂Therefore, the hardness of the microcrystalline glass is obviously improved.

In addition, in the prior art, the color of the microcrystalline glass of the single pure lithium-aluminum-silicon system is light yellow to brown, various microcrystalline crystals can be generated in the crystallization process by reasonably designing the components and the content thereof, and the size and uniformity of crystal particles are proper, so that the whiteness and the transparency of the microcrystalline glass are greatly improved.

As a preferred technical scheme:

the preparation method of the microcrystalline glass with high hardness, high strength and high transparency comprises the following casting processes: the mixture is melted for 8-9 hours at 1600-1630 ℃, and then poured or pressed for molding, wherein the casting temperature and time can be properly adjusted, but are not too small, otherwise the mixture is easily melted unevenly, and the microcrystalline glass is easily broken due to stress.

According to the preparation method of the microcrystalline glass with high hardness, high strength and high transparency, crystallization treatment is divided into two stages, wherein the temperature of the first stage is 670-690 ℃, and the time is 3-5 hours; the temperature of the second stage is 930-950 ℃, and the time is 2-3 h.

According to the preparation method of the microcrystalline glass with high hardness, high strength and high transparency, annealing treatment is carried out after crystallization treatment, the annealing treatment temperature is 670-690 ℃, the annealing treatment time is 3-5 hours, and the annealing treatment aims at eliminating the structural stress of the product.

The invention also provides the high-hardness, high-strength and high-transparency glass ceramics prepared by the preparation method of the high-hardness, high-strength and high-transparency glass ceramics, which mainly comprises a glass matrix, and spodumene crystals (the shape of which is regulated and controlled by controlling the temperature and time of crystallization treatment) which are distributed in a dendritic manner, spinel crystals which are distributed in a granular manner and cubic zirconium oxide crystals which are distributed in a granular manner, which are dispersed in the glass matrix. The spodumene crystal has the characteristics of high strength, the spinel crystal and the cubic zirconia crystal have the characteristics of high hardness, the microcrystalline glass has the characteristics of high strength and high hardness due to the existence of various crystals, and the transparency of the microcrystalline glass can be improved by controlling the particle size and the uniformity of the various crystals.

As a preferred technical scheme:

the microcrystalline glass with high hardness, high strength and high transparency has a melting point of 1590-1630 ℃; the density is 2.85 to 3.28g/cm³(ii) a The thermal expansion coefficient is 72.8 multiplied by 10 under the temperature condition of 0-50 DEG C^-7～73.8×10^-7V deg.C (i.e., the coefficient of thermal expansion of the glass-ceramic is measured by heating it from 0 deg.C to 50 deg.C); the thermal expansion coefficient is 73.6 multiplied by 10 under the temperature condition of 30-700 DEG C^-7～74.3×10^-7V. (i.e. the coefficient of thermal expansion of the glass-ceramic is measured by heating it from 30 ℃ to 700 ℃); the visible light transmittance is more than or equal to 92.0% when the thickness is 0.7mm (the wavelength of visible light is 400-800 nm, the prior art including Japan steppe and Germany Schottky microcrystalline glass can not reach the level, and the higher visible light transmittance provides guarantee for the subsequent color spraying, the brightness of a coating film and the transmission of signals); plate glass loaded with 100gThe Vickers hardness HV is (823-898) + -20 kg/mm²(ii) a The Mohs hardness is 6.5-7.0; the elastic modulus is (9.2 +/-0.1) multiplied by 10⁵kg/cm²。

The invention provides application of the microcrystalline glass with high hardness, high strength and high transparency, and the microcrystalline glass with high hardness, high strength and high transparency is used for preparing high-strength wear-resistant transparent microcrystalline glass glaze.

As a preferred technical scheme:

the application comprises the following process flows: mixing → cooling → pressing into thin sheets → crushing → ball milling and screening → inspection → packaging → warehousing, wherein the melting adopts an electric melting furnace or a total oxygen natural gas pool furnace, the cooling temperature is 1440-1480 ℃, and the mesh number after ball milling and screening is 60-100; the glazed wear resistance of a finished ceramic tile product made of the high-strength wear-resistant transparent microcrystalline glass glaze is 1500 revolutions, the finished ceramic tile product is classified into 4 grades, and the Mohs hardness is 5.4-5.7.

The invention also provides another application of the microcrystalline glass with high hardness, high strength and high transparency, and the microcrystalline glass with high hardness, high strength and high transparency is used for preparing a mobile phone panel.

As a preferred technical scheme:

the application comprises the following process flows: batching → mixing → melting → cooling → overflow method forming or float forming → annealing treatment → heat treatment → inspection → packaging → warehousing, wherein the melting adopts an electric melting furnace or a total oxygen natural gas pool furnace, the cooling temperature is 1420-1460 ℃, the annealing treatment temperature is 680 ℃, and the time is 1 h; the Mohs hardness of the mobile phone panel is 6.5-7.2, and the mobile phone panel is not broken after being impacted by a steel ball which is 150g in weight and freely falls from 750mm high altitude when the thickness is 0.6-0.7 mm.

The classified wear-resisting grade of the existing ceramic tile products can only reach 2-3 grades, the Mohs hardness can only reach about 4, the microcrystalline glass provided by the invention has high hardness, high strength and high transparency, the problem that the ceramic tile cannot be used in large-scale public places due to poor wear resistance is solved when the microcrystalline glass is used for preparing glass glaze, the high-temperature fluidity of the microcrystalline glass is good, the glazed surface of the ceramic tile is flat and bubble-free, and the crystallization transparency is high.

The microcrystalline glass with high hardness, high strength and high transparency is also an optimal material for manufacturing a mobile phone panel, the best mobile phone panel glass in the market at present is GG6 of American Corning, the glass comprises high-alumina glass, and the Vickers hardness of the tempered glass is 640-700 kg/mm²The Mohs hardness is 5.6-6.0, and the performance of the glass ceramics of the invention is superior to that of high alumina glass.

Has the advantages that:

(1) the preparation method of the microcrystalline glass with high hardness, high strength and high transparency is simple and easy to implement and has great popularization value;

(2) the microcrystalline glass with high hardness, high strength and high transparency has a lower melting point and excellent forming and processing properties;

(3) the microcrystalline glass with high hardness, high strength and high transparency can be used for preparing glass glaze and mobile phone panels.

Detailed Description

The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.