WO2016078473A1 - 高硬度透明微晶玻璃及其制备方法 - Google Patents

高硬度透明微晶玻璃及其制备方法 Download PDF

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WO2016078473A1
WO2016078473A1 PCT/CN2015/090236 CN2015090236W WO2016078473A1 WO 2016078473 A1 WO2016078473 A1 WO 2016078473A1 CN 2015090236 W CN2015090236 W CN 2015090236W WO 2016078473 A1 WO2016078473 A1 WO 2016078473A1
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glass
temperature
hardness
transparent glass
raw material
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PCT/CN2015/090236
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English (en)
French (fr)
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原保平
于天来
苏学剑
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成都光明光电股份有限公司
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Priority to US15/514,023 priority Critical patent/US10252939B2/en
Priority to JP2017517051A priority patent/JP6546276B2/ja
Publication of WO2016078473A1 publication Critical patent/WO2016078473A1/zh

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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
    • C03C10/0036—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 a divalent metal oxide as main constituents
    • C03C10/0045—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 a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties

Definitions

  • the invention relates to a high hardness transparent glass ceramic and a preparation method thereof, and belongs to the technical field of glass ceramics.
  • the cover plate is an indispensable protective component, and the glass cover plate gradually becomes the mainstream of the cover plate due to its high permeability and strong scratch resistance.
  • the high alumina silicate cover glass on the market generally has a Mohs hardness value of 6, and the glass component of the hardness is assembled on a mobile phone, a flat panel, a touch notebook, and the gravel or dust contains silicon dioxide (SiO 2 , Mohs hardness 7H), when it rubs into the smart phone cover glass, it is easy to produce scratches and minor damage, which not only shortens the service life of the equipment, but also increases the maintenance cost.
  • sapphire glass which has a Mohs hardness of 9H.
  • the Mohs hardness is 7H, which can resist the abrasion caused by the gravel.
  • Sapphire has better impact resistance than glass, but sapphire glass is more than about 10 times more expensive than aluminosilicate glass, and consumes about 100 times more energy.
  • the visible light transmittance of 1mm sapphire is 80%.
  • the relatively low transmission rate means shortening the battery life and having the disadvantages of being fragile.
  • Glass-ceramic is a multi-phase solid material containing a large amount of microcrystals obtained by controlling the crystallization of glass during heat treatment. It has the advantages of high transparency of glass and good mechanical properties of ceramics, and provides a glass for improving hardness. Effective Ways.
  • the technical problem to be solved by the present invention is to provide a high-hardness transparent glass ceramic.
  • the invention also provides a preparation method of the above high hardness transparent glass ceramic.
  • the technical solution adopted by the invention solves the technical problem: high hardness transparent glass ceramics, the weight percentage composition thereof comprises: SiO 2 55.0-70.0%; Al 2 O 3 15.0-20.0%; MgO 0-10.0%; ZnO 0- 12.5%, and it must contain one of MgO or ZnO, the crystallized glass of which contains crystallites of spinel crystals.
  • MgO is 4-10.0% and/or ZnO is 4-12.5%.
  • the glass has a Mohs hardness of >7, and a visible light transmittance of 1 mm is greater than 80%.
  • a method for preparing a high hardness transparent glass ceramic comprising the steps of:
  • the precursor glass raw material is put into a melting furnace, melted and clarified at a high temperature, and the precursor glass raw material is dissolved into a high temperature glass stock solution, and bubbles and foreign matter in the high temperature glass stock solution are removed;
  • the molten high temperature glass stock solution is formed at a certain furnace temperature, and then subjected to rough annealing;
  • the rough-annealed glass is placed in a high-temperature furnace for heat treatment, and after completion of the heat treatment, crystallites of spinel crystals can be formed in the glass to obtain the high-hardness glass ceramic of the present invention.
  • the melting in the step (b) is at a temperature of 1550 to 1600 ° C for 4 to 8 hours; the clarification is at a temperature of 1600 to 1650 ° C for 4 to 10 hours.
  • the tapping temperature in the step (c) is 1500-1600 ° C; the molding is formed by cooling in a hot mold, or by a float method or a press molding method.
  • the hot mold is such that the mold temperature is ensured to be 100-200 ° C during the molding process; the cooling is that the high temperature glass liquid is poured into the mold, and the preheating mold is subjected to blow cooling.
  • the heat treatment described in the step (d) includes two stages of crystal nucleation and crystal growth; the temperature required for the nucleation stage is 650-800 ° C, and the duration is 1-4 h; The required temperature for the stage is 850-1000 ° C and the duration is 0.5-4 h.
  • the beneficial effects of the invention are: heat treatment using a suitable precursor glass, from the glass base Crystallization of crystallites in the body to prepare high transparent high hardness glass ceramics, the preparation process of the invention is simple, low cost, suitable for large-scale production; the Mohs hardness of the high hardness transparent glass ceramics of the invention is >7, The visible light transmittance of the glass of 1 mm is more than 80%, and the physicochemical property of the glass is high and the hardness of the ceramic is high; the glass ceramic of the invention has high mechanical strength, high thermal stability, good chemical stability and resistance. Good grinding property, good electrical insulation, good visible light performance and photochemical processing, which overcomes the problem of easy scratching of ordinary optical glass. It can be used on mobile phone protection panels, optical instruments and communication equipment. Protective mirrors, disk substrates, liquid crystal displays. Panel or other optoelectronic protective mirrors, etc.
  • the high hardness transparent glass ceramic of the invention adopts a ZnO (MgO)-Al 2 O 3 -SiO 2 system, and a precursor glass is prepared by a melting process, and the precursor glass is annealed and heat treated to prepare a high hardness glass ceramic.
  • SiO 2 and Al 2 O 3 and MgO or ZnO are main components constituting the glass of the present invention, and according to the MgO (or ZnO)-Al 2 O 3 -SiO 2 phase diagram, in the present invention, the content of SiO 2 is 55.0-70.0. %; Al 2 O 3 content is 15.0-20.0%, MgO content is 0-10.0%, ZnO content is 0-1-2%, and the present invention must contain one component of MgO and ZnO, when MgO and ZnO When the content exceeds this range, other crystals appear in the glass, which lowers the transparency of the glass and does not meet the requirements.
  • the content of the above components may range from magnesium aluminate spinel or/and zinc aluminum spinel crystallites in the glass.
  • the content of MgO is 4-10.0%; and the content of ZnO is 4-12.5%.
  • ZrO 2 , P 2 O 5 and TiO 2 are nucleating agents for crystals in glass. Generally, a variety of nucleating agents are used, which can promote the number of crystal nuclei, and the crystal size is small and uniform after crystallization, and the transmittance is uniform.
  • ZrO 2 has a high melting temperature and the content generally does not exceed 10.0%; if the P 2 O 5 content is excessive, phase separation occurs, generally not exceeding 2.0%; TiO 2 is the main nucleating agent, and the content generally does not exceed 7.0%.
  • the nucleation of the titanate is low in hardness, which affects the hardness of the glass.
  • Sb 2 O 3 and CeO 2 are clarifying agents, and the two are not used at the same time.
  • the content of Sb 2 O 3 is not more than 1.5%, and the excessive amount does not provide clarification; the content of CeO 2 does not exceed 0.5%, and excessively causes the glass to be visible light. The transmission rate has dropped.
  • Na 2 O and K 2 O are cosolvents, which lower the melting temperature and the clarification temperature, but the contents of Na 2 O and K 2 O cannot exceed 2%, and too much may cause the hardness of the glass to decrease.
  • Y 2 O 3 and La 2 O 3 additional additives can slightly lower the glass melting temperature without lowering the glass hardness, but not too much, the content of Y 2 O 3 should not exceed 2.0%, and the content of La 2 O 3 cannot More than 1.0%.
  • the preparation method of the invention comprises the following steps:
  • the content is based on the weight composition of the precursor glass, wherein MgO, Na 2 O, K 2 O is introduced as a carbonate, a nitrate or a sulfate, and the other components are introduced in the form of an oxide. Weigh the raw material according to the weight ratio, pour into the mixer, mix well and use as the precursor glass raw material;
  • the precursor glass raw material is put into a melting furnace, melted and clarified at a high temperature, and the precursor glass raw material is dissolved into a high temperature glass stock solution, and bubbles and foreign matter in the high temperature glass stock solution are removed;
  • the molten high-temperature glass stock solution is formed by cooling in a hot mold at a certain furnace temperature, or is formed by a float method or a press molding method, and the formed glass is roughly annealed in a muffle furnace;
  • the rough-annealed glass is placed in a high-temperature furnace muffle furnace for heat treatment, and after completion of the heat treatment, crystallites of spinel crystals can be formed in the glass to obtain the high-hardness glass ceramic of the present invention.
  • the mixer 7 in the above step (a) may employ a V-shaped mixer.
  • the temperature is melted at a high temperature, the temperature is 1550-1600 ° C, the time is 4-8 h; the clarification is carried out at a high temperature, the temperature is 1600-1650 ° C, and the time is 4-10 h; the melting furnace adopts an electric furnace or a crucible furnace.
  • the hot mold is discharged at a temperature of 1500-1600 ° C; the hot mold means that the mold temperature is maintained at 100-200 ° C during the molding process; cooling means that the high temperature molten glass is poured into the mold, and The preheating mold is subjected to blow cooling; the heat treatment process in the above step (d) includes two stages of crystal nucleation and crystal growth, wherein the temperature required for the nucleation stage is 650-800 ° C, and the duration is 1-4 h. The temperature required for the growth phase of the crystallites is 850-1000 ° C and the duration is 0.5-4 h.
  • the invention adopts a method of heat-treating the precursor glass to crystallize and deposit crystallites from the glass matrix to prepare a high-hardness glass ceramic with a Mohs hardness of >7 or even 7.5 or more.
  • the visible light transmittance of 1mm glass is greater than 80%.
  • the high hardness glass ceramic prepared by the invention has high hardness, high mechanical strength, high thermal stability, good chemical stability, good wear resistance, good electrical insulation, good transparency and photochemical processing.
  • the prepared precursor glass raw material is put into an electric furnace, melted at 1600 ° C for 8 hours, clarified at 1650 ° C for 10 hours, and then the molten glass liquid is discharged at 1600 ° C, and is molded by a mold.
  • the temperature was 200 ° C, and air cooling was performed during molding, and the obtained glass was roughly annealed at 680 ° C in a muffle furnace.
  • the prepared glass is placed in a high-temperature furnace for heat treatment, and the heat treatment process includes two stages of crystal nucleation and crystal growth, wherein the temperature in the muffle furnace is maintained at 750 ° C for 2 h. As many crystal nuclei are produced in the glass, and then the temperature in the muffle furnace is raised to about 950 ° C and enters the growth stage of the crystallites for 2 h to form uniform magnesium aluminate spinel crystallites in the glass.
  • a high-hardness glass-ceramic with a Mohs hardness of 8 and a visible light transmittance of 1 mm glass-ceramic is 80% or more.
  • the prepared precursor glass raw material is put into an electric furnace, melted at 1600 ° C for 4 hours, clarified at 1650 ° C for 4 hours, and then the molten glass liquid is discharged at 1550 ° C, and the glass is obtained by float forming. , rough annealing at 680 ° C in a muffle furnace.
  • the prepared glass is placed in a high temperature furnace for heat treatment, and the heat treatment process includes two stages of crystal nucleation and crystal growth, wherein the temperature in the muffle furnace is maintained at 700 during the nucleation stage. °C, for 4h, to produce as many crystal nuclei as possible in the glass, then increase the temperature in the muffle furnace to about 900 °C and enter the microcrystalline growth stage for 3h to form a uniform magnesium-aluminum spinel in the glass. Stone microcrystals, high-hardness glass-ceramics with a Mohs hardness of 8 are obtained, and the visible light transmittance of 1 mm glass-ceramics is above 80%.
  • the prepared precursor glass raw material is put into an electric furnace, melted at a temperature of 1550 ° C for 8 hours, and clarified at a temperature of 1650 ° C for 8 hours, and then the molten glass liquid is discharged at 1550 ° C, and is formed by a press molding method.
  • the glass was obtained and roughly annealed at 680 ° C in a muffle furnace.
  • the prepared glass is placed in a high-temperature furnace for heat treatment, and the heat treatment process includes two stages of crystal nucleation and crystal growth, wherein the temperature in the muffle furnace is maintained at 700 ° C for 4 hours. As many crystal nuclei are produced in the glass, and then the temperature in the muffle furnace is raised to about 900 ° C and enters the growth stage of the crystallites for 4 h to form uniform magnesium aluminate spinel crystals in the glass.
  • a high-hardness glass-ceramic with a hardness of 8 and a visible light transmittance of 1 mm glass-ceramic is 80% or more.
  • test conditions and steps are the same as in the third embodiment, that is, a uniform magnesium aluminate spinel crystallite can be formed in the glass, and a high hardness glass ceramic having a Mohs hardness of 8 is obtained, and the visible light transmittance of the 1 mm glass ceramic is 80%. the above.
  • test conditions and steps are the same as in the third embodiment, that is, uniform magnesium aluminate spinel and zinc aluminum spinel crystallites can be formed in the glass, and a high hardness glass ceramic having a Mohs hardness of 8 is obtained, and the visible light of the 1 mm crystallized glass is transparent.
  • the rate is over 80%.
  • the prepared precursor glass raw material is put into an electric furnace, melted at 1600 ° C for 8 hours, clarified at 1650 ° C for 8 hours, and then the molten glass liquid is discharged at 1600 ° C, and is molded by a mold.
  • the temperature was 200 ° C, and air cooling was performed during molding, and the produced glass was roughly annealed at 680 ° C in a muffle furnace.
  • the prepared glass is placed in a high-temperature furnace for heat treatment, and the heat treatment process includes two stages of crystal nucleation and crystal growth, wherein the temperature in the muffle furnace is maintained at 800 ° C for 4 hours. As many crystal nuclei are produced in the glass, and then the temperature in the muffle furnace is raised to about 1000 ° C to enter the microcrystalline growth stage for 3 h, and the zinc-aluminum spinel crystallites formed in the glass can be obtained.
  • High-hardness glass-ceramic with a hardness of 8.0, the transmittance of visible light of 1 mm glass is greater than 85%.
  • the prepared precursor glass raw material is put into an electric furnace, melted at 1600 ° C for 8 hours, clarified at 1650 ° C for 8 hours, and then the molten glass liquid is discharged at 1600 ° C, and is molded by a mold.
  • the temperature was 200 ° C, and air cooling was performed during molding, and the produced glass was roughly annealed at 680 ° C in a muffle furnace.
  • the prepared glass is placed in a high-temperature furnace for heat treatment, and the heat treatment process includes two stages of crystal nucleation and crystal growth, wherein the temperature in the muffle furnace is maintained at 750 ° C for 2 h. As many crystal nuclei are produced in the glass, and then the temperature in the muffle furnace is raised to about 950 ° C to enter the microcrystalline growth stage for 1 h, and uniform zinc-aluminum spinel crystallites can be formed in the glass. High-hardness glass-ceramic with a Mohs hardness of 7.5, the transmittance of visible light of 1 mm glass is greater than 80%.
  • the prepared precursor glass raw material is put into an electric furnace, melted at 1600 ° C for 8 hours, and clarified at 1650 ° C for 8 hours, and then the molten glass liquid is discharged at 1550 ° C, and is molded by a mold.
  • the temperature was 100 ° C, and air cooling was performed during molding, and the prepared glass piece was roughly annealed at 680 ° C in a muffle furnace.
  • the prepared glass is placed in a high-temperature furnace for heat treatment, and the heat treatment process includes two stages of crystal nucleation and crystal growth, wherein the temperature in the muffle furnace is maintained at 850 ° C for 2 h. As many crystal nuclei are produced in the glass, and then the temperature in the muffle furnace is raised to about 950 ° C to enter the microcrystalline growth stage for 0.5 h, and uniform zinc-aluminum spinel crystallites can be formed in the glass.
  • a high-hardness glass-ceramic having a Mohs hardness of 7.5 was obtained, and the transmittance of visible light of 1 mm glass was more than 80%.
  • Example 8 Other test conditions and procedures are the same as in Example 8, that is, uniform zinc-aluminum spinel crystallites can be formed in the glass to obtain a high-hardness glass ceramic having a Mohs hardness of 8, and the transmittance of visible light of 1 mm glass is greater than 80%.

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Abstract

一种高硬度透明微晶玻璃及其制备方法。该微晶玻璃重量百分比组成含有：SiO2 55.0-70.0％；Al2O3 15.0-20.0％；MgO 0-10.0％；ZnO 0-12.5％，且其必须含有MgO或ZnO中的一种，其晶化的玻璃中含有尖晶石晶体的微晶。该制备方法采用合适的前驱体玻璃进行热处理，从玻璃基体中晶化析出微晶，制备出的微晶玻璃具有莫氏硬度>7，玻璃1mm可见光透过率大于80％。该微晶玻璃可用于手机保护面板、光学仪器和通信设备上保护镜、磁盘基板、液晶显示器面板或其它光电子器件保护镜等。

Description

高硬度透明微晶玻璃及其制备方法 技术领域
本发明涉及一种高硬度透明微晶玻璃及其制备方法，属于玻璃陶瓷技术领域。
背景技术
在进入以苹果产品为标志的触控时代以来，电容式触摸屏凭借其性能稳定、触感良好等优势，成为手机、平板、触控笔记本等终端的首选。无论何种触控技术，盖板都是必不可少的保护部件，而玻璃盖板由于其高透过性、强防刮性等特性，逐渐成为盖板的主流。
目前市场上的高铝硅酸盐盖板玻璃莫氏硬度值一般在6，该硬度下的玻璃元件装配在手机、平板、触控笔记本上，而砂砾或灰尘中含有二氧化硅(SiO2，莫氏硬度7H)，当其摩擦到智能手机盖板玻璃，就容易产生划痕和细微损伤，这样不仅缩短了设备使用寿命，更提高了维修成本。
为了提高玻璃盖板的硬度，有商家开始关注蓝宝石玻璃，其莫氏硬度在9H。作为盖板材料的莫氏硬度大7H，可以抵挡住砂砾造成的磨损。蓝宝石的冲击耐受力比玻璃强，但是蓝宝石玻璃相比高铝硅酸盐玻璃，其价格超出约10倍，其消耗的能量多出约100倍，1mm蓝宝石的可见光透过率在80％，透过率相对较低，意味要缩短电池寿命，并具有易碎等缺点。
微晶玻璃是玻璃在热处理过程中通过控制玻璃晶化获得的一种含有大量微晶体的多相固体材料，兼有玻璃的透明度高和陶瓷的机械性能好等优点，为玻璃提高硬度提供一个有效途径。
发明内容
本发明所要解决的技术问题是提供一种高硬度透明微晶玻璃。
本发明还要提供一种上述高硬度透明微晶玻璃的制备方法。
本发明解决技术问题所采用的技术方案是：高硬度透明微晶玻璃，其重量百分比组成含有：SiO255.0-70.0％；Al2O315.0-20.0％；MgO 0-10.0％；ZnO 0-12.5％，且其必须含有MgO或ZnO中的一种，其晶化的玻璃中含有尖晶石晶体的微晶。
进一步的，还含有：ZrO20-10.0％；P2O50-2.0％；TiO20-7.0％；Sb2O30-1.5％；CeO20-0.5％；Na2O 0-2.0％；K2O 0-2.0％；Y2O30-2.0％；La2O30-1.0％。
进一步的，其中，MgO 4-10.0％和/或ZnO 4-12.5％。
进一步的，所述玻璃的莫氏硬度>7，1mm可见光透过率大于80％。
高硬度透明微晶玻璃的制备方法，该方法包括以下步骤：
(a)配料
按照重量比例称量原料的重量，倒入混合机中，混合均匀后作为前驱体玻璃原料；
(b)熔炼
将上述前驱体玻璃原料投入到熔炼炉中，在高温下经熔化和澄清，将前驱体玻璃原料溶解为高温玻璃原液，同时去除高温玻璃原液中的气泡和异物；
(c)成型及退火
将熔融好的高温玻璃原液在一定出炉温度下，成型后进行粗退火；
(d)热处理
将上述粗退火后的玻璃放入高温炉里进行热处理，热处理结束后即可在玻璃中生成尖晶石晶体的微晶，获得本发明的高硬度微晶玻璃。
进一步的，步骤(a)所述原料，其中MgO、Na2O、K2O以碳酸盐或硝酸盐或硫酸盐的形式引入，其它组分以氧化物的形式引入。
进一步的，步骤(b)所述熔化为，温度在1550-1600℃，时间在4-8h；所述澄清为，温度在1600-1650℃，时间在4-10h。
进一步的，步骤(c)所述出炉温度为1500-1600℃；所述成型为通过在热模具中冷却下成型，或通过浮法、压型法成型。
进一步的，所述热模具为，在成型过程中保证模具温度在100-200℃；所述冷却为，在高温玻璃液倒入到模具中，要对预热模具进行吹风冷却。
进一步的，步骤(d)所述的热处理包括晶核析出和微晶成长两个阶段；所述晶核析出阶段所需温度为650-800℃，持续时间为1-4h；所述微晶成长阶段所需温度为850-1000℃，持续时间为0.5-4h。
本发明的有益效果是：采用合适的前驱体玻璃进行热处理，从玻璃基 体中晶化析出微晶，制备出高透明高硬度微晶玻璃，本发明的制备过程简单，成本低，适合大规模的生产；本发明的高硬度透明微晶玻璃的莫氏硬度>7，玻璃1mm可见光透过率大于80％，兼有玻璃的透明度高和陶瓷的高硬度的物化性能；本发明的微晶玻璃具有高的机械强度、高的热稳定性、良好的化学稳定性、耐磨性好、电绝缘性好、较好的可见光性能及光化学加工等特点，克服了普通光学玻璃容易划伤的问题，可用手机保护面板、光学仪器和通信设备上保护镜、磁盘基板、液晶显示器面板或其它光电子器件保护镜等。
具体实施方式
本发明的高硬度透明微晶玻璃采用ZnO(MgO)-Al2O3-SiO2系统，通过熔融过程制备出前驱体玻璃，前驱体玻璃经退火和热处理，制备出高硬度微晶玻璃。
SiO2和Al2O3以及MgO或者ZnO是构成本发明的玻璃的主要成分，根据MgO(或ZnO)-Al2O3-SiO2相图，本发明中，SiO2的含量为55.0-70.0％；Al2O3的含量为15.0-20.0％，MgO的含量为0-10.0％，ZnO的含量为0-12.5％，本发明必须含有MgO和ZnO中的一种组分，当MgO和ZnO的含量超出这个范围后，在玻璃中会出现其它晶体，这样会降低玻璃的透明度，达不到要求。以上组分的含量范围可以在玻璃中形成镁铝尖晶石或/和锌铝尖晶石微晶。优选的，MgO的含量为4-10.0％；ZnO的含量为4-12.5％。
ZrO2、P2O5和TiO2为玻璃中晶体的成核剂，一般会使用多种成核剂，这样可以促使晶核数量多，晶化后晶体尺寸小而均匀，透过率均匀。ZrO2熔化温度高，含量一般不超过10.0％；P2O5含量过多会出现分相，一般不超过2.0％；TiO2为主要成核剂，含量一般不超过7.0％，含量过多时，成核形成的钛酸盐硬度低，会影响玻璃的硬度。
Sb2O3和CeO2为澄清剂，两者不同时使用，Sb2O3含量不超过1.5％，过多起不到澄清作用；CeO2含量不超过0.5％，过多会导致玻璃在可见光透过率下降。
Na2O和K2O为助溶剂，降低熔化温度和澄清温度，但是Na2O、K2O的含量都不能超过2％，过多会导致玻璃的硬度下降。
Y2O3和La2O3额外添加剂，在不降低玻璃硬度前提下，可以稍微降低玻璃熔化温度，但是不能太多，Y2O3的含量不能超过2.0％，La2O3的含量不能超过1.0％。
本发明的制备方法包括以下步骤：
(a)配料
根据前驱体玻璃的重量组成含量，其中MgO、Na2O、K2O以碳酸盐、硝酸盐或硫酸盐引入，其它组分以氧化物形式引入。按照重量比例，称量原料的重量，倒入混合机中，混合均匀后作为前驱体玻璃原料；
(b)熔炼
将上述前驱体玻璃原料投入到熔炼炉中，在高温下经熔化和澄清，将前驱体玻璃原料溶解为高温玻璃原液，同时去除高温玻璃原液中的气泡和异物；
(c)成型及退火
将熔融好的高温玻璃原液在一定出炉温度下，通过热模具中冷却下成型，或通过浮法、压型法成型，成型好的玻璃在马弗炉中粗退火；
(d)热处理
将上述粗退火的玻璃放入高温炉马弗炉里进行热处理，热处理结束后即可在玻璃中生成尖晶石晶体的微晶，获得本发明的高硬度微晶玻璃。
上述步骤(a)中的混合机7可采用V形混合机。上述步骤(b)中高温下熔化，温度在1550-1600℃，时间在4-8h；高温下澄清，温度在1600-1650℃，时间在4-10h；所述熔炼炉采用电炉或坩埚炉。上述步骤(c)中热模具出炉温度为1500-1600℃；热模具是指，在成型过程中保证模具温度在100-200℃；冷却是指，在高温玻璃液倒入到模具中，要对预热模具进行吹风冷却；上述步骤(d)中的热处理过程包括晶核析出和微晶成长两个阶段，其中，晶核析出阶段所需的温度为650-800℃，持续时间为1-4h；微晶成长阶段所需的温度为850-1000℃，持续时间为0.5-4h。
本发明采用对成前驱玻璃再进行热处理，从玻璃基体中晶化析出微晶方法，制备出高硬度的微晶玻璃，莫氏硬度>7，甚至可以达到7.5以上， 1mm玻璃可见光透过率大于80％。本发明制备的高硬度微晶玻璃具有高硬度、高的机械强度、高的热稳定性、良好的化学稳定性、耐磨性好、电绝缘性好、较好的透明性及能光化学加工等特点，可用手机保护面板、光学仪器和通信设备上保护镜、磁盘基板、液晶显示器面板等。
实施例1：
首先按照重量比将62％的SiO2、18％的Al2O3、10％的MgO以及5％的TiO2、3％的ZrO2、0.5％的P2O5和1.5％的澄清剂Sb2O3称量出来，然后将其全部放入V形混合机充分搅拌混合后作为前驱体玻璃原料。
接着将配制好的前驱体玻璃原料投入电炉内，在1600℃温度下进行熔化8小时，在1650℃温度下进行澄清10小时，然后将熔融好的玻璃液在1600℃出炉，通过模具成型，模具温度在200℃，成型时进行吹风冷却，制得的玻璃在马弗炉680℃粗退火。
将制得的玻璃放入高温炉内进行热处理，该热处理过程包括晶核析出和微晶成长两个阶段，其中晶核析出阶段中，使马弗炉内的温度保持在750℃，持续2h使玻璃中产生尽可能多晶核，接着将马弗炉内的温度升高到950℃左右进入到微晶成长阶段并持续2h，即可在玻璃中生成均一的镁铝尖晶石微晶，获得莫氏硬度为8的高硬度微晶玻璃，1mm微晶玻璃可见光透过率在80％以上。
实施例2：
首先按照重量比将60％的SiO2、20％的Al2O3、8％的MgO、1％的K2O、1％的Na2O、5％的TiO2、3％的ZrO2、0.5％的P2O5和1.5％的澄清剂Sb2O3称量出来，然后将其全部放入混合机充分搅拌混合后作为前驱体玻璃原料；
接着将配制好的前驱体玻璃原料投入电炉内，在1600℃温度下熔化4小时，在1650℃温度下澄清4小时，然后将熔融好的玻璃液在1550℃出炉，通过浮法成型制得玻璃，在马弗炉680℃粗退火。
将制得的玻璃放入高温炉内进行热处理，该热处理过程包括晶核析出和微晶成长两个阶段，其中晶核析出阶段中，使马弗炉内的温度保持在700 ℃，持续4h使玻璃中产生尽可能多晶核，接着将马弗炉内的温度升高到900℃左右进入到微晶成长阶段并持续3h，即可在玻璃中生成均一的镁铝尖晶石微晶，获得莫氏硬度为8的高硬度微晶玻璃，1mm微晶玻璃可见光透过率在80％以上。
实施例3：
首先按照重量比将55％的SiO2、20％的Al2O3、10％的MgO、2％的K2O、7％的TiO2、5.5％的ZrO2和0.5％的澄清剂Sb2O3称量出来，然后将其全部放入混合机充分搅拌混合后作为前驱体玻璃原料；
接着将配制好的前驱体玻璃原料投入电炉内，在1550℃温度下进行熔化8小时，在1650℃温度下进行澄清8小时，然后将熔融好的玻璃液在1550℃出炉，通过压型法成型制得玻璃，在马弗炉680℃粗退火。
将制得的玻璃放入高温炉内进行热处理，该热处理过程包括晶核析出和微晶成长两个阶段，其中晶核析出阶段中，使马弗炉内的温度保持在700℃，持续4h使玻璃中产生尽可能多晶核，接着将马弗炉内的温度升高到900℃左右进入到微晶成长阶段并持续4h，即可在玻璃生成均一的镁铝尖晶石微晶，获得莫氏硬度为8的高硬度微晶玻璃，1mm微晶玻璃可见光透过率在80％以上。
实施例4：
首先按照重量比将65％的SiO2、15％的Al2O3、10％的MgO、2％的Na2O、5％的TiO2、1％的ZrO2、0.5％的P2O5和1.5％的澄清剂Sb2O3称量出来，然后将其全部放入混合机充分搅拌混合后作为前驱体玻璃原料；
其它试验条件和步骤同实施例3，即可在玻璃中生成均一的镁铝尖晶石微晶，获得莫氏硬度为8的高硬度微晶玻璃，1mm微晶玻璃可见光透过率在80％以上。
实施例5：
首先按照重量比将62％的SiO2、20％的Al2O3、4％的MgO、4％的ZnO、1％ 的K2O、1％的Na2O、5％的TiO2、1％的ZrO2、0.5％的P2O5和1.5％的Sb2O3称量出来，然后将其全部放入混合机充分搅拌混合后作为前驱体玻璃原料；
其它试验条件和步骤同实施例3，即可在玻璃中生成均一的镁铝尖晶石和锌铝尖晶石微晶，获得莫氏硬度为8的高硬度微晶玻璃，1mm微晶玻璃可见光透过率在80％以上。
实施例6：
首先按照重量比将65.0％的SiO2、16.0％的Al2O3、12.5％的ZnO、6.0％的ZrO2和0.5％的Sb2O3称量出来，然后将其全部放入混合机充分搅拌混合后作为前驱体玻璃原料；
接着将配制好的前驱体玻璃原料投入电炉内，在1600℃温度下进行熔化8小时，在1650℃温度下进行澄清8小时，然后将熔融好的玻璃液在1600℃出炉，通过模具成型，模具温度在200℃，成型时进行吹风冷却，制的玻璃在马弗炉680℃粗退火。
将制得的玻璃放入高温炉内进行热处理，该热处理过程包括晶核析出和微晶成长两个阶段，其中晶核析出阶段中，使马弗炉内的温度保持在800℃，持续4h使玻璃中产生尽可能多晶核，接着将马弗炉内的温度升高到1000℃左右进入到微晶成长阶段并持续3h，即可在玻璃中生成的锌铝尖晶石微晶，获得莫氏硬度为8.0的高硬度微晶玻璃，1mm玻璃可见光的透过率大于85％。
实施例7：
首先按照重量比将60.5％的SiO2、16％的Al2O3、12.5％的ZnO、2.0％的Y2O3、1.0％的La2O3、1.0％的Na2O、0.5％的K2O、6.0％的ZrO2和0.5％的CeO2称量出来，然后将其全部放入混合机充分搅拌混合后作为前驱体玻璃原料；
接着将配制好的前驱体玻璃原料投入电炉内，在1600℃温度下进行熔化8小时，在1650℃温度下进行澄清8小时，然后将熔融好的玻璃液在1600℃出炉，通过模具成型，模具温度在200℃，成型时进行吹风冷却，制的玻璃在马弗炉680℃粗退火。
将制得的玻璃放入高温炉内进行热处理，该热处理过程包括晶核析出和微晶成长两个阶段，其中晶核析出阶段中，使马弗炉内的温度保持在750℃，持续2h使玻璃中产生尽可能多晶核，接着将马弗炉内的温度升高到950℃左右进入到微晶成长阶段并持续1h，即可在玻璃中生成均一的锌铝尖晶石微晶，获得莫氏硬度为7.5的高硬度微晶玻璃，1mm玻璃可见光的透过率大于80％。
实施例8：
首先按照重量比将60％的SiO2、17.5％的Al2O3、12.5％的ZnO、2％的Y2O3、1％的La2O3、0.3％的Na2O、0.2％的K2O、6.0％的ZrO2和0.5％的CeO2称量出来，然后将其全部放入混合机充分搅拌混合后作为前驱体玻璃原料；
接着将配制好的前驱体玻璃原料投入电炉内，在1600℃温度下进行熔化8小时，在1650℃温度下进行澄清8小时，然后将熔融好的玻璃液在1550℃出炉，通过模具成型，模具温度在100℃，成型时进行吹风冷却，制的玻璃片在马弗炉680℃粗退火。
将制得的玻璃放入高温炉内进行热处理，该热处理过程包括晶核析出和微晶成长两个阶段，其中晶核析出阶段中，使马弗炉内的温度保持在850℃，持续2h使玻璃中产生尽可能多晶核，接着将马弗炉内的温度升高到950℃左右进入到微晶成长阶段并持续0.5h，即可在玻璃中生成均一的锌铝尖晶石微晶，获得莫氏硬度为7.5的高硬度微晶玻璃，1mm玻璃可见光的透过率大于80％。
实施例9：
首先按照重量比将62％的SiO2、16％的Al2O3、12.3％的ZnO、2％的Y2O3、1％的La2O3、0.1％的Na2O、0.1％的K2O、6.0％的ZrO2和0.5％的CeO2称量出来，然后将其全部放入混合机充分搅拌混合后作为前驱体玻璃原料；
其它试验条件和步骤同实施例8，即可在玻璃中生成均一的锌铝尖晶石微晶，获得莫氏硬度为8的高硬度微晶玻璃，1mm玻璃可见光的透过率大于80％。

Claims (10)

  1. 高硬度透明微晶玻璃，其特征在于：其重量百分比组成含有：SiO255.0-70.0％；Al2O3 15.0-20.0％；MgO 0-10.0％；ZnO 0-12.5％，且其必须含有MgO或ZnO中的一种，其晶化的玻璃中含有尖晶石晶体的微晶。
  2. 如权利要求1所述的高硬度透明微晶玻璃，其特征在于：还含有：ZrO2 0-10.0％；P2O5 0-2.0％；TiO2 0-7.0％；Sb2O3 0-1.5％；CeO2 0-0.5％；Na2O 0-2.0％；K2O 0-2.0％；Y2O3 0-2.0％；La2O3 0-1.0％。
  3. 如权利要求1或2所述的高硬度透明微晶玻璃，其特征在于：其中，MgO 4-10.0％和/或ZnO 4-12.5％。
  4. 如权利要求1或2所述的高硬度透明微晶玻璃，其特征在于：所述玻璃的莫氏硬度>7，1mm可见光透过率大于80％。
  5. 高硬度透明微晶玻璃的制备方法，其特征在于：该方法包括以下步骤：
    (a)配料
    按照重量比例称量原料的重量，倒入混合机中，混合均匀后作为前驱体玻璃原料；
    (b)熔炼
    将上述前驱体玻璃原料投入到熔炼炉中，在高温下经熔化和澄清，将前驱体玻璃原料溶解为高温玻璃原液，同时去除高温玻璃原液中的气泡和异物；
    (c)成型及退火
    将熔融好的高温玻璃原液在一定出炉温度下，成型后进行粗退火；
    (d)热处理
    将上述粗退火后的玻璃放入高温炉里进行热处理，热处理结束后即可在玻璃中生成尖晶石晶体的微晶，获得本发明的高硬度微晶玻璃。
  6. 如权利要求5所述的高硬度透明微晶玻璃的制备方法，其特征在于：步骤(a)所述原料，其中MgO、Na2O、K2O以碳酸盐或硝酸盐或硫酸盐的形 式引入，其它组分以氧化物的形式引入。
  7. 如权利要求5所述的高硬度透明微晶玻璃的制备方法，其特征在于：步骤(b)所述熔化为，温度在1550-1600℃，时间在4-8h；所述澄清为，温度在1600-1650℃，时间在4-10h。
  8. 如权利要求5所述的高硬度透明微晶玻璃的制备方法，其特征在于：步骤(c)所述出炉温度为1500-1600℃；所述成型为通过在热模具中冷却下成型，或通过浮法、压型法成型。
  9. 如权利要求8所述的高硬度透明微晶玻璃的制备方法，其特征在于：所述热模具为，在成型过程中保证模具温度在100-200℃；所述冷却为，在高温玻璃液倒入到模具中，要对预热模具进行吹风冷却。
  10. 如权利要求5所述的高硬度透明微晶玻璃的制备方法，其特征在于：步骤(d)所述的热处理包括晶核析出和微晶成长两个阶段；所述晶核析出阶段所需温度为650-800℃，持续时间为1-4h；所述微晶成长阶段所需温度为850-1000℃，持续时间为0.5-4h。
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