WO2021249032A1 - 一种具有深层高压应力的强化微晶玻璃及其制备方法 - Google Patents

一种具有深层高压应力的强化微晶玻璃及其制备方法 Download PDF

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WO2021249032A1
WO2021249032A1 PCT/CN2021/088650 CN2021088650W WO2021249032A1 WO 2021249032 A1 WO2021249032 A1 WO 2021249032A1 CN 2021088650 W CN2021088650 W CN 2021088650W WO 2021249032 A1 WO2021249032 A1 WO 2021249032A1
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glass
compressive stress
ceramics
deep
stress
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PCT/CN2021/088650
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English (en)
French (fr)
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王键
林美灵
张熊熊
黄小杰
洪立昕
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科立视材料科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C03B25/02—Annealing glass products in a discontinuous way
    • 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
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • 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

Definitions

  • the invention relates to the field of glass-ceramics, in particular to a strengthened glass-ceramics with deep high-pressure stress and a preparation method thereof.
  • the glass cover protection screen used for smart phones has been upgraded from the conventional one-step strengthening to the lithium-aluminum-silicon secondary strengthening in order to improve the anti-drop performance.
  • the lithium-aluminum-silicon secondary strengthened glass contains lithium element, which can carry out Na-Li (first step) and K-Na (second step) ion exchange, with high surface compressive stress (CS) and deep stress layer (DOL) ), which can improve the impact resistance of glass to a certain extent, especially in terms of resistance to the impact of flat objects.
  • CS surface compressive stress
  • DOL deep stress layer
  • the strengthening effect of lithium aluminum silicate glass is affected by the nature of the bulk glass and the strengthening process.
  • the nature of the bulk glass determines the limit value of CT (central tensile stress).
  • CT central tensile stress
  • the actual value of CT is related to CS and DOL.
  • CS and DOL increase, CT also increases at the same time.
  • the actual CT value of the glass is close to or greater than the CT limit value, the glass will break.
  • the secondary strengthened lithium aluminum silicate glass has a relatively large CT value, and the glass is prone to breakage in the strengthening experiment of increasing the deep lamination stress value.
  • the method used to improve the deep lamination stress is low temperature and long time ion exchange, which takes a long time and increases production cost.
  • Another method is to increase the diffusion rate by increasing the intensity of temperature to reduce the exchange time, but due to the existence of the stress relaxation phenomenon, the applicable temperature cannot be too high. Therefore, the effect of increasing the penetration depth of ions by increasing the intensity temperature is limited, and the deep lamination stress is more difficult to increase, which restricts the drop resistance of the lithium aluminum silicon chemically strengthened glass.
  • the inventor introduced microcrystalline particles into the lithium aluminum silicon-based glass.
  • the microcrystalline particles have a higher network structure strength than glass due to the crystalline phase, which can increase the toughness of the glass and increase the maximum CT. Tolerance;
  • the microcrystalline particles are relatively stable at high temperatures, which can reduce the amount of stress relaxation.
  • the inventor took advantage of the particularity of the microcrystalline particle structure, through a certain formula design and heat treatment process, introduced a certain amount of microcrystalline phase into the lithium aluminum silicate glass, and carried out ion exchange under the limited chemical strengthening process conditions to improve the microstructure.
  • the compressive stress value at the deep inner layer of the crystal glass product is obtained to obtain a glass-ceramic product with a high compressive stress value at the inner deep layer.
  • the present invention provides a strengthened glass-ceramic with deep high-pressure stress.
  • the strengthened glass-ceramic product includes two corresponding compressive stress layers; the compressive stress The layers extend inward from the upper and lower surfaces and sequentially include surface compressive stress zones and deep compressive stress zones; the total thickness of the surface compressive stress zones and deep compressive stress zones is 50-100um; the thickness of the surface compressive stress zones is 0- 20um, the stress CS of the surface compressive stress zone is greater than or equal to 800 MPa; in the deep compressive stress zone, the absolute value of the slope of the internal stress distribution is less than 2, CS-30 is greater than or equal to 115 MPa, and CS-50 is greater than or equal to 80 MPa.
  • the thickness t of the glass-ceramics is 0.55mm ⁇ t ⁇ 0.8mm; and the thickness of the compressive stress layer is >0.2t.
  • the thickness of the compressive stress layer is greater than or equal to 0.22t.
  • the stress CS of the surface compressive stress zone is greater than or equal to 850 MPa.
  • CS-50 ⁇ 85MPa Preferably, in the deep compressive stress zone, CS-50 ⁇ 85MPa.
  • the CT value of the strengthened glass-ceramic is -50 ⁇ -90MPa
  • the Vickers hardness is ⁇ 6.50GPa
  • the 4PB test value is >700N/mm 2
  • the single-rod static pressure loss rate of the strengthened glass-ceramic is ⁇ 10%
  • the present invention provides a method for preparing a strengthened glass ceramic with deep high pressure stress according to the first aspect of the present invention, which includes the following steps:
  • First ion exchange Put the basic glass ceramics into the first bath salt for the first ion exchange.
  • the first bath salt is composed of KNO 3 and NaNO 3 , and the Na/K molar ratio in the first bath salt is 1.2 ⁇ 6.7 :1; ion exchange temperature>480°C, exchange time is 3 ⁇ 6h;
  • Secondary ion exchange Put the basic glass ceramics after the first ion exchange into the second bath salt for secondary ion exchange.
  • the composition of the second bath salt is 100wt% KNO 3 or sodium ion molar percentage content ⁇ 10% In the mixture of potassium and sodium ions; the secondary ion exchange temperature is 10-30°C lower than the first ion exchange temperature, and the exchange time is 0.5-2h to obtain a glass-ceramic with deep high-pressure stress.
  • the molar ratio of Na/K needs to be limited; higher potassium content is easy to accumulate on the shallow surface of the glass, which is not conducive to the continuous entry of subsequent ions and affects the depth of the stress layer; too large a sodium content To a certain extent, it will facilitate the Na-Li exchange, increase the depth and deep compressive stress, but at the same time will form a sodium-rich layer on the surface, which affects the chemical stability of the glass.
  • the ion exchange bath salt ratio limits the Na/K molar ratio to 1.2-6.7; the ion exchange temperature is higher than 480°C, in some embodiments, the exchange temperature is higher than 530°C, and the effective exchange time is 3-6 hours.
  • the average transmittance of the basic glass-ceramics at a thickness of 0.75 mm at a light wave band of 380 to 780 nm is> 89%;
  • the preparation of the basic glass-ceramics includes the following steps:
  • Basic glass preparation Weigh and mix the components according to the following mass percentages, and then melt, shape, and anneal to obtain the basic glass;
  • SiO 2 is 55% ⁇ 68%
  • Al 2 O 3 is 18% ⁇ 22%
  • Li 2 O is 4% ⁇ 7%
  • TiO 2 is 0.5% ⁇ 1.8%
  • Na 2 O is 3% ⁇ 6%
  • alkaline earth Metal oxide RO is 0% to 1%
  • B 2 O 3 is 0.5% to 2%
  • P 2 O 5 is 1.5% to 4%
  • ZrO 2 is 1% to 5%
  • clarifying agent is 0.15% to 0.4% ;
  • SiO 2 constitutes the main structure of the basic glass and glass ceramics, and is also the main component of the crystal phase. Too low its content will lead to changes in the composition of the crystal phase, and will also weaken the overall performance of the glass.
  • the content of SiO 2 should not be less than 55wt%. However, a higher SiO 2 content will cause difficulty in melting and molding, and the composition also contains high aluminum and zirconium components.
  • the present invention controls the content of SiO 2 between 55 wt% and 68 wt%.
  • Al 2 O 3 Since Al 2 O 3 has a larger volume than silicon-oxygen tetrahedron in the glass structure, it can provide a strengthening channel for the glass during the ion strengthening process. The higher its content, the better the glass ion strengthening. Its content should not be less than 18wt%; but Al 2 O 3 is an extremely refractory oxide, which can quickly increase the high-temperature viscosity of the glass, which makes it more difficult to clarify and homogenize the glass, and it is difficult to discharge bubble defects, so the content is controlled to be less than 22wt%.
  • Li 2 O can lower the crystallization temperature of glass and promote the crystallization of glass. It is also the main component of ion exchange, which enhances the depth and strength of deep stress. In order to obtain better deep-seated stress, its Li 2 O content should not be less than 4wt%. However, too high Li 2 O is very easy to crystallize, which makes it difficult to control glass crystallizing, and the cost of lithium is higher, which increases production costs. Therefore, the content of Li 2 O in the base glass is controlled not to be higher than 7wt%.
  • TiO 2 is a nucleating agent, which facilitates nucleation and the formation and growth of crystal grains. It can work with Li 2 O to lower the crystallization temperature. Taking into account the Li 2 O content in the composition, the TiO 2 content is controlled within 0.5% to 1.8%.
  • Na 2 O can significantly reduce the viscosity of the base glass and promote the melting and clarification of the base glass.
  • Na ions are also the main participants in ion exchange. Too little Na ion content is not conducive to ion exchange.
  • an increase in the content of Na 2 O will lead to changes in the types of crystalline phases, resulting in a variety of crystals with different properties, making it difficult to control the crystallization process and easily devitrifying or inhomogeneous glass. Therefore, from the perspective of ion exchange, in order to enable the exchange of K + and Na + ions in the glass-ceramics in the later stage, high compressive stress is formed on the glass surface, and the minimum content is not less than 3wt%. From the perspective of crystal phase control , The content of Na 2 O in the base glass should not be higher than 6wt%.
  • the alkaline earth metal oxide RO is contained, and R 2+ can be Mg 2+ , Ca 2+ , Zn 2+ or Ba 2+ , which can improve the chemical stability and mechanical strength of the glass.
  • R 2+ affects the ion diffusion rate, and the larger the diameter, the more significant the effect.
  • the larger ion radius has a certain blocking effect on the alkali ion channel. Therefore, the component content of RO is set to be 0 wt% to 1 wt%. Mg 2+ or Zn 2+ having a smaller ion diameter is more preferable.
  • B 2 O 3 is a network forming body oxide, which can reduce the high-temperature melt viscosity of the glass and improve the melting characteristics. Its proper amount helps to improve ion diffusibility and increase ion exchange capacity. However, B 2 O 3 can cause phase separation. As the content increases, it will affect the transmittance of the glass after crystallization. Excessive content will also destroy the main network structure and reduce the mechanical strength. Therefore, the component content of B 2 O 3 is set at 0.5 wt% to 2 wt%.
  • P 2 O 5 is one of the network forming components of the basic glass. It uses [PO4] tetrahedrons to connect to each other to form a network, which makes the glass network structure loose, and the network gap becomes larger, which is beneficial to the mutual diffusion of ions. Therefore, the content of P 2 O 5 is at least 1.5% by weight. However , if the content of P 2 O 5 is too high, it will cause serious phase separation of the glass and affect the permeability of the glass-ceramic . The content of P 2 O 5 is at most 4 wt%.
  • ZrO 2 helps reduce the size of the crystal grains during the crystallization process, thereby increasing the transmittance of the glass, and can quickly improve the chemical stability of the glass and a certain degree of toughening.
  • ZrO 2 contributes to the stability of the main crystalline phase; if there is no ZrO 2 , it is easy to cause the main crystalline phase to undergo a crystalline transformation, which affects the uniformity and permeability of the glass as a whole. Therefore, the minimum component content of ZrO 2 is not less than 1 wt%.
  • ZrO 2 is a refractory component, which can quickly increase the viscosity of the base glass. Excessive ZrO 2 content will result in the presence of unmelted ZrO 2 in the glass. Therefore, the ZrO 2 content is controlled at 5wt% at most.
  • the glass of the present invention contains chemical clarifiers, which can be decomposed at high temperature during the glass melting process to produce gas during gasification or reduce the viscosity of the glass liquid to promote the elimination of bubbles in the glass liquid or dissolution and absorption , So as to achieve a better melting effect.
  • the clarifying agent does not contain Sb 2 O 3 , preferably one or more of CeO 2 and SnO 2 , and the content of the clarifying agent is controlled within 0.15% to 0.4%.
  • the present invention needs to limit 21% ⁇ P 2 O 5 +Al 2 O 3 -RO ⁇ 24%, 8% ⁇ R 2 O(Li 2 O+Na 2 O ) ⁇ 11%, 0.7% ⁇ Li 2 O/Li 2 O+TiO 2 ⁇ 1%.
  • Microcrystallization heat treatment Put the basic glass into a crystallization furnace, heat it up to the nucleation temperature Tg ⁇ Tg+30°C at 8 ⁇ 12°C/min, keep it for 120 ⁇ 240min, and then heat it up to crystal at 2 ⁇ 5°C/min The temperature is 730 ⁇ 760°C, the temperature is kept for 60 ⁇ 120min, and then the temperature is reduced to Tg-30 ⁇ Tg-20°C at 2 ⁇ 5°C/min, and the temperature is kept for 110 ⁇ 130min. Finally, the temperature is reduced to 550 ⁇ 570°C at 2°C/min. Heat treatment for 30 min, and obtain basic glass-ceramics after cooling.
  • the content of the glass phase in the basic glass-ceramics is 72 wt% to 86 wt%, and the glass phase is composed of lithium aluminum silicate crystal grains with an average crystal grain size of less than 30 nm.
  • the clarifying agent is one or a combination of SnO 2 or CeO 2.
  • the Tg temperature is 624°C to 655°C.
  • the present invention includes at least the following beneficial effects: providing a glass-ceramic product with deep high-pressure stress, which can realize deep-seated glass products under high temperature and strong conditions by introducing microcrystalline phase particles. It has high compressive stress, and no stress relaxation or cracking occurs.
  • the glass product has a surface compressive stress area CS greater than 800MPa within the thickness range of 0.55mm ⁇ t ⁇ 0.8mm, and the absolute value of the stress distribution slope in the deep inner (20-100um) area is less than 2, CS-30 ⁇ 115MPa, CS-50 ⁇ 80MPa high compressive stress value; its stress layer DOC depth is greater than 0.2 times the glass thickness; its CT value is between 50-90MPa, Vickers hardness is greater than 6.50GPa, 4PB test value is greater than 700N/mm 2 , single rod
  • the static pressure loss rate is less than 10%, (prefabricated defects under 500kgf/15s), and the fracture threshold is greater than 5kgf, which greatly improves the related properties of strengthened glass-ceramics.
  • Figure 1 is a schematic longitudinal cross-sectional view of a sample of Example 1-6;
  • Figure 2 is the deep-level stress curve of the sample in Example 2;
  • Figure 3 is a scanning electron microscope (SEM) image of a sample of Example 2;
  • Figure 4 is a graph of the transmittance of the sample in Example 2 from 300nm to 1200nm;
  • Figure 5 is the indentation diagram of the Vickers hardness tester of the sample of Example 2 under 5kgf/15s;
  • Figure 6 is the XRD pattern of the sample in Example 2.
  • Fig. 7 is a graph showing the deep-layer stress distribution curve of the samples of Examples 1-6;
  • Fig. 8 is a box diagram of samples of Examples 1-6 at 30 um and 50 um deep layer stress and better amorphous secondary strengthened glass on the market.
  • Examples 1 to 6 of the present invention were prepared by the following methods:
  • Component weighing and mixing select the corresponding introduced raw materials according to the ratio of each component, SiO 2 is 55% to 68%, Al 2 O 3 is 18% to 22%, and Li 2 O is 4% to 7% , TiO 2 is 0.5% to 1.8%, Na 2 O is 3% to 6%, alkaline earth metal oxide RO is 0% to 1%, B 2 O 3 is 0.5% to 2%, and P 2 O 5 is 1.5% ⁇ 4%, ZrO 2 is 1% ⁇ 5%, clarifying agent is 0.15% ⁇ 0.4%; of which 21% ⁇ P 2 O 5 +Al 2 O 3 -RO ⁇ 24%, 8% ⁇ Li 2 O+Na 2 O ⁇ 11%, 0.7% ⁇ Li 2 O/(Li 2 O+TiO 2 ) ⁇ 1%; weigh and mix according to its purity, moisture and proportion range, and obtain a meltable mixture. See Table 1 for examples of components and mass percentages in Examples 1-6.
  • the homogeneous mixture into a platinum or platinum-rhodium crucible.
  • the casted glass block is put into an annealing furnace at 600-650°C for annealing. After annealing is completed, the furnace is cooled to room temperature and taken out to obtain a basic glass block.
  • the heat treatment process parameters are shown in Table 1.
  • the first stage is heated at 8-12°C/min, and the second stage is heated at 2-5°C/min.
  • the temperature is lowered at 1 to 2°C/min, and in the fourth stage, the temperature is lowered at 2°C/min.
  • After the heat treatment it is cooled in the furnace and the basic glass-ceramics are taken out.
  • Cut, grind and polish the basic glass-ceramic block to form sheet glass A two-step method is adopted for ion exchange. The steps are as follows: place the sheet sample in a 450°C preheating furnace for 30 minutes, and then place the basic glass-ceramics in molten salt twice for ion strengthening (1IOX and 2IOX). The ion strengthening process parameters are shown in Table 1. Place the glass in a muffle furnace to cool quickly.
  • Table 1 Example 1-6 sample composition, process parameters and performance table
  • Tg Glass transition point temperature, measured by DSC.
  • Amorphous content The XRD diffraction peaks are compared with the database pattern to determine the crystalline phase, and the ratio of the crystalline phase diffraction intensity to the overall pattern intensity is calculated by the Rietveld method to obtain the crystallinity and amorphous content.
  • CS-30/CS-50 The compressive stress value at 30/50um (perpendicular to the surface) in the glass-ceramic, tested with SLP-1000 surface stress meter.
  • DOC The depth at which the stress changes from compression to tension in the glass-ceramics, that is, the depth of the stress layer, tested with SLP-1000 surface stress meter.
  • CT Central tensile stress, tested with SLP-1000 surface stress meter.
  • T2 slope value the internal stress distribution slope of the deep compressive stress zone is calculated by using the SLP-1000 surface stress meter to test the stress data.
  • t value thickness of glass-ceramic, measured by electronic vernier caliper.
  • Residual strength use Vickers hardness tester to carry out prefabricated defects under 500kgf/15s, and then carry out single-rod static pressure test by universal testing machine;
  • Fracture threshold measured by a high-pressure Vickers hardness tester, with a loading force of 5kgf and a loading time of 15S.
  • Figure 1 is a schematic diagram of the longitudinal section of the samples of Examples 1-6.
  • the samples of thickness t extend inward from the upper and lower surfaces, and respectively have surface compressive stress areas of thickness t 1 and t 1 ′; and corresponding t 2 and t 2 'deep compressive stress zone thickness; extending interiorly to the total zero stress at a compressive stress layer (DOC) thickness; cross-sectional direction seen nanocrystalline grain distribution in the glass phase;
  • DOC compressive stress layer
  • Figure 2 is the deep-level stress curve of the sample of Example 2, the slope in the range of 20-100um>-2MPa/um, DOC>130um;
  • Figure 3 is a scanning electron microscope (SEM) image of the sample of Example 2.
  • the average size of the crystal grains is less than 30nm, and the crystal grains are filled with glass phase, and the glass phase accounts for 84.2%;
  • Figure 4 is a graph of the transmittance of the sample in Example 2 from 300nm to 1200nm, and its average transmittance is >90% in the visible light band of 380-780nm;
  • Figure 5 is the indentation diagram of the Vickers hardness tester of Example 2 under 5kgf/15s. There are no extension cracks at the four points in the indentation diagram, and it can be seen that the fracture threshold is higher than 5kgf;
  • Figure 6 is the XRD pattern of the sample in Example 2.
  • the diffraction peaks in the figure are not sharp enough, and there are some steamed bread peaks. It can be seen that the crystallization is not complete enough, and the crystallinity is low.
  • the crystalline phase material is compared with the database map as silicic acid.
  • Fig. 7 is a deep-layer stress distribution curve diagram of the samples of Examples 1-6.
  • the slope distribution of the stress curve in the range of 20-100um is relatively close and >-2MPa/um, and its DOC>120um;
  • Figure 8 is a box diagram of the samples of Example 1-6 at 30um and 50um deep layer stress and the better amorphous secondary strengthened glass on the market. It can be seen from Figure 8 that the samples of the example have higher stresses at 30um and 50um. Value, its mean value and large scale range value are more superior.
  • the glass product has a surface compressive stress area CS greater than 800MPa within the thickness range of 0.55mm ⁇ t ⁇ 0.8mm, and the absolute value of the stress distribution slope in the deep inner (20-100um) area is less than 2, CS-30 ⁇ 115MPa, CS-50 ⁇ 80MPa high compressive stress value; its stress layer DOC depth is greater than 0.2 times the glass thickness; its CT value is between 50-90MPa, Vickers hardness is greater than 6.50GPa, 4PB test value is greater than 700N/mm 2 , single rod
  • the static pressure loss rate is less than 10%, (prefabricated defects under 500kgf/15s), and the fracture threshold is greater than 5kgf, which greatly improves the related properties of strengthened glass-ceramics.

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Abstract

一种具有深层高压应力的强化微晶玻璃及其制备方法，包括两个对应的压缩应力层；压缩应力层由上下表面向内延伸，依次包括表面压缩应力区和深层压缩应力区；表面压缩应力区和深层压缩应力区的总厚度为50～100um；表面压缩应力区的厚度为20um，表面压缩应力区的应力CS≥800MPa；深层压缩应力区中，内应力分布斜率的绝对值＜2，CS-30≥115MPa，CS-50≥80MPa，其CT值介于50-90MPa，维氏硬度大于6.50GPa，4PB测试值大于700N/mm 2，单杆静压强度损失率小于10％，断裂阀值大于5kgf。其制备包括两次离子交换步骤。

Description

一种具有深层高压应力的强化微晶玻璃及其制备方法 技术领域
本发明涉及微晶玻璃领域，特别涉及一种具有深层高压应力的强化微晶玻璃及其制备方法。
背景技术
目前，用于智能手机的玻璃盖板保护屏，为提高抗跌落性能，已从常规的一步化强升级到锂铝硅系二次强化。锂铝硅系二次强化玻璃含有锂元素,可进行Na-Li(第一步)及K-Na(第二步)离子交换，具有高表面压缩应力(CS)和较深的应力层(DOL),可一定程度上提升玻璃的抗冲击性能，特别是在抗平整物体冲击方面有很好的表现。但是，在抗尖锐物体冲击性能上，如在粗糙地面上(水泥、砂石等)则很容易破碎。化学强化虽可通过在玻璃的表面处或一定深度的压缩应力层处为裂纹穿透提供一些阻力，但这些阻力较为有限，一旦穿透压缩应力层进入玻璃，就不再有效。因此，为更好的提高玻璃的抗尖锐物体冲击性能，不仅需高表面压缩应力和较深的应力层，还需深层位置处具有较高的压缩应力值。
锂铝硅玻璃的强化效果受本体玻璃性质及化强工艺的影响，本体玻璃性质决定着CT(中心张应力)极限值，CT实际值又与CS和DOL有关，当CS与DOL增大时，CT也同时增大，当玻璃实际CT值接近或大于CT极限值时，玻璃会发生破裂。二次强化后的锂铝硅玻璃CT值较大，在提升深层压应力值的化强实验中容易发生玻璃的破裂。目前，用于提高深层压应力的方法为低温长时间离子交换，此方法耗时较久，提高生产成本。另一方法，通过提升化强温度增加扩散速率从而减少交换时间，但由于应力松弛现象的存在，可适用的温度不能太高。因此，通过升高化强温度增大离子进入深度的作用有限，深层压应力较难提升，从而制约了锂铝硅系化学强化玻璃的抗跌落性能。
发明内容
为此，为解决以上问题，发明人通过在锂铝硅系玻璃中引入微晶颗粒，微晶颗粒由于具有结晶相，较玻璃具有较高的网络结构强度，其可增加玻璃韧性，提升最大CT容纳度；同时，微晶颗粒在高温下较为稳定，可减少应力松弛量。发明人利用微晶颗粒结构的特殊性，通过一定的配方设计及热处理工艺，在锂铝硅系玻璃中引入一定含量的微晶相，并在限定的化学强化工艺条件下进行离子交换，改善微晶玻璃制品内部深层处的压缩应力值，获得内部深层处具有高压缩应力值的微晶玻璃制品。
为达到上述目的，在本发明的第一个方面，本发明提供了一种具有深层高压应力的强化微晶玻璃，所述强化微晶玻璃制品包括两个对应的压缩应力层；所述压缩应力层由上下表面向内延伸，依次包括表面压缩应力区和深层压缩应力区；所述表面压缩应力区和深层压缩应力区的总厚度为50～100um；所述表面压缩应力区的厚度为0～20um，所述表面压缩应力区的应力CS≥800MPa；所述深层压缩应力区中，内应力分布斜率的绝对值＜2，CS-30≥115MPa，CS-50≥80MPa。
优选的，所述微晶玻璃的厚度t，0.55mm≤t＜0.8mm；所述压缩应力层的厚度＞0.2t。
优选的，所述压缩应力层的厚度≥0.22t。
优选的，所述表面压缩应力区应力CS≥850MPa。
优选的，所述深层压缩应力区内，CS-30≥120MPa，
优选的，所述深层压缩应力区内，CS-50≥85MPa。
优选的，所述强化微晶玻璃的CT值为-50～-90MPa、维氏硬度≥6.50GPa、4PB测试值＞700N/mm 2，所述强化微晶玻璃的单杆静压强度损失率＜10％，断裂阀值＞5kgf。
为达到上述目的，在本发明的第二个方面，本发明提供了本发明第一方面所述具有深层高压应力的强化微晶玻璃的制备方法，包括以下步骤：
首次离子交换(IOX)：将基础微晶玻璃放入第一浴盐中进行首次离子交换，第一浴盐组成为KNO 3和NaNO 3，第一浴盐中Na/K摩尔比为1.2～6.7：1；离子交换温度＞480℃，交换时间为3～6h；
二次离子交换(IOX)：将首次离子交换后的基础微晶玻璃放入第二浴盐中进行二次离子交换，第二浴盐组成为100wt％KNO 3或钠离子摩尔百分比含量＜10％的钾钠离子混合物中；二次离子交换温度较首次离子交换温度低10～30℃，交换时间为0.5～2h，得到具有深层高压应力的微晶玻璃。
首次离子交换中，为保证化强效果，需限定其Na/K摩尔比例；较高的钾含量易在玻璃浅表层积聚，不利于后续离子的持续进入，影响应力层深度；钠含量过大一定程度上会利于Na-Li交换，提高深度及深层压缩应力，但同时会在表层形成富钠层，影响玻璃的化学稳定性。因此，离子交换浴盐配比限定Na/K摩尔比为1.2～6.7；离子交换温度大于480℃，部分实施例中交换温度高于530℃，有效交换时间为3～6h。
优选的，所述基础微晶玻璃在380～780nm光波段处0.75mm厚度平均透过率＞89％；
优选的，所述基础微晶玻璃制备包括以下步骤：
基础玻璃制备：按照以下质量百分比对各组分进行称量、混合，再经过熔化、成型、退火后，得到基础玻璃；
SiO 2为55％～68％，Al 2O 3为18％～22％，Li 2O为4％～7％，TiO 2为0.5％～1.8％，Na 2O为3％～6％，碱土金属氧化物RO为0％～1％，B 2O 3为0.5％～2％，P 2O 5为1.5％～4％，ZrO 2为1％～5％、澄清剂为0.15％～0.4％；
其中21％＜P 2O 5+Al 2O 3-RO＜24％、8％＜Li 2O+Na 2O≤11％，0.7％＜Li 2O/(Li 2O+TiO 2)＜1％；
SiO 2构成了基础玻璃及微晶玻璃的主体结构，也是构成晶相的主要成分。其含量过低会导致晶相成分的变化，同时也会弱化玻璃整体性能。SiO 2含量不应低于55wt％。但较高的SiO 2含量，又会导致熔制成型困难，且组分中还含有高铝及锆成分。综合考虑：本发明将SiO 2的含量控制在55wt％～68wt％之间。
Al 2O 3由于在玻璃结构中体积比硅氧四面体体积要大，可为玻璃在离子强化过程中提供强化通道，其含量越高越能促进玻璃离子强化。其含量不应低于18wt％；但Al 2O 3属于极难熔氧化物，能快速提高玻璃高温粘度，致使玻璃澄清均化难度加大，气泡缺陷不易排出，控制其含量低于22wt％。
Li 2O能降低玻璃的晶化温度，促进玻璃的晶化，也是离子交换，提升深层应力深度及强度的主要成分。为获取较优的深层应力，其Li 2O含量不应低于4wt％。但过高的Li 2O极易析晶，会使得玻璃析晶较难控制，且锂成本较高，增加生产成本。因此，控制基础玻璃中Li 2O含量不高于7wt％。
TiO 2是一种成核剂，可方便成核及晶粒的形成及生长。其可与Li 2O共同作用降低晶化温度。考虑到组成中Li 2O含量，其TiO 2成分控制在0.5％～1.8％。
Na 2O能显著降低基础玻璃的粘度，促使基础玻璃的熔化和澄清。同时，Na离子也是离子交换的主要参与者。Na离子含量过少，不利于离子交换。但Na 2O含量的增多又会导致结晶相种类的变化，生成多种性能各异的晶体，使得晶化过程难以控制，容易使玻璃失透或不均匀。因此，从离子交换的角度考虑，为了能够使微晶玻璃后期可进行K +与Na +离子的交换，在玻璃表面形成高压缩应力，其最小含量不低于3wt％，从晶相控制的角度，基础玻璃中Na 2O含量不宜高于6wt％。
在某些实施例中，含有碱土金属氧化物RO，R 2+可为Mg 2+、Ca 2+、Zn 2+或Ba 2+，其能提高玻璃的化学稳定性和机械强度。但R 2+影响离子扩散速率，其直径越大影响越显著，同时较大离子半径对碱离子通道有一定的堵塞作用。因此，RO的组份含量设定为0wt％～1wt％。较优选离子直径较小的Mg 2+或Zn 2+。
B 2O 3属于网络形成体氧化物，可降低玻璃高温熔融粘度，改善熔化特性。其适量有助于改良离子扩散性，提高离子交换能力。但B 2O 3可导致分相，随着含量的增多会影响晶化后玻璃的透过率，含量过高还会破坏主体网络结构，机械强度下降。因此，B 2O 3的组份含量设定为0.5wt％～2wt％。
P 2O 5属于基础玻璃的网络形成体成分之一，其以[PO4]四面体相互连成网络，使玻璃网络结构呈疏松状态，网络空隙变大，有利于离子进行相互扩散。因此，P 2O 5含量至少为1.5wt％。但P 2O 5含量过高，会使玻璃分相严重，影响微晶玻璃的透过性，P 2O 5含量至多为4wt％。
ZrO 2有助于降低晶化过程中晶粒尺寸大小，从而提高玻璃的透过率，并能快速提高玻璃的化学稳定性及一定的增韧作用。在本组分中，Zr0 2有助于主晶相的稳定性；如没有Zr0 2，则容易导致主晶相发生晶型转变，影响玻璃整体的均匀性和透过性。因此，ZrO 2的组份含量最低不少于1wt％。但ZrO 2属于一种难熔成分，能快速提高基础玻璃粘度，过高的ZrO 2含量会导致玻璃中ZrO 2未熔物存在。因此，ZrO 2含量最多控制在5wt％。
除上述的氧化物之外，本发明的玻璃中含有化学澄清剂，澄清剂可以在玻璃熔制过程中高温分解，气化产生气体或者降低玻璃液的粘度，促使玻璃液中气泡消除或溶解吸收，从而达到更好的熔制效果。本发明中，澄清剂不含Sb 2O 3，可优选CeO 2及SnO 2中的一种或多种，澄清剂含量控制在0.15％～0.4％。
特别的，本发明为兼顾离子的快速扩散及晶化特性，需限制21％＜P 2O 5+Al 2O 3-RO＜24％、8％＜R 2O(Li 2O+Na 2O)≤11％，0.7％＜Li 2O/Li 2O+TiO 2＜1％。
微晶化热处理：将基础玻璃放入晶化炉内，以8～12℃/min升温至核化温度Tg～Tg+30℃，保温120～240min,然后以2～5℃/min升温至晶化温度730～760℃，保温60～120min，再以2～5℃/min降温至Tg-30～Tg-20℃,保温110～130min；最后以2℃/min降至550～570℃，保温热处理30min，冷却后得到基础微晶玻璃。
所述基础微晶玻璃中玻璃相的含量为72wt％～86wt％，所述玻璃相由平均晶粒尺寸＜30nm的硅酸铝锂晶粒构成。
优选的，所述澄清剂为SnO 2或CeO 2中的一种或两种组合。
优选的，所Tg温度为624℃～655℃。
相比于现有技术，本发明至少包括如下所述的有益效果：提供一种具有深层高压应力的微晶玻璃制品，其通过引入微晶相颗粒，在高温化强条件下可实现玻璃制品深层处具有高压缩应力，且不发生应力松弛及破裂现象。其玻璃制品在其厚度0.55mm≤t＜0.8mm范围内，具有表面压缩应力区CS大于800MPa，内部深层处(20-100um)区域内应力分布斜率的绝对值＜2，CS-30≥115MPa，CS-50≥80MPa的高压缩应力值；其应力层DOC深度大于0.2倍的玻璃厚度；其CT值介于50-90MPa，维氏硬度大于6.50GPa，4PB测试值大于700N/mm 2，单杆静压强度损失率小于10％，(500kgf/15s下的预制缺陷)，断裂阀值大于5kgf，极大改善了强化微晶玻璃的相关性能。
附图说明
图1为实施例1-6样品的纵截面示意图；
图2为实施例2样品的深层次应力曲线；
图3为实施例2样品的扫描电子显微镜(SEM)图；
图4为实施例2样品的从300nm-1200nm波长透过率图；
图5为实施例2样品的维氏硬度计5kgf/15s下的压痕图；
图6为实施例2样品的XRD图；
图7为实施例1-6样品的深层应力分布曲线图；
图8为实施例1-6样品在深层应力30um及50um处与市面上较优非晶二次强化玻璃的箱线图。
具体实施方式
为详细说明技术方案的技术内容、构造特征、所实现目的及效果，以下结合具体实施例并配合说明书附图1-8详予说明。
本发明的实施例1～6通过如下方法制备：
1、组分称量、混合：按各组分的比例选择相应的引入原料，SiO 2为55％～68％，Al 2O 3为18％～22％，Li 2O为4％～7％，TiO 2为0.5％～1.8％，Na 2O为3％～6％，碱土金属氧化物RO为0％～1％，B 2O 3为0.5％～2％，P 2O 5为1.5％～4％，ZrO 2为1％～5％、澄清剂为0.15％～0.4％；其中21％＜P 2O 5+Al 2O 3-RO＜24％、8％＜Li 2O+Na 2O≤11％，0.7％＜Li 2O/(Li 2O+TiO 2)＜1％；按其纯度、水分及比例范围进行称量并混合均匀，获得可熔制的混合料。实施例1-6中各组分以及质量百分比例见表1。
2、基础玻璃块制备：
将均匀的混合料放入铂制或铂铑制的坩埚中，根据玻璃组成的熔化难易度，在电炉内1600～1650℃的温度范围内进行4～6小时熔化，搅拌2-3次使其均匀后，降至适当的温度并浇铸到模具中，将浇铸成型的玻璃块放入600～650℃的退火炉内进行退火，退火完成后随炉冷却至常温取出，得到基础玻璃块。
3、微晶化热处理：
将基础玻璃块放入晶化炉内，分四个阶段进行热处理；热处理工艺参数见表1，其中第一阶段以8-12℃/min升温，第二阶段以2～5℃/min升温，第三阶段以1～2℃/min降温，第四阶段以2℃/min降温，热处理后随炉冷却，取出基础微晶玻璃。
4、强化微晶玻璃制备：
将基础微晶玻璃块进行切割、研磨及抛光制成片状玻璃。采取两步法进行离子交换。其步骤为：将片状样品放置450℃预热炉内保温30min,随后将基础微晶玻璃2次置入熔盐中进行离子强化(1IOX和2IOX)，离子强化工艺参数见表1，结束后将玻璃置于马弗炉内快速冷却。
采用热水清洗基础玻璃块和已化学强化玻璃的表面残留物，进行测试，结果见下表1以及图1-8。
表1实施例1‐6样品成分、工艺参数及性能表
Figure PCTCN2021088650-appb-000001
实施例1-6物理性质其定义及解释如下所示：
(1)Tg：玻璃转变点温度，采用DSC测试。
(2)平均晶粒尺寸：利用SEM扫描电镜进行测定，微晶玻璃通过在HF酸中进行表面处理，再对微晶玻璃表面进行喷铬镀膜，在SEM扫描电镜下进行表面扫描，观察到颗粒的直径，并通过加总所有晶粒剖面的平均直径尺寸，除以SEM影像中的晶粒数。
(3)非晶含量：将XRD衍射峰与数据库图谱进行对比确定晶相，通过Rietveld方法计算结晶相衍射强度在整体图谱强度中所占比例得出结晶度及非晶含量。
(4)透过率：采用紫外可见分光光度计测试。
(5)维氏硬度：采用维氏硬度计测量，加载力为200g，加载时间为15S。
(6)CS:微晶玻璃中表层应力值，采用日本折原工业有限公司FSM-6000表面应力计进行测试。
(7)CS-30/CS-50：微晶玻璃内30/50um(与表面垂直距离)处压应力值，采用SLP-1000表面应力仪测试。
(8)DOC：微晶玻璃中应力从压缩变化到拉伸的深度，即应力层深度，采用SLP-1000表面应力仪测试。
(9)CT：中心张应力，采用SLP-1000表面应力仪测试。
(10)t2斜率值：深层压缩应力区的内应力分布斜率采用SLP-1000表面应力仪测试应力数据后计算得到。
(11)t值：微晶玻璃厚度，采用电子游标卡尺测出。
(12)4PB：采用万能试验机测试；
(13)剩余强度：采用维氏硬度计进行500kgf/15s下的预制缺陷，再通过万能试验机进行单杆静压测试；
(14)断裂阀值：采用高压力维氏硬度计测量，加载力为5kgf，加载时间为15S。
图1-8解释说明：
图1为实施例1-6样品的纵截面示意图，厚度t的样品，由上、下表面向内延伸，分别有t 1及t 1’厚度的表面压缩应力区；以及对应的t 2及t 2’厚度的深层压缩应力区；往内部延伸到应力总值为零处为压缩应力层(DOC)厚度；截面方向可见纳米晶粒分布在玻璃相中；
图2为实施例2样品的深层次应力曲线，其20-100um范围内斜率＞-2MPa/um，DOC＞130um；
图3为实施例2样品的扫描电子显微镜(SEM)图,其晶粒平均尺寸＜30nm，晶粒与晶粒间被玻璃相填充，其玻璃相占比为84.2％；
图4为实施例2样品的从300nm-1200nm波长透过率图，其在可见光380-780nm光波段处平均透过率＞90％；
图5为实施例2样品的维氏硬度计5kgf/15s下的压痕图，其压痕图四点处无延伸裂纹，可知其断裂阀值高于5kgf；
图6为实施例2样品的XRD图，图中衍射峰不够尖锐，有部分馒头峰的存在，可知其晶化不够彻底，为较低结晶度，其晶相物质与数据库图谱进行对比为硅酸铝锂；
图7为实施例1-6样品的深层应力分布曲线图，其在20-100um范围内应力曲线斜率分布较为接近且＞-2MPa/um，其DOC＞120um；
图8为实施例1-6样品在深层应力30um及50um处与市面上较优非晶二次强化玻璃的箱线图，从图8中可见，实施例样品在30um及50um处具有较高应力值，其均值及大比例范围值更为优越。
由表1和图1-8可以看出，通过一定的配方设计及热处理工艺，在锂铝硅系玻璃中引入一定含量的微晶相，并在限定的化学强化工艺条件下进行离子交换，改善微晶玻璃制品内部深层处的压缩应力值，获得内部深层处具有高压缩应力值的微晶玻璃制品。其通过引入微晶相颗粒，在高温化强条件下可实现玻璃制品深层处具有高压缩应力，且不发生应力松弛及破裂现象。其 玻璃制品在其厚度0.55mm≤t＜0.8mm范围内，具有表面压缩应力区CS大于800MPa，内部深层处(20-100um)区域内应力分布斜率的绝对值＜2，CS-30≥115MPa，CS-50≥80MPa的高压缩应力值；其应力层DOC深度大于0.2倍的玻璃厚度；其CT值介于50-90MPa，维氏硬度大于6.50GPa，4PB测试值大于700N/mm 2，单杆静压强度损失率小于10％，(500kgf/15s下的预制缺陷)，断裂阀值大于5kgf，极大改善了强化微晶玻璃的相关性能。
需要说明的是，在本文中，诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者终端设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者终端设备所固有的要素。在没有更多限制的情况下，由语句“包括……”或“包含……”限定的要素，并不排除在包括所述要素的过程、方法、物品或者终端设备中还存在另外的要素。此外，在本文中，“大于”、“小于”、“超过”等理解为不包括本数；“以上”、“以下”、“以内”等理解为包括本数。
需要说明的是，尽管在本文中已经对上述各实施例进行了描述，但并非因此限制本发明的专利保护范围。因此，基于本发明的创新理念，对本文所述实施例进行的变更和修改，或利用本发明说明书及附图内容所作的等效结构或等效流程变换，直接或间接地将以上技术方案运用在其他相关的技术领域，均包括在本发明的专利保护范围之内。

Claims (12)

  1. 一种具有深层高压应力的强化微晶玻璃，其特征在于，所述强化微晶玻璃包括两个对应的压缩应力层；所述压缩应力层由上、下表面向内延伸，依次包括表面压缩应力区和深层压缩应力区；所述表面压缩应力区和深层压缩应力区的总厚度为50～100um；
    所述表面压缩应力区的厚度为20um，所述表面压缩应力区的应力CS≥800MPa；
    所述深层压缩应力区中，内应力分布斜率的绝对值＜2，CS-30≥115MPa，CS-50≥80MPa。
  2. 根据权利要求1所述的强化微晶玻璃，其特征在于，所述微晶玻璃的厚度t，0.55mm≤t＜0.8mm；所述压缩应力层的厚度＞0.2t。
  3. 根据权利要求2所述的强化微晶玻璃，其特征在于，所述压缩应力层的厚度≥0.22t。
  4. 根据权利要求1所述的强化微晶玻璃，其特征在于，所述表面压缩应力区应力CS≥850MPa。
  5. 根据权利要求1所述的强化微晶玻璃，其特征在于，所述深层压缩应力区内，CS-30≥120MPa，
  6. 根据权利要求1所述的强化微晶玻璃，其特征在于，所述深层压缩应力区内，CS-50≥85MPa。
  7. 根据权利要求1所述的强化微晶玻璃，其特征在于，所述强化微晶玻璃的CT值为-50～-90MPa、维氏硬度≥6.50GPa、4PB测试值＞700N/mm 2、单杆静压强度损失率＜10％，断裂阀值＞5kgf。
  8. 权利要求1-7任一所述具有深层高压应力的强化微晶玻璃的制备方法，其特征在于，所述具有深层高压应力的微晶玻璃的制备包括以下步骤：
    首次离子交换：将基础微晶玻璃放入第一浴盐中进行首次离子交换，第一浴盐组成为KNO 3和NaNO 3，第一浴盐中Na/K摩尔比为1.2～6.7：1；离子交 换温度＞480℃，交换时间为3～6h；
    二次离子交换：将首次离子交换后的基础微晶玻璃放入第二浴盐中进行二次离子交换，第二浴盐组成为100wt％KNO 3或钠离子摩尔百分比含量＜10％的钾钠离子混合物中；二次离子交换温度较首次离子交换温度低10～30℃，交换时间为0.5～2h，得到具有深层高压应力的微晶玻璃。
  9. 根据权利要求8所述强化微晶玻璃的制备方法，其特征在于，所述基础微晶玻璃在380～780nm光波段处0.75mm厚度平均透过率＞89％。
  10. 根据权利要求8所述强化微晶玻璃的制备方法，其特征在于，所述基础微晶玻璃制备包括以下步骤：
    基础玻璃制备：按照以下质量百分比对各组分进行称量、混合，再经过熔化、成型、退火后，得到基础玻璃；
    SiO 2为55％～68％，Al 2O 3为18％～22％，Li 2O为4％～7％，TiO 2为0.5％～1.8％，Na 2O为3％～6％，碱土金属氧化物RO为0％～1％，B 2O 3为0.5％～2％，P 2O 5为1.5％～4％，ZrO 2为1％～5％、澄清剂为0.15％～0.4％；
    其中21％＜P 2O 5+Al 2O 3-RO＜24％、8％＜Li 2O+Na 2O≤11％，0.7％＜Li 2O/(Li 2O+TiO 2)＜1％；
    微晶化热处理：将基础玻璃放入晶化炉内，以8～12℃/min升温至Tg～Tg+30℃，保温120～240min,然后以2～5℃/min升温至晶化温度730～760℃，保温60～120min，再以2～5℃/min降温至Tg-30～Tg-20℃,保温110～130min；最后以2℃/min降至550～570℃，保温热处理30min，冷却后得到基础微晶玻璃；
    所述基础微晶玻璃中玻璃相的含量为72wt％～86wt％，所述玻璃相由平均晶粒尺寸＜30nm的硅酸铝锂晶粒构成。
  11. 根据权利要求10所述强化微晶玻璃的制备方法，其特征在于，所述澄清剂为SnO 2或CeO 2中的一种或两种组合。
  12. 根据权利要求10所述强化微晶玻璃的制备方法，其特征在于，所述Tg温度为624℃～655℃。
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