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CN116199426A - High-strength glass composition, microcrystalline glass and preparation method thereof - Google Patents

High-strength glass composition, microcrystalline glass and preparation method thereof Download PDF

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Publication number
CN116199426A
CN116199426A CN202111445164.1A CN202111445164A CN116199426A CN 116199426 A CN116199426 A CN 116199426A CN 202111445164 A CN202111445164 A CN 202111445164A CN 116199426 A CN116199426 A CN 116199426A
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glass
crystallization
nucleation
crystal
heat treatment
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吴波
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Shenzhen Weisiteng New Material Technology Co ltd
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Shenzhen Weisiteng New Material Technology Co ltd
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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
    • C03C10/0009—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Glass Compositions (AREA)

Abstract

The invention provides a preparation method of high-strength glass ceramics, glass ceramics and a glass composition thereof, wherein the glass composition comprises the following components in percentage by mole 2 ：70%~80%；Al 2 O 3 ：2%~5%；Na 2 O：0.1%~5%；ZrO 2 ：1%~5%；P 2 O 5 ：0.5%~2.5%；Li 2 O:15% -25%. The invention improves the crystallization amount of the glass ceramics by the design of the material prescription and the control of the heat treatment process system, remarkably improves the bulk strength of the glass ceramics, can obtain the high-strength glass ceramics even without chemical strengthening, is widely applied to intelligent terminals, reduces the process and reduces the production cost.

Description

High-strength glass composition, microcrystalline glass and preparation method thereof
Technical Field
The invention relates to the field of glass manufacturing, in particular to a high-strength glass composition, microcrystalline glass and a preparation method thereof.
Background
Glass ceramics, which are also called glass ceramics, are one of the finely divided products of glass, and because of their excellent performances in terms of drop resistance and impact resistance, the applications of glass ceramics in high-end electronic display products are expanded in recent years, and the glass ceramics gradually replace high-aluminum one-strength and two-strength glass, and become the preferred materials of high-end type cover plate glass. The microcrystalline glass is a compact, nonporous and uniform sintered body composed of crystalline phase and residual glass phase, a certain amount of nucleating agent (not added in some cases) is added into certain base glass, and then the base glass is subjected to heating (called thermosensitive) or (and) illumination (called photosensitive) treatment, so that a large amount of fine crystals are uniformly precipitated in the glass body, and the transparent or opaque material is prepared. The microcrystalline glass for the display terminal combines the advantages of high transmittance, low haze, high strength and high toughness of the ceramic, and greatly improves the durability of the electronic product.
The strength of the glass ceramics is related to the content of the microcrystalline phase, when the content of the microcrystalline phase is low, the glass phase is large in proportion, the glass phase becomes a continuous matrix, the crystalline phase is uniformly distributed in the glass phase in an isolated manner, and the strength of the glass ceramics is close to that of the glass. And as the content of the microcrystalline phase increases, the glass phase ratio gradually decreases, and the mechanical properties of the microcrystalline glass approach those of ceramics. When the content of the glass phase is extremely low, the glass phase is dispersed between the crystals and the network structure of the crystals, and the bulk strength of the glass ceramics reaches the maximum. Therefore, the transparent glass ceramics are applied to the terminal cover plate glass, and the strength, especially the drop resistance and the impact resistance of the glass ceramics are improved as much as possible on the premise of ensuring the basic optical properties such as transmittance, haze and the like. One method of increasing the strength of glass ceramics is to increase the crystal content in the glass ceramics and thereby increase the bulk strength of the glass ceramics. However, the high content of the crystals causes the decrease of the transmittance and the increase of the haze of the glass ceramics, and the optical performance requirements can be met only by ensuring the small grain size and the large quantity of the grains. How to ensure that the transmittance of glass is improved and the haze of the glass is reduced when the crystallization amount is high, and the corresponding material prescription design and the control of a heat treatment process system become the key for improving the performance of the glass ceramics.
Disclosure of Invention
In order to improve the strength of the glass ceramics on the premise of ensuring the basic optical properties such as transmittance, haze and the like, the invention provides a preparation method of the high-strength glass ceramics, glass and a glass composition thereof.
In order to achieve the above purpose, the invention provides a glass composition, which comprises the following components in mole percent: siO (SiO) 2 ：70%~80%；Al 2 O 3 ：2%~5%；Na 2 O：0.1%~5%；ZrO 2 ：1%~5%；P 2 O 5 ：0.5%~2.5%；Li 2 O：15%~25%。
Preferably, the above glass composition satisfies the following conditions:
[SiO 2 ]＞8×[Al 2 O 3 ]+2×([Li 2 O]-[Al 2 O 3 ])
[Al 2 O 3 ]＜[Li 2 O]/4
[Na 2 O]+[SiO 2 ]-6[Al 2 O 3 ]-2[Li 2 O]＜30%
[ZrO 2 ]/[P 2 O 5 ]≥2
in order to achieve the above purpose, the invention also provides a preparation method of the glass ceramics, which comprises the following steps:
step one: the basic glass is manufactured through the design, the batching and the mixing of the above-mentioned material prescription;
step two: performing nucleation heat treatment, namely treating the prepared base glass to a T1 nucleation temperature, wherein the T1 nucleation temperature ranges from 500 ℃ to 700 ℃, and the T1 nucleation time ranges from 10h to 48h;
step three: crystallization heat treatment, namely treating the base glass subjected to the nucleation heat treatment to a T2 crystallization temperature, wherein the T2 crystallization temperature ranges from 720 ℃ to 900 ℃, and the T2 crystallization time ranges from 10h to 48h;
step four: and cooling, namely cooling the base glass subjected to crystallization heat treatment to room temperature.
Preferably, the T1 nucleating temperature ranges from 520 ℃ to 680 ℃ and the T1 nucleating time ranges from 24 hours to 40 hours.
Preferably, the crystallization temperature of T2 ranges from 720 ℃ to 800 ℃, and the crystallization time of T2 ranges from 24h to 40h.
In order to achieve the above object, the present invention also provides a glass-ceramic, which is produced by the above production method, wherein the glass-ceramic has a total crystallinity of C < A+B+ [ ZrO ] 2 ]+[P 2 O 5 ]The content is more than 60wt%, wherein A is the crystallization amount of petalite in the microcrystalline glass, and B is the crystallization amount of lithium disilicate in the microcrystalline glass.
Preferably, the crystallization amount of petalite in the glass ceramic is a=8× [ Al 2 O 3 ]~10×[Al 2 O 3 ]The content range is 20wt% to 50wt%.
Preferably, the devitrification amount b=2.5× ([ Li) of lithium disilicate in glass ceramic 2 O]-[Al 2 O 3 ])~3×([Li 2 O]-[Al 2 O 3 ]) The content range is 25wt% to 50wt%.
According to the invention, petalite and lithium disilicate are used as a double-crystal phase system, the formula of the petalite and the lithium disilicate is used as a material formula, a large number of tiny microcrystalline phases are separated out as a starting point, and the heat treatment process system is combined to control, so that the total crystallinity in the microcrystalline glass is maximized as far as possible on the premise of meeting the optical performance, the bulk strength of the microcrystalline glass is improved to the greatest extent, the prepared microcrystalline glass does not need chemical strengthening, the visible light transmittance is more than 80%, the haze is less than 0.5, and the b value is less than 4, and the glass can be widely applied to the field of intelligent display.
Detailed Description
The invention provides high-strength glass ceramics, a glass composition and a preparation method thereof, and aims to make the purposes, the technical scheme and the effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Endpoints of the present disclosure and any values are not limited to the precise range or value, and are understood to include values approaching the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are considered to be specifically disclosed herein.
The first aspect of the invention provides a glass composition comprising, in mole percent: siO (SiO) 2 ：70%~80%；Al 2 O 3 ：2%~5%；Na 2 O：0.1%~5%；ZrO 2 ：1%~5%；P 2 O 5 ：0.5%~2.5%；Li 2 O：15%~25%。
Preferably, the above glass composition satisfies the following conditions:
[SiO 2 ]＞8×[Al 2 O 3 ]+2×([Li 2 O]-[Al 2 O 3 ])
[Al 2 O 3 ]＜[Li 2 O]/4
[Na 2 O]+[SiO 2 ]-6[Al 2 O 3 ]-2[Li 2 O]＜30%
[ZrO 2 ]/[P 2 O 5 ]≥2
in the invention, petalite and lithium disilicate are used as a bicrystal phase system, and the material formula design is mainly carried out according to molecular formulas of the two crystal phases. Wherein the molecular formula of petalite is LiAlSi 4 O 10 To oxide of 1/2Li 2 O·1/2Al 2 O 3 ·4SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Lithium disilicate of formula Li 2 Si 2 O 5 To Li as oxide 2 O·2SiO 2 Starting from the precipitation of a large number of fine microcrystalline phases.
In petalite, siO 2 With Al 2 O 3 The mol percentage ratio of (2) is 8:1, li 2 O and Al 2 O 3 The mole percentage ratio of (2) is 1:1, thus SiO 2 Li (lithium ion battery) 2 The required amount of O is Al 2 O 3 8 times and 1 time of the total number of the components. In lithium disilicate, siO 2 With Li 2 The mole percentage ratio of O is 2:1. thus SiO 2 As a silicon source of petalite and lithium disilicate, the two crystal phases need to form a pair of SiO 2 Basic requirement of content, i.e. [ SiO ] 2 ]＞8×[Al 2 O 3 ]+2×([Li 2 O]-[Al 2 O 3 ]). If the content is insufficient, al in the glass ceramics is caused 2 O 3 And/or Li 2 The excessive O can not enter into crystal lattice to form crystal phase, and can only exist in the form of glass phase, so that the total crystal phase content of the final product is low, and the advantage of high bulk strength of the glass ceramics can not be fully exerted. And SiO 2 The content should not be too high, if too highDue to lack of Al 2 O 3 And/or Li 2 O, leading to SiO 2 Can only be used to form the network framework structure in the glass phase, again resulting in a lower total crystalline phase content of the final article.
Al 2 O 3 When the content is too high, the glass has high viscosity at high temperature, and even undesirable crystal phases such as eucryptite are generated. In addition, al 2 O 3 In the invention, the aluminum source is mainly used as an aluminum source for forming petalite crystal phase, and mutual promotion and mutual inhibition capability of the petalite crystal phase and the lithium disilicate crystal phase are exerted for forming an interlocking structure of the double crystal phase. Preferably, [ Al ] 2 O 3 ]＜[Li 2 O]/4，Al 2 O 3 The content cannot be excessively high because the formation proportion of petalite crystal phase is large when the content is excessively high, the crystal grain is easy to grow, the proportion of microcrystals is semitransparent even devitrified due to heavy growth, and the visible light transmittance is reduced and the haze is increased due to light weight.
Na 2 O is difficult to participate in the formation of a crystal phase in the present invention due to its low content, [ SiO ] 2 ]-6[Al 2 O 3 ]-2[Li 2 O]For SiO forming glass phase skeleton structure remaining except for participating in crystal phase formation 2 The sum of the two being the theoretical content of the glass phase. Preferably, [ Na ] 2 O]+[SiO 2 ]-6[Al 2 O 3 ]-2[Li 2 O]To ensure high crystallinity, the chemical composition of the amorphous phase is limited, [ Na ] 2 O]+[SiO 2 ]-6[Al 2 O 3 ]-2[Li 2 O]At > 10%, na 2 O and SiO not used for forming crystalline phase 2 The higher content of (c) leads to the generation of undesirable crystal phases such as nepheline and beta-quartz, or increases the glass phase ratio, and the performance advantage of high bulk strength of the glass ceramics cannot be fully exerted.
ZrO 2 And P 2 O 5 The crystal nucleus agent is uniformly diffused in the base glass at the glass melting forming temperature, the unstable decomposition of the glass is promoted in the nucleation heat treatment stage, the liquid-liquid surface activation energy is reduced to separate phases, further the development of phase interfaces caused by liquid phase crystallization and unstable decomposition is realized, and the nucleation is reducedAn activation energy or energy barrier, and a crystal phase surrounds a crystal nucleus for crystal growth in the crystallization heat treatment stage. P (P) 2 O 5 Is a common nucleating agent for microcrystalline glass of a lithium disilicate system, and lithium orthophosphate Li is used in the initial stage of crystallization 3 PO 4 Nucleation as an epitaxial center for lithium disilicate nucleation, zrO 2 The single crystal of zirconia precipitated during the nucleation heat treatment is used as a crystal nucleus to reduce the activation energy of crystallization. Firstly, the compound crystal nucleus agent can play a better nucleation effect than a single crystal nucleus agent, secondly, the double crystal nucleus agent promotes the formation of petalite crystal phase and lithium disilicate crystal phase, in the crystallization stage, as a silicon source and a lithium source are important compositions of the two crystal phases, in the process of crystal growth, the two crystal phases compete for the silicon source and the lithium source, the formed crystal phase structure of the opposite crystal phase is destroyed to form a self crystal phase, namely the crystal phase is continuously destroyed and the crystal phase is formed, and finally, the crystal grain size of the two crystal phases is gradually thinned to realize that the grain size of the crystal phase is smaller than 100nm, so that the basic requirement of optical visibility is met, and the process is not realized by a single crystal phase system. Therefore, in order to realize the preparation of high crystallinity and high transparency microcrystalline glass, a large number of crystal nuclei are required to be provided for realizing the process of mutually competing for grain size refinement of the bi-crystalline phase, and the inventor has verified through a large number of experiments that only when [ ZrO 2 ]/[P 2 O 5 ]And when the crystal phase quantity of the petalite and the lithium disilicate which are finally formed is more than or equal to 2, the precondition that the mutual competing and the grain refinement are met is satisfied.
The invention provides a preparation method of high-strength glass ceramics, which comprises the following steps:
step one: the basic glass is manufactured through the design, the batching and the mixing of the above-mentioned material prescription;
step two: performing nucleation heat treatment, namely treating the prepared base glass to a T1 nucleation temperature, wherein the T1 nucleation temperature ranges from 500 ℃ to 700 ℃, and the T1 nucleation time ranges from 10h to 48h;
step three: crystallization heat treatment, namely treating the base glass subjected to the nucleation heat treatment to a T2 crystallization temperature, wherein the T2 crystallization temperature ranges from 720 ℃ to 900 ℃, and the T2 crystallization time ranges from 10h to 48h;
step four: and cooling, namely cooling the base glass subjected to crystallization heat treatment to room temperature.
Preferably, the T1 nucleating temperature ranges from 520 ℃ to 680 ℃ and the T1 nucleating time ranges from 24 hours to 40 hours.
Preferably, the crystallization temperature of T2 ranges from 720 ℃ to 800 ℃, and the crystallization time of T2 ranges from 24h to 40h.
In order to realize the preparation of microcrystalline glass with high crystallinity and high transparency, i.e. the content of crystalline phase is high and the size of crystalline grain is small, the number of crystal nuclei must be enough to support the continuous refinement of the crystalline grain size by competing the two crystalline phase systems in the crystallization heat treatment stage, the nucleation temperature and the nucleation time are particularly critical, and the nucleation temperature is ZrO 2 And P 2 O 5 On the premise of nucleation, the nucleation time is the premise of large proportion of the nucleating agent and even complete precipitation nucleation. In one embodiment, the nucleation temperature range is: 500 ℃ to 700 ℃, more preferably 520 ℃ to 680 ℃, the nucleation temperature is not too low, and ZrO is not needed to be used when the nucleation temperature is too low 2 And P 2 O 5 The nucleation cannot be performed, the nucleation temperature is not too high, and when the nucleation temperature is too high, the nucleating agent is not sufficiently separated out and enters a crystallization heat treatment stage, so that a crystal phase grows around the individual nucleating agent, and the grain size is difficult to control. In one embodiment, the nucleation time range is: 10-48 h, more preferably 24-40 h, the nucleation time is not too short, the nucleus is difficult to be completely separated out too short, the nucleation time is not too long, and energy is wasted when too long.
The single crystal phase system has larger grain size along with the extension of crystallization time, and finally leads to translucency and even devitrification of the glass, while the double crystal phase system of the invention has destroyed structure of formed crystal phase because of competing with lithium source and silicon source of opposite crystal phase in the forming stage, and along with the extension of crystallization time, the grain size is finer, the microcrystalline glass is more transparent, the haze is lower, and the CIE b value is more similar to that of transparent glass. In one embodiment, the crystallization temperature ranges are: the crystallization temperature is preferably 720-900 ℃, more preferably 720-800 ℃, and the crystallization temperature is not too low, enough crystallization energy cannot be provided when the crystallization temperature is too low, crystals are difficult to grow and separate out, the crystallization temperature is not too high, the crystal grains grow rapidly when the crystallization temperature is too high, and the crystal grain size is difficult to control. In one embodiment, the crystallization time ranges are: 10-48 h, more preferably 24-40 h, the crystallization time is not too short, the crystals are difficult to be completely separated out in too short time, and energy is wasted in too long time.
The third aspect of the present invention also provides a high-strength glass-ceramic, which is prepared by the above preparation method, and has a total crystallinity of C < A+B + [ ZrO ] 2 ]+[P 2 O 5 ]The content is more than 60wt%, wherein A is the crystallization amount of petalite in the microcrystalline glass, and B is the crystallization amount of lithium disilicate in the microcrystalline glass.
Petalite is a monoclinic crystal with folded Si through Li and Al tetrahedral bonding 2 O 6 In the three-dimensional framework structure of the layered structure of the layers, the thermal expansion coefficient of the petalite crystal phase of the single crystal is close to 0, and the thermal expansion coefficient is increased along with the reduction of the content of the petalite, and the crystallization amount A=8× [ Al ] of the petalite in the invention 2 O 3 ]~10×[Al 2 O 3 ]The content range is 20-50 wt%, the thermal expansion coefficient is low, and the thermal shock resistance is high.
The lithium disilicate crystal has a rod-shaped microstructure, and when the lithium disilicate content is high and the lithium disilicate crystal has a high length-diameter ratio, the glass ceramics has optimal mechanical properties, in particular bending strength and fracture toughness. In the microcrystalline glass, the crystal phase of lithium disilicate is an irregularly and unoriented interlocked microstructure, so that the crack is forced to bend along the path when passing through the crystal, thereby preventing the crack from expanding and improving the strength and toughness of the microcrystalline glass. The crystallization amount of lithium disilicate in the present invention b=2.5× ([ Li) 2 O]-[Al 2 O 3 ])~3×([Li 2 O]-[Al 2 O 3 ]) The content range is 25wt% to 50wt%.
The prepared glass ceramic does not need chemical strengthening, has visible light transmittance of more than 80%, haze of less than 0.5 and b value of less than 4, and can be applied to the field of intelligent display.
The present invention will be described in detail by way of examples, and unless otherwise indicated, the methods used are conventional in the art. As shown in table 1, wherein examples 1 to 32 are examples of the glass composition claimed in the present invention, examples 33 to 44 are inverse examples.
TABLE 1
Figure DEST_PATH_IMAGE002
Table 1, below
Figure DEST_PATH_IMAGE004
Table 1, below
Figure DEST_PATH_IMAGE006
Table 1, below
Figure DEST_PATH_IMAGE008
Table 1, below
Figure DEST_PATH_IMAGE010
Table 1, below
Figure DEST_PATH_IMAGE012
Wherein, in examples 33 and 34, siO 2 The content is less than 70mol%, and less than 8 x [ Al 2 O 3 ]+2×（[Li 2 O]-[Al 2 O 3 ]) Resulting in insufficient supply of silicon source for forming the crystalline phase and insufficient formation of the crystalline phase.
In example 35, siO 2 Content > 80mol%, li 2 O content < 15mol% results in an excessive silicon source for forming the crystalline phase, while the lithium source is supplied too little, expressed as [ Na ] 2 O]+[SiO 2 ]-6[Al 2 O 3 ]-2[Li 2 O]More than 30mol%, a sufficiently large number of crystal phases cannot be formed.
In example 36, zrO 2 The content is more than 5mol percent, the content of the crystal nucleus agent is excessive, the crystal is easy to grow up rapidly, and the nucleation and crystallization heat treatment is difficult to control.
In example 37, al 2 O 3 The content is more than 5mol percent, so that the aluminum source for forming the crystal phase is excessive, the petalite crystal phase is high in content, the aim of inhibiting the petalite crystal phase and the lithium disilicate crystal phase mutually and refining the crystal grain size can not be achieved, and the petalite crystal phase is easy to semitransparent and even devitrify in the heat treatment stage.
In example 38, na 2 O content is more than 5mol%, sodium is not expected to participate in the formation process of crystalline phases, undesirable crystalline phases such as natrheline and the like can be generated, an interlocking structure of the bi-crystalline phases is destroyed, and when the sodium content is too high, the formation proportion of glass phases is increased.
In example 39, P 2 O 5 The content is > 2.5mol% such that [ ZrO 2 ]/[P 2 O 5 ]Less than 2, too much crystal nucleus agent content, easy rapid growth of crystal, and difficult control of nucleation and crystallization heat treatment.
In example 40, [ Al ] 2 O 3 ]＞[Li 2 O]And/4, the petalite crystal phase proportion is larger than that of the lithium disilicate crystal phase, so that the aim of inhibiting the lithium disilicate crystal phase and refining the crystal grain size cannot be fulfilled.
In examples 41 and 42, [ Na ] 2 O]+[SiO 2 ]-6[Al 2 O 3 ]-2[Li 2 O]More than 30% by weight of the glass phase, the high strength characteristics of the high-crystallite phase cannot be fully exhibited.
In example 43, siO 2 The content is less than 8 x [ Al 2 O 3 ]+2×（[Li 2 O]-[Al 2 O 3 ]) Resulting in insufficient supply of silicon source for forming the crystalline phase and insufficient formation of the crystalline phase.
In example 44, siO 2 The content is less than 70mol%, and less than 8 x [ Al 2 O 3 ]+2×([Li 2 O]-[Al 2 O 3 ])，Al 2 O 3 The content is more than 5mol%, the petalite crystal phase is difficult to form, and the crystal phase is converted into beta-eucryptite and/or beta-quartz and other undesirable crystal phases.
Taking example 3 as an example, a brief description of the heat treatment process control procedure is provided below, as shown in table 2, wherein examples 45 to 60 are claimed examples of the present invention, and examples 61 to 66 are reverse examples. The control flow of the heat treatment process of the high-strength glass ceramics is as follows:
1) Preparing base glass: ingredients were prepared according to the formulation set forth in example 3 and the materials were mixed well. Melting the raw materials at 1450-1600 ℃ to prepare glass liquid, and then clarifying, homogenizing, forming, annealing, cooling and the like to prepare the base glass.
2) And (3) nuclear heat treatment: placing the base glass into a heat treatment furnace for nucleation heat treatment, wherein the nucleation temperature range is as follows: 500-700 ℃, more preferably 520-680 ℃, and the nucleating time range is as follows: 10 to 48 hours, more preferably 24 to 40 hours.
3) Crystallization heat treatment: the base glass after the nucleation heat treatment is further subjected to crystallization heat treatment, and the crystallization temperature range is as follows: 720-900 ℃, more preferably 720-800 ℃, and the crystallization time range is: 10 to 48 hours, more preferably 24 to 40 hours.
4) And cooling to obtain the microcrystalline glass.
TABLE 2
Figure DEST_PATH_IMAGE014
Continuous table 2
Figure DEST_PATH_IMAGE016
Continuous table 2
Figure DEST_PATH_IMAGE018
In example 61, the nucleation temperature was less than 500 ℃, and the temperature was insufficient to precipitate the crystal nucleus agent from the glass phase, and even when the nucleation time was longer than 10 hours, the insufficient amount of crystal nucleus precipitation resulted in insufficient total crystallization amount even after the final crystallization heat treatment, and the advantage of the glass ceramics of high-ratio crystal phase could not be exhibited.
In example 62, the nucleation temperature was > 700 ℃, and the crystallization heat treatment stage was essentially skipped to directly enter the crystallization heat treatment stage, and although the crystallization phase was also precipitated, the total crystallization amount was relatively high, but the grain size was difficult to control, and the transmittance was low, the haze was large, and the CIE b value was large.
In example 63, the nucleation time was less than 10 hours, and too short, resulting in incomplete precipitation of ZrO2 and P2O5 as nuclei, insufficient total crystallization, and failure to exert the advantage of the glass ceramics of high-ratio crystalline phase.
In example 64, the crystallization temperature was less than 720 ℃, and the crystallization temperature was substantially equal to or lower than 720 ℃ in the nucleation heat treatment stage, and the crystallization amount was low.
In example 65, the crystallization temperature was > 900 ℃, the crystallization speed was difficult to control, and the rapid growth of the crystalline phase resulted in translucency, even devitrification.
In example 66, the crystallization time is less than 10 hours, the crystallization time is too short, the petalite crystal phase and the lithium disilicate crystal phase do not have sufficient time to grow up, and the mutual competing refined crystal grain size of the other two crystal phases does not reach the technical effect.
While the preferred embodiments of the present invention have been described in detail, it is to be understood that the invention is not limited in its application to the particular examples described above, and that modifications and variations may be made by those skilled in the art in light of the foregoing description, all such modifications and variations being intended to be included within the scope of the invention as defined in the following claims.

Claims (8)

1. A glass composition comprising, in mole percent, the following components: siO (SiO) 2 ：70%~80%；Al 2 O 3 ：2%~5%；Na 2 O：0.1%~5%；ZrO 2 ：1%~5%；P 2 O 5 ：0.5%~2.5%；Li 2 O：15%~25%。
2. The glass composition according to claim 1, wherein: the glass composition satisfies the following conditions:
[SiO 2 ]＞8×[Al 2 O 3 ]+2×([Li 2 O]-[Al 2 O 3 ])
[Al 2 O 3 ]＜[Li 2 O]/4
[Na 2 O]+[SiO 2 ]-6[Al 2 O 3 ]-2[Li 2 O]＜30%
[ZrO 2 ]/[P 2 O 5 ]≥2。
3. a preparation method of microcrystalline glass comprises the following steps:
step one: compounding a glass composition according to any one of claims 1-2 to complete the manufacture of a base glass;
step two: performing nucleation heat treatment, namely treating the prepared base glass to a T1 nucleation temperature, wherein the T1 nucleation temperature ranges from 500 ℃ to 700 ℃, and the T1 nucleation time ranges from 10h to 48h;
step three: crystallization heat treatment, namely treating the base glass subjected to the nucleation heat treatment to a T2 crystallization temperature, wherein the T2 crystallization temperature ranges from 720 ℃ to 900 ℃, and the T2 crystallization time ranges from 10h to 48h;
step four: and cooling, namely cooling the base glass subjected to crystallization heat treatment to room temperature.
4. A method of preparation according to claim 3, characterized in that: the nucleation temperature range of T1 is 520-680 ℃, and the nucleation time range of T1 is 24-40 h.
5. A method of preparation according to claim 3, characterized in that: the crystallization temperature range of T2 is 720-800 ℃, and the crystallization time range of T2 is 24-40 h.
6. A glass ceramic prepared by the method according to any one of claims 3 to 5, wherein the glass ceramic has a total crystallinity C < A+B+ [ ZrO 2 ]+[P 2 O 5 ]The content is more than 60wt%, wherein A is the crystallization amount of petalite in the microcrystalline glass, and B is the crystallization amount of lithium disilicate in the microcrystalline glass.
7. The glass-ceramic according to claim 6, wherein the petalite in the glass-ceramic has a devitrification amount a=8× [ Al 2 O 3 ]~10×[Al 2 O 3 ]The content range is 20wt% to 50wt%.
8. The glass ceramic according to claim 6, wherein the crystallization amount b=2.5× ([ Li 2 O]-[Al 2 O 3 ])~3×([Li 2 O]-[Al 2 O 3 ]) The content range is 25wt% to 50wt%.
CN202111445164.1A 2021-11-30 2021-11-30 High-strength glass composition, microcrystalline glass and preparation method thereof Pending CN116199426A (en)

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CN113387586A (en) * 2021-08-06 2021-09-14 成都光明光电股份有限公司 Glass ceramics, glass ceramics product and manufacturing method thereof
CN113698082A (en) * 2021-09-10 2021-11-26 成都光明光电股份有限公司 Method for producing glass-ceramic molded body

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CN110143759A (en) * 2019-06-13 2019-08-20 科立视材料科技有限公司 A high-strength transparent glass-ceramic
CN113387586A (en) * 2021-08-06 2021-09-14 成都光明光电股份有限公司 Glass ceramics, glass ceramics product and manufacturing method thereof
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