Glass ceramic with high reliability, chemically strengthened glass ceramic and glass preparation method

Abstract

The invention provides glass ceramics with high signal resistance, chemically strengthened glass ceramics and a glass preparation method, and relates to the technical field of materials, the glass ceramics comprise a glass phase and a crystal phase, the proportion of the glass phase in the glass ceramics is 10-50% by mass, and the components of the glass phase meet the following relational expression: t = (19.8 * F + 16.7 * I) / (0.43 * M), 130 < t < 380; wherein F represents the mass percent content of a network forming body in the glass phase, I represents the mass percent content of a network intermediate in the glass phase, M represents the mass percent content of a network outer body in the glass phase, and F is equal to 22%-48%, I is equal to 1%-12%, and M is equal to 2%-10%. According to the scheme, the proportion of the glass phase and the content of the network former, the network intermediate and the network outer body in the glass phase are optimally designed, so that positive ions can stably exist in the glass phase, the glass has better reliability and tolerance, and the weather resistance, the mechanical property and the optical property of the glass are improved.

Description

Technical Field

[0001] The present application relates to the field of material technology, and in particular to the field of microcrystalline glass technology. Specifically, the present application discloses a microcrystalline glass with high reliability and durability, a chemically strengthened microcrystalline glass, and a glass preparation method. Background Art

[0002] Glass-ceramics, a composite material composed of glass and crystalline phases, contains tiny crystals. It is widely used due to its relatively excellent mechanical properties, chemical stability, and heat resistance. However, traditional glass-ceramics still lack weather resistance and mechanical strength. In particular, they are prone to corrosion and breakage in high-temperature, high-humidity, and acidic and alkaline environments, resulting in reduced optical performance.

[0003] It is important to note that the techniques described in this section are not necessarily those that have been previously conceived or employed. Unless otherwise indicated, it should not be assumed that any technique described in this section is prior art simply because it is included in this section. Similarly, unless otherwise indicated, the issues mentioned in this section should not be considered to have been recognized as prior art. Summary of the Invention

[0004] The present application provides a microcrystalline glass with high reliability and durability, a chemically strengthened microcrystalline glass and a glass preparation method, aiming to solve at least one of the problems in the related art to a certain extent.

[0005] In a first aspect, the present application provides a glass-ceramic with high reliability and durability, characterized in that the glass-ceramic includes a glass phase and a crystalline phase, the proportion of the glass phase in the glass-ceramic is 10% to 50% by mass, and the composition of the glass phase satisfies the following relationship:

[0006] t=(19.8*F+16.7*I) / (0.43*M),

[0007] 130<t<380;

[0008] Wherein, F represents the mass percentage content of the network former in the glass phase, I represents the mass percentage content of the network intermediate in the glass phase, M represents the mass percentage content of the network exosome in the glass phase, and F = 22% to 48%, I = 1% to 12%, and M = 2% to 10%.

[0009] Optionally, the network former includes at least one of the following: SiO2, Al2O3, B2O3, P2O5.

[0010] Optionally, the calculation formula for the mass percentage content of the network former is expressed as:

[0011] F=(A-68.9%*a-76.8%*b-63.8%*c-60.4%*de)+(B-12.7*a-36.1*d)+C+D;

[0012] Among them, a represents the mass percentage of the petalite crystal phase in the entire microcrystalline glass, b represents the mass percentage of the lithium disilicate crystal phase in the entire microcrystalline glass, c represents the mass percentage of the lithium silicate crystal phase in the entire microcrystalline glass, d represents the mass percentage of the spodumene crystal phase in the entire microcrystalline glass, e represents the mass percentage of the quartz crystal phase in the entire microcrystalline glass, A represents the mass percentage of SiO2, B represents the mass percentage of Al2O3, C represents the mass percentage of B2O3, and D represents the mass percentage of P2O5.

[0013] Optionally, the network intermediate includes at least one of the following: TiO2, ZrO2, Y2O3, La2O3.

[0014] Optionally, the network outer body includes: Li2O, Na2O, K2O and RO, and RO includes at least one of CaO, MgO, ZnO and BaO.

[0015] Optionally, the calculation formula for the mass percentage content of the network exosome is expressed as:

[0016] M=(O-4.9*a-19.9*b-33.2*c-8.0*d)+P+Q+R;

[0017] Among them, a represents the mass percentage of the petalite crystal phase in the entire microcrystalline glass, b represents the mass percentage of the lithium disilicate crystal phase in the entire microcrystalline glass, c represents the mass percentage of the lithium silicate crystal phase in the entire microcrystalline glass, d represents the mass percentage of the spodumene crystal phase in the entire microcrystalline glass, O represents the mass percentage of Li2O, P represents the mass percentage of Na2O, Q represents the mass percentage of K2O, and R represents the mass percentage of RO.

[0018] Optionally, the crystalline phase includes at least one of the following: lithium disilicate, petalite, quartz and quartz solid solution, spodumene, lithium metasilicate, nautilus, spinel, wollastonite, and cordierite.

[0019] Optionally, the glass-ceramics satisfies the following relationship:

[0020] τ=(A-78.5*a-80.1*b-66.8*c-64.6*de)+(B-16.7*a-27.4*d)+(w*F+x*I+y*M)

[0021] / (O-4.9*a-19.9*b-33.2*c-8.0*d);

[0022] 17<τ<98;

[0023] Wherein, τ represents the reliability evaluation index, a represents the mass percentage of the petalite crystal phase in the entire glass-ceramics, b represents the mass percentage of the lithium disilicate crystal phase in the entire glass-ceramics, c represents the mass percentage of the lithium silicate crystal phase in the entire glass-ceramics, d represents the mass percentage of the spodumene crystal phase in the entire glass-ceramics, e represents the mass percentage of the quartz crystal phase in the entire glass-ceramics, A represents the mass percentage of SiO2, B represents the mass percentage of Al2O3, O represents the mass percentage of Li2O, M represents the mass percentage of the network former, N represents the mass percentage of the network intermediate, Z represents the mass percentage of the network outer body, w = 0.15 ~ 0.76, x = 12.7 ~ 38.5, y = 2.4 ~ 19.5;

[0024] Furthermore, the mass percentage wt(i) of a certain oxide component in the glass-ceramics satisfies the following relationship:

[0025] wt(i)=M(i)*n(i) / (∑M(x)*n(x));

[0026] Wherein, M(i) and n(i) are respectively the molar mass and molar percentage of a certain oxide component in the microcrystalline glass, and M(x) and n(x) are respectively the molar mass and molar percentage of any other oxide component in the microcrystalline glass.

[0027] Optionally, the glass-ceramics satisfies the following relationship:

[0028] X=n[(Li2O)+9*n(Na2O)+13*n(K2O)] / 33*n(RO)];

[0029] 0<X<0.03;

[0030] Wherein, X represents an ion exchange capacity evaluation index, n(Li2O) represents the molar percentage of the Li2O component, n(Na2O) represents the molar percentage of the Na2O component, n(K2O) represents the molar percentage of the K2O component, and n(RO) represents the molar percentage of the alkaline earth metal oxide component.

[0031] Optionally, the components of the glass-ceramics, expressed in mole percentage, include:

[0032] SiO2 greater than or equal to 60% and less than or equal to 78%;

[0033] 1.5% or more and 5.5% or less of Al2O3;

[0034] 18% or more and 26.8% or less of Li2O;

[0035] P2O5 greater than or equal to 0.1% and less than or equal to 2.5%;

[0036] ZrO2 greater than or equal to 0 and less than or equal to 5%;

[0037] RO is greater than or equal to 0 and less than or equal to 3.4%, and RO includes at least one of CaO, MgO, ZnO, and BaO;

[0038] greater than or equal to 0 and less than or equal to 6.5% Na2O;

[0039] K2O greater than or equal to 0 and less than or equal to 4%;

[0040] Greater than or equal to 0 and less than or equal to 1% of clarifier.

[0041] Optionally, the components of the microcrystalline glass, in molar percentage, also include: B2O3 greater than or equal to 0 and less than or equal to 4.8%; and / or TiO2 greater than or equal to 0% and less than or equal to 4%; and / or Y2O3 greater than or equal to 0 and less than or equal to 4%; and / or La2O3 greater than or equal to 0 and less than or equal to 0.5%.

[0042] Optionally, the components of the microcrystalline glass include, in molar percentage, greater than or equal to 22.2% and less than or equal to 25.8% of Li2O, greater than or equal to 0 and less than or equal to 3.1% of Na2O, and greater than or equal to 0 and less than or equal to 1.2% of K2O.

[0043] Optionally, the composition of the glass phase, expressed in molar percentage, satisfies the following relationship: Li2O / (Na2O+K2O)=0.8-20.

[0044] Optionally, the crystalline phase is lithium disilicate, and the lithium disilicate crystalline phase meets the following indicators: an average grain size is less than or equal to 38 to 45.7 nm, and a crystallinity is greater than or equal to 56.38%.

[0045] Optionally, the lithium disilicate crystalline phase meets the following indicators: the size of 98% of the grains in the overall crystalline phase is less than or equal to 60 nm, the size of 95% of the grains in the overall crystalline phase is less than or equal to 55 nm, and the size of 80% of the grains in the overall crystalline phase is less than or equal to 50 nm; the crystallinity is greater than or equal to 61.22%.

[0046] Optionally, the lower limit crystallization temperature of the glass-ceramics is 553-639°C, and the upper limit crystallization temperature is 989-1123°C.

[0047] Optionally, the glass-ceramics meets the following performance indicators: elastic modulus greater than or equal to 99.87 GPa, shear modulus greater than or equal to 40.23 GPa, fracture toughness greater than or equal to 1.01 MPa·m 1 / 2 , Poisson's ratio is greater than or equal to 0.20.

[0048] A second aspect of the present application provides a chemically strengthened microcrystalline glass with high reliability. The chemically strengthened microcrystalline glass is obtained by subjecting the microcrystalline glass of the first aspect to ion exchange treatment.

[0049] Optionally, the ratio of the surface compressive stress value of the chemically strengthened glass-ceramics to the depth of the compressive stress layer is greater than or equal to 7.5.

[0050] Optionally, the surface compressive stress value of the chemically strengthened microcrystalline glass is 240~276MPa, the compressive stress value at a depth of 50μm from the surface is 102~125MPa, the compressive stress value at a depth of 80μm from the surface is 65~75MPa, the depth of the compressive stress layer is 113~130μm, the absolute value of the maximum tensile stress is 105~108MPa, and the absolute value of the average tensile stress is 58~63MPa.

[0051] Optionally, the chemically strengthened microcrystalline glass meets the following performance indicators: when the thickness is 0.55 mm, the whole machine drop test height based on 80 mesh sandpaper is greater than 1100 mm; when the thickness is 0.55 mm, the whole machine drop test height based on 180 mesh sandpaper is greater than 1500 mm; the four-point bending test strength is greater than 1120 MPa; and the nine-point drop ball test height based on a 32g steel ball is greater than 1300 mm.

[0052] Optionally, the chemically strengthened microcrystalline glass meets the following performance indicators: the transmittance of visible light with a wavelength of 550nm when the thickness is 0.55mm is greater than or equal to 91.05%, the |B| value is less than or equal to 0.57%, and the haze is less than or equal to 0.14%; and the chemically strengthened microcrystalline glass with a thickness of 0.55mm meets the following performance indicators after 120 hours of double 85 test: the transmittance of visible light with a wavelength of 550nm is greater than or equal to 91.04%, the |B| value is less than or equal to 0.55%, and the haze is less than or equal to 0.15%.

[0053] A third aspect of the present application provides a glass preparation method, comprising:

[0054] The raw materials are mixed evenly according to the glass formula, melted at a preset melting temperature and melting time, and then formed and annealed to obtain a precursor glass;

[0055] heat-treating the precursor glass to obtain glass-ceramics;

[0056] The glass-ceramics includes a glass phase and a crystalline phase. The proportion of the glass phase in the glass-ceramics is 10-50% by mass. The composition of the glass phase satisfies the following relationship:

[0057] t=(19.8*F+16.7*I) / (0.43*M),

[0058] 130<t<380;

[0059] Wherein, F represents the mass percentage content of the network former in the glass phase, I represents the mass percentage content of the network intermediate in the glass phase, M represents the mass percentage content of the network exosome in the glass phase, and F = 22% to 48%, I = 1% to 12%, and M = 2% to 10%.

[0060] Optionally, the glass formula comprises, in mole percentage:

[0061] SiO2 greater than or equal to 60% and less than or equal to 78%;

[0062] 1.5% or more and 5.5% or less of Al2O3;

[0063] 18% or more and 26.8% or less of Li2O;

[0064] P2O5 greater than or equal to 0.1% and less than or equal to 2.5%;

[0065] ZrO2 greater than or equal to 0 and less than or equal to 5%;

[0066] RO is greater than or equal to 0 and less than or equal to 3.4%, and RO includes at least one of CaO, MgO, ZnO, and BaO;

[0067] greater than or equal to 0 and less than or equal to 6.5% Na2O;

[0068] K2O greater than or equal to 0 and less than or equal to 4%;

[0069] Greater than or equal to 0 and less than or equal to 1% of clarifier.

[0070] Optionally, the glass preparation method also includes: immersing the microcrystalline glass in a chemically strengthened salt bath for ion exchange treatment to obtain chemically strengthened microcrystalline glass; wherein the chemically strengthened salt bath includes, by mass percentage: greater than or equal to 9.99% and less than or equal to 39.99% KNO3, greater than or equal to 59.99 and less than or equal to 89.99% NaNO3, and greater than or equal to 0.03% and less than or equal to 0.1% LiNO3.

[0071] Optionally, the temperature of the chemical strengthening salt bath is 460-490° C., and the duration of the ion exchange treatment is 4-10 hours.

[0072] Optionally, the heat treatment of the precursor glass includes: placing the precursor glass in a crystallization furnace, heating it to 560-590°C at a heating rate of 8-12°C / min and keeping it warm for 220-250 minutes, then heating it to 750-790°C at a heating rate of 8-12°C / min and keeping it warm for 70-90 minutes, and finally cooling it at a cooling rate less than or equal to 2°C / min.

[0073] Optionally, the glass preparation method further includes: performing hot bending treatment on the microcrystalline glass through a hot bending workstation; wherein the pressure of the hot bending workstation is 0.7 to 1.1 MPa, and the operating time of a single workstation is 70 to 110 seconds.

[0074] Optionally, the hot bending treatment needs to go through four preheating workstations, three hot pressing workstations and two cooling workstations; wherein, the operating temperature of the first preheating workstation is 430-470°C, the operating temperature of the second preheating workstation is 530-570°C, the operating temperature of the third preheating workstation is 630-670°C, the operating temperature of the fourth preheating workstation is 710-730°C, the operating temperature of the first hot pressing workstation is 740-760°C, the operating temperature of the second hot pressing workstation is 740-760°C, the operating temperature of the third hot pressing workstation is 580-620°C, the operating temperature of the first cooling workstation is 430-470°C, and the operating temperature of the second cooling workstation is 280-320°C.

[0075] As can be seen from the above, according to the microcrystalline glass with high reliability and durability provided by the present application, the chemically strengthened microcrystalline glass and glass preparation method include a glass phase and a crystalline phase, the glass phase accounts for 10 to 50% by mass in the microcrystalline glass, and the composition of the glass phase satisfies the following relationship: t = (19.8*F + 16.7*I) / (0.43*M), 130 < t < 380; wherein F represents the mass percentage content of the network former in the glass phase, I represents the mass percentage content of the network intermediate in the glass phase, and M represents the mass percentage content of the network exosome in the glass phase, and F = 22% to 48%, I = 1% to 12%, and M = 2% to 10%. The present application optimizes the glass phase ratio and the content of the network former, network intermediate, and network exosome in the glass phase, so that cations can be stably present in the glass phase, resulting in good reliability and improved weather resistance, mechanical properties, and optical properties of the glass.

[0076] It should be understood that the content described in this section is not intended to identify the key or important features of the present application, nor is it intended to limit the scope of the present application. The further effects of the above non-conventional optional manner will be described below in conjunction with specific embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0077] The accompanying drawings illustrate exemplary embodiments and constitute a part of the specification. Together with the description of the specification, they serve to explain exemplary implementations of the embodiments. The drawings are shown for illustrative purposes only and do not limit the scope of the claims. Throughout the drawings, the same reference numerals designate similar, but not necessarily identical, elements.

[0078] Figure 1 This is a DSC test curve of the glass-ceramics corresponding to Example 4 provided in this application;

[0079] Figure 2 This is an XRD test graph of the glass-ceramics corresponding to Example 4 provided in this application;

[0080] Figure 3 This is a scanning electron microscope image of the glass-ceramics corresponding to Example 4 provided in this application;

[0081] Figure 4 The viscosity-temperature curve of the microcrystalline glass corresponding to Example 4 provided in this application. DETAILED DESCRIPTION

[0082] In order to make the purpose, features, and advantages of the invention of this application more obvious and easy to understand, the technical solutions in the embodiments of this application will be clearly and completely described below in conjunction with the drawings in the embodiments of this application. Obviously, the described embodiments are only part of the embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without making creative efforts shall fall within the scope of protection of this application.

[0083] In the description of the embodiments of the present application, the term "multiple" means two or more, unless otherwise clearly and specifically limited; the term "including" indicates the presence of the described features, wholes, steps, operations, elements and / or components, but does not exclude the presence or addition of one or more other features, wholes, steps, operations, elements, components and / or their collections; the term "and / or" describes the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B may include the existence of A alone, the existence of A and B at the same time, and the existence of B alone. The character " / " generally indicates that the related objects before and after are in an "or" relationship; the term "about" means that the content, size, parameter, etc. are not and do not need to be exact. If necessary, they can be approximate or higher or lower. Generally speaking, regardless of whether there is an explicit description, the content, size, parameter, etc. should be "about" or "approximate"; the terms "preferably" and "optional" are not used to limit the scope of the present application, nor do they mean that certain technical features are critical or indispensable to the implementation methods of the present application. Instead, they should be understood as merely indicating specific aspects of the embodiments of the present application.

[0084] Unless otherwise indicated in specific circumstances, the numerical ranges described in the examples of the present application are intended to include the endpoints of the numerical range and all integers and fractions within the range. When an amount, solubility or other parameter is described in the form of a preferred range or preferred value, it should be understood that it is equivalent to revealing any range by combining any preferred range with a preferred range, a preferred value with a preferred value, or a preferred range with a preferred value, without considering whether such pairwise combinations are specifically explained in the examples.

[0085] Unless otherwise specified in specific circumstances, the component contents described in the examples of the present application are expressed in molar percentage (mol%).

[0086] At present, traditional microcrystalline glass has the following three major problems: 1) Glass with high lithium content is prone to form a microcrack network on the surface during the strengthening process, affecting the mechanical strength of the glass; 2) Deep ion exchange leads to unstable stress distribution, and the imbalance of stress distribution may lead to local stress concentration, making microcracks more likely to form and expand on the surface or inside; 3) The accumulation of lithium ions in the salt bath causes salt bath poisoning, reducing the efficiency of chemical strengthening and affecting the effect and stability of chemical strengthening.

[0087] In response to the shortcomings of traditional micro-ceramics provided in the related art, the applicant has found that the glass phase composition of micro-ceramics has a significant impact on its reliability. In order to improve the comprehensive performance of micro-ceramics, such as weather resistance, mechanical properties, and optical properties, an embodiment of the present application provides a micro-ceramic with high reliability. The micro-ceramic includes a glass phase and a crystalline phase. The proportion of the glass phase in the micro-ceramic is 10% to 50% by mass. The composition of the glass phase satisfies the following relationship:

[0088] t=(19.8*F+16.7*I) / (0.43*M),

[0089] 130<t<380;

[0090] Wherein, F represents the mass percentage content of the network former in the glass phase, I represents the mass percentage content of the network intermediate in the glass phase, M represents the mass percentage content of the network exosome in the glass phase, and F = 22% to 48%, I = 1% to 12%, and M = 2% to 10%.

[0091] In an optional implementation manner of this embodiment, the value of t can be 131, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370, 375, 379. In addition, the value range of t can be 131-379, 135-375, 140-370, 145-365, 150-360, 155-355, 160-350, 165-345, 170-340, 175-335, 180-330, 185-325, 190-320, 195-315, 200-310, 205-305, 210-300, 215-295, 220-290, 225-285, 230-280, 235-275, 240-270, 245-265, and 250-260.

[0092] It is worth mentioning that in order to improve the weather resistance of microcrystalline glass, this embodiment proposes to control the glass phase ratio. However, if the glass phase ratio is too low in order to simply increase the crystal ratio, the glass phase composition will be uncontrollable, and the following defects will occur: 1. The glass phase composition contains a large amount of alkali metals, and the network formers such as Si and Al account for a relatively small proportion, which makes the glass less resistant and produces ion precipitates during subsequent processing and use, affecting practical applications; 2. Due to its own characteristics, the glass phase is the main force for stress changes caused by ion exchange during chemical strengthening. A low glass phase ratio means that the ion channels are reduced, which hinders ion exchange; at the same time, the higher content of alkali metals and alkaline earth metal oxides in the glass phase composition is also an obstacle to ion exchange channels.

[0093] Based on this, this embodiment also proposes a coordinated optimization of the glass phase components, and designs the contents of network formers, network intermediates, and network exosomes in the glass phase to satisfy the above-mentioned relationship. Then, cations can exist stably in the glass phase, making the microcrystalline glass have better reliability and endurance.

[0094] In an optional implementation manner of this embodiment, the crystalline phase includes at least one of the following: lithium disilicate, petalite, quartz and quartz solid solution, spodumene, lithium metasilicate, nautilus, spinel, wollastonite, and cordierite.

[0095] In an optional implementation manner of this embodiment, the network former includes at least one of the following: SiO2, Al2O3, B2O3, P2O5.

[0096] Furthermore, in an optional implementation manner of this embodiment, the calculation formula for the mass percentage content of the network former is expressed as:

[0097] F=(A-68.9%*a-76.8%*b-63.8%*c-60.4%*de)+(B-12.7*a-36.1*d)+C+D;

[0098] Among them, a represents the mass percentage of the petalite crystal phase in the entire microcrystalline glass, b represents the mass percentage of the lithium disilicate crystal phase in the entire microcrystalline glass, c represents the mass percentage of the lithium silicate crystal phase in the entire microcrystalline glass, d represents the mass percentage of the spodumene crystal phase in the entire microcrystalline glass, e represents the mass percentage of the quartz crystal phase in the entire microcrystalline glass, A represents the mass percentage of SiO2, B represents the mass percentage of Al2O3, C represents the mass percentage of B2O3, and D represents the mass percentage of P2O5.

[0099] In an optional implementation manner of this embodiment, the network intermediate includes at least one of the following: TiO2, ZrO2, Y2O3, and La2O3.

[0100] Furthermore, in an optional implementation manner of this embodiment, the calculation formula for the mass percentage content of the network intermediate is expressed as:

[0101] I=H+J+K+L;

[0102] Wherein, H represents the mass percentage of TiO2, J represents the mass percentage of ZrO2, K represents the mass percentage of Y2O3, and L represents the mass percentage of La2O3.

[0103] In an optional implementation manner of this embodiment, the network outer body includes: Li2O, Na2O, K2O and RO, and RO includes at least one of CaO, MgO, ZnO, and BaO.

[0104] Furthermore, in an optional implementation manner of this embodiment, the calculation formula for the mass percentage content of the network exosome is expressed as:

[0105] M=(O-4.9*a-19.9*b-33.2*c-8.0*d)+P+Q+R;

[0106] Among them, a represents the mass percentage of the petalite crystal phase in the entire microcrystalline glass, b represents the mass percentage of the lithium disilicate crystal phase in the entire microcrystalline glass, c represents the mass percentage of the lithium silicate crystal phase in the entire microcrystalline glass, d represents the mass percentage of the spodumene crystal phase in the entire microcrystalline glass, O represents the mass percentage of Li2O, P represents the mass percentage of Na2O, Q represents the mass percentage of K2O, and R represents the mass percentage of RO.

[0107] Furthermore, in an optional implementation manner of this embodiment, the microcrystalline glass satisfies the following relationship: τ = (A-78.5*a-80.1*b-66.8*c-64.6*de)+(B-16.7*a-27.4*d)+(w*F+x*I+y*M)

[0108] / (O-4.9*a-19.9*b-33.2*c-8.0*d);

[0109] 17<τ<98;

[0110] Wherein, τ represents the reliability evaluation index, a represents the mass percentage of the petalite crystal phase in the entire glass-ceramics, b represents the mass percentage of the lithium disilicate crystal phase in the entire glass-ceramics, c represents the mass percentage of the lithium silicate crystal phase in the entire glass-ceramics, d represents the mass percentage of the spodumene crystal phase in the entire glass-ceramics, e represents the mass percentage of the quartz crystal phase in the entire glass-ceramics, A represents the mass percentage of SiO2, B represents the mass percentage of Al2O3, O represents the mass percentage of Li2O, M represents the mass percentage of the network former, N represents the mass percentage of the network intermediate, Z represents the mass percentage of the network outer body, w = 0.15 ~ 0.76, x = 12.7 ~ 38.5, y = 2.4 ~ 19.5;

[0111] Furthermore, the mass percentage wt(i) of a certain oxide component in the glass-ceramics satisfies the following relationship:

[0112] wt(i)=M(i)*n(i) / (∑M(x)*n(x));

[0113] Wherein, M(i) and n(i) are the molar mass and molar percentage of a certain oxide component in the glass-ceramics, respectively; M(x) and n(x) are the molar mass and molar percentage of any other oxide component in the glass-ceramics, respectively.

[0114] In an optional implementation manner of this embodiment, the value of τ can be 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97. In addition, the value range of τ can be 18-97, 20-95, 25-90, 30-85, 35-80, 40-75, 45-70, 50-65, 55-60.

[0115] Through research, the applicant found that a higher Li content is beneficial to ion exchange during chemical strengthening, but an excessively high Li content will increase the risk of precipitates forming in the glass phase in a more severe water vapor environment. Based on theoretical calculations and actual experimental results, the applicant proposed a reliability evaluation index τ to guide the control of Li content in the glass formulation and crystallization process, thereby facilitating the regulation of the reliability and reliability of the glass phase.

[0116] In an optional implementation manner of this embodiment, the glass-ceramics satisfies the following relationship:

[0117] X=n[(Li2O)+9*n(Na2O)+13*n(K2O)] / 33*n(RO)];

[0118] 0<X<0.03;

[0119] Wherein, X represents an ion exchange capacity evaluation index, n(Li2O) represents the molar percentage of the Li2O component, n(Na2O) represents the molar percentage of the Na2O component, n(K2O) represents the molar percentage of the K2O component, and n(RO) represents the molar percentage of the alkaline earth metal oxide component.

[0120] In an optional implementation manner of this embodiment, the value of X can be 0.01, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019, 0.02, 0.021, 0.022, 0.023, 0.024, 0.025, 0.026, 0.027, 0.028, 0. 029. In addition, the value range of X can be 0.01~0.029, 0.011~0.028, 0.012~0.027, 0.013~0.026, 0.014~0.025, 0.015~0.024, 0.016~0.023, 0.017~0.022, 0.018~0.021, and 0.019~0.02.

[0121] The applicants' research has found that the mixed alkali effect can improve the chemical stability of glass, enhance mechanical strength, increase the degree of glass atom stacking, reduce alkali metal migration, and inhibit the formation of corrosion products (such as sodium silicate). Furthermore, alkaline earth metal oxides can enhance relaxation and disperse the glass network, helping to build ion channels and accelerate ion exchange efficiency. In this embodiment, the contents of alkali metal oxides and alkaline earth metal oxide components are designed to satisfy the above relationship, resulting in a glass-ceramic with good ion exchange capacity.

[0122] The components of the microcrystalline glass of this embodiment, measured in molar percentage, include: SiO2 greater than or equal to 60% and less than or equal to 78%; Al2O3 greater than or equal to 1.5% and less than or equal to 5.5%; Li2O greater than or equal to 18% and less than or equal to 26.8%; P2O5 greater than or equal to 0.1% and less than or equal to 2.5%; ZrO2 greater than or equal to 0 and less than or equal to 5%; RO greater than or equal to 0 and less than or equal to 3.4%, and RO includes at least one of CaO, MgO, ZnO, and BaO; Na2O greater than or equal to 0 and less than or equal to 6.5%; K2O greater than or equal to 0 and less than or equal to 4%; and a clarifier greater than or equal to 0 and less than or equal to 1%.

[0123] SiO2 is a basic component of the glass composition provided in this application. It is a network structure former of glass and glass-ceramics and can form lithium silicate and lithium disilicate after crystallization. It should be noted that if the SiO2 content is low, the crystals formed in the glass-ceramics will be fewer and the crystals will be more coarse, affecting the haze and drop ball test height of the glass-ceramics and glass-ceramics products. Therefore, the lower limit of the SiO2 content is set at 60%. In addition, if the SiO2 content is higher than a certain level, the glass melting temperature will be high, the material will be difficult to form, and it will not be easy to form, affecting the consistency of the glass. Therefore, the upper limit of the SiO2 content is set at 78%. In some embodiments, the glass composition may contain about 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, or 78% SiO2. In some embodiments, the glass composition may further include SiO2 in an amount such as greater than or equal to 61% and less than or equal to 77%, greater than or equal to 62% and less than or equal to 76%, greater than or equal to 63% and less than or equal to 75%, greater than or equal to 64% and less than or equal to 74%, greater than or equal to 65% and less than or equal to 73%, greater than or equal to 66% and less than or equal to 72%, greater than or equal to 67% and less than or equal to 71%, or greater than or equal to 68% and less than or equal to 70%.

[0124] Al2O3 can be a component that forms the glass network structure or a cationic network member that acts as a charge balancer. In this application, Al2O3 is fully incorporated into the glass network structure, increasing the depth of the ion exchange layer and the surface compressive stress of the glass-ceramic product, enhancing the chemical stability of the glass, and improving its mechanical properties. On the one hand, if its content is below a certain level, it will result in poor results. Therefore, the lower limit of the Al2O3 content by mass is 1.5%. On the other hand, if the Al2O3 content is above a certain level, the glass's meltability and resistance to devitrification will be reduced, and the crystals will tend to grow larger during crystallization, reducing the strength of the glass-ceramic and glass-ceramic products. Therefore, the upper limit of the Al2O3 content is 5.5%. In some embodiments, the glass composition may contain approximately 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, or 5.5%. In some embodiments, the glass composition may further include Al2O3 in an amount such as greater than or equal to 2% and less than or equal to 5%, 2.5% and less than or equal to 4.5%, or greater than or equal to 3% and less than or equal to 4%.

[0125] Li2O is an essential component that forms a crystalline phase upon crystallization, contributing to the formation of lithium-containing crystalline phases such as lithium disilicate, petalite, and lithium silicate. It is also essential for chemical strengthening. However, if its content falls below a certain level, the effect is poor. Therefore, the lower limit of the Li2O content is 18%. Furthermore, if its content exceeds a certain level, the chemical stability of the glass is negatively impacted. Therefore, the upper limit of the Li2O content is preferably 26.8%. In some embodiments, the glass composition may include approximately 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, or 26.8% Li2O. In some embodiments, the glass composition may further include Li2O in an amount such as greater than or equal to 18.5% and less than or equal to 26.5%, greater than or equal to 19% and less than or equal to 26%, greater than or equal to 19.5% and less than or equal to 25.5%, greater than or equal to 20% and less than or equal to 25%, greater than or equal to 20.5% and less than or equal to 24.5%, greater than or equal to 21% and less than or equal to 24%, greater than or equal to 21.5% and less than or equal to 23.5%, or greater than or equal to 22% and less than or equal to 23%.

[0126] P2O5 helps improve the low-temperature melting property of glass, can phase separate and form crystal nuclei in the glass, and improve the thermal expansion stability of the glass during the crystallization process. The lower limit of the P2O5 content may be 0.1%. If the P2O5 content is too high, the devitrification resistance of the glass will be reduced, phase separation of the glass will occur, and the mechanical properties of the glass will tend to deteriorate. Therefore, the upper limit of the P2O5 content is 2.5%. In some embodiments, the glass composition may include approximately 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, or 2.5% P2O5. In some embodiments, the glass composition may further include PO in an amount such as greater than or equal to 0.2% and less than or equal to 2.4%, greater than or equal to 0.3% and less than or equal to 2.3%, greater than or equal to 0.4% and less than or equal to 2.2%, greater than or equal to 0.5% and less than or equal to 2.1%, greater than or equal to 0.6% and less than or equal to 2.0%, greater than or equal to 0.7% and less than or equal to 1.9%, greater than or equal to 0.8% and less than or equal to 1.8%, greater than or equal to 0.9% and less than or equal to 1.7%, greater than or equal to 1.0% and less than or equal to 1.6%, greater than or equal to 1.1% and less than or equal to 1.5%, greater than or equal to 1.2% and less than or equal to 1.4%.

[0127] ZrO2 acts as a nucleating agent and helps improve the chemical stability of the glass. In this embodiment, the lower limit of the ZrO2 content can be 0. However, if too much ZrO2 is contained, the glass's resistance to devitrification can be easily reduced, and the control of the glass crystallization process becomes more difficult, requiring an increase in the crystallization temperature. Therefore, the upper limit of the ZrO2 content is 5%. In some embodiments, the glass composition may include approximately 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5% ZrO2. In some embodiments, the glass composition may also include ZrO2 in amounts such as: greater than or equal to 0.5% and less than or equal to 4.5%, greater than or equal to 1% and less than or equal to 4%, greater than or equal to 1.5% and less than or equal to 3.5%, or greater than or equal to 2% and less than or equal to 3%.

[0128] Na2O helps lower the glass transition temperature and crystallization temperature and inhibits the precipitation of unintended impurities. Its lower limit can be 0. However, if the Na2O content is too high, it increases the thermal expansion coefficient of the glass and reduces its thermal stability. Therefore, its upper limit is set at 6.5%. In some embodiments, the glass composition may include approximately 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, or 6.5% Na2O. In some embodiments, the glass composition may also include Na2O in amounts such as greater than or equal to 0.5% and less than or equal to 6%, greater than or equal to 1% and less than or equal to 5.5%, greater than or equal to 1.5% and less than or equal to 5%, greater than or equal to 2% and less than or equal to 4.5%, greater than or equal to 2.5% and less than or equal to 4%, or greater than or equal to 3% and less than or equal to 3.5%.

[0129] This embodiment optionally introduces 0-4% molar percentage of K2O into the glass composition, for example, 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, and 4% K2O. In some embodiments, the glass composition may further include K2O in amounts such as: greater than or equal to 0.5% and less than or equal to 4%, greater than or equal to 1% and less than or equal to 3.5%, greater than or equal to 1.5% and less than or equal to 3%, and greater than or equal to 2% and less than or equal to 2.5%. It is worth noting that the presence of multiple alkali metal oxides in the glass composition can exert a mixed alkali effect during the chemical strengthening of the glass-ceramics, restricting the migration of alkali metal ions during ion diffusion and helping to improve the chemical stability of the glass. Furthermore, the interaction of multiple alkali metal oxides can enhance the low-temperature melting and formability of the glass, and has a certain effect on lowering the softening point and molding temperature of the glass, thereby reducing the difficulty of chemical strengthening the glass-ceramics.

[0130] RO is an alkaline earth metal oxide, including at least one of CaO, MgO, ZnO, and BaO. CaO helps reduce the high-temperature viscosity of the glass and increase its density; MgO helps reduce the viscosity of the glass, inhibits crystallization during glass forming, and improves low-temperature melting properties; ZnO improves the melting properties of the glass, improves the chemical stability of the glass, and refines the grain size during crystallization; and BaO improves the glass's glass-forming properties. The lower limit of the alkaline earth metal oxide content is 0, and the upper limit is 3.4%. In some embodiments, the glass composition may include approximately 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, or 3.4% of the alkaline earth metal oxide. In some embodiments, the glass composition may also include alkaline earth metal oxides in amounts such as greater than or equal to 0.5% and less than or equal to 3%, greater than or equal to 1% and less than or equal to 2.5%, or greater than or equal to 1.5% and less than or equal to 2%.

[0131] The glass composition of this embodiment may further include a fining agent, comprising one or more of SnO2, Sb2O3, and CeO2. The lower limit of the fining agent content is 0% and the upper limit is 1%. In some embodiments, the glass composition may include approximately 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% of the fining agent. In some embodiments, the glass composition may further include a fining agent in an amount such as greater than or equal to 0.1% and less than or equal to 0.9%, greater than or equal to 0.2% and less than or equal to 0.8%, greater than or equal to 0.3% and less than or equal to 0.7%, or greater than or equal to 0.4% and less than or equal to 0.6%.

[0132] In an optional implementation manner of this embodiment, the components of the microcrystalline glass, expressed in molar percentage, further include: B2O3 greater than or equal to 0 and less than or equal to 4.8%; and / or, TiO2 greater than or equal to 0% and less than or equal to 4%; and / or, Y2O3 greater than or equal to 0 and less than or equal to 4%; and / or, La2O3 greater than or equal to 0 and less than or equal to 0.5%.

[0133] B2O3 can lower the melting temperature of glass and remain in the glass phase after crystallization, ensuring the structural stability of the glass phase and improving the chemical stability of microcrystalline glass. However, too much B2O3 will increase volatilization during the glass melting process and increase the difficulty of glass homogenization. Based on this, the upper limit of the B2O3 content is set at 4.8%. In some embodiments, the glass composition may contain approximately 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, and 4.8% B2O3. In some embodiments, the glass composition may also contain B2O3 in amounts such as: greater than or equal to 0.5% and less than or equal to 4.8%, greater than or equal to 1% and less than or equal to 4.5%, greater than or equal to 1.5% and less than or equal to 4%, greater than or equal to 2% and less than or equal to 3.5%, and greater than or equal to 2.5% and less than or equal to 3%.

[0134] TiO2 helps lower the melting temperature of glass and improve its chemical stability. By introducing less than 4% by mass of TiO2, the glass crystallization process can be easily controlled. This embodiment optionally includes approximately 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, or 4% TiO2. In some embodiments, the glass composition may further include TiO2 in amounts such as greater than or equal to 0.5% and less than or equal to 3.5%, greater than or equal to 1% and less than or equal to 3%, or greater than or equal to 1.5% and less than or equal to 2.5%.

[0135] An appropriate amount of Y2O3 can increase the density of the glass phase and enhance the overall strength of the glass-ceramics. However, if the Y2O3 content is too high, it will be difficult to obtain a large compressive stress value during the chemical strengthening treatment of the glass-ceramics. This embodiment optionally includes approximately 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, and 4% Y2O3. In some embodiments, the glass composition may also include Y2O3 in amounts such as greater than or equal to 0.5% and less than or equal to 3.5%, greater than or equal to 1% and less than or equal to 3%, and greater than or equal to 1.5% and less than or equal to 2.5%.

[0136] In an optional implementation manner of this embodiment, the microcrystalline glass also includes: La2O3, Nb2O5, Ta2O5, HfO2, and Bi2O3.

[0137] La2O3 has a high field strength and an accumulation effect, and can strongly attract surrounding non-bridging oxygen (NBO, i.e., broken Si-O bonds), making the glass structure denser. At the same time, it can form La-O bonds with higher bond strength, thereby improving the chemical stability of the glass. La2O3 is a commonly used oxide in optical glass, which can reduce dispersion and improve the optical properties of the glass. This embodiment optionally contains approximately 0, 0.1%, 0.15%, 0.25%, 0.3%, 0.5%, 1%, 1.5%, and 2% La2O3. In some embodiments, the glass composition may contain La2O3 and / or Y2O3 in the following content ranges: greater than or equal to 0% and less than or equal to 2%, greater than or equal to 0.1% and less than or equal to 1%, and greater than or equal to 0.15% and less than or equal to 0.3%.

[0138] Nb2O5 and TaO5 have high field strength and also have the function of improving chemical stability, reducing glass dispersion and improving optical properties. Among them, TaO5 has lower dispersion, higher Abbe number, and extremely strong corrosion resistance, which can significantly improve chemical stability. Nb2O5 also has the function of promoting melting and increasing glass hardness and scratch resistance. This embodiment optionally contains approximately 0, 0.1%, 0.15%, 0.25%, 0.3%, 0.5%, and 1% Nb2O5 and / or TaO5. In some embodiments, the glass composition may contain Nb2O5 and / or TaO5 in the following content ranges: greater than or equal to 0% and less than or equal to 1%, greater than or equal to 0.15% and less than or equal to 0.5%, and greater than or equal to 0.2% and less than or equal to 0.3%.

[0139] In addition to having a high field strength that can improve chemical stability, HfO also has strong absorption of ultraviolet wavelengths, which can improve radiation protection and has a significant effect on protecting human eye health. This embodiment optionally includes approximately 0%, 0.1%, 0.15%, 0.25%, 0.3%, 0.5%, and 1% HfO. In some embodiments, the glass composition may include HfO in the following content ranges: greater than or equal to 0% and less than or equal to 1%, greater than or equal to 0.15% and less than or equal to 0.5%, and greater than or equal to 0.2% and less than or equal to 0.3%.

[0140] BiO has the properties of an extremely high refractive index and low dispersion, and also has a relatively low melting point, which can reduce the crystallization temperature of the glass. This embodiment optionally includes approximately 0%, 0.1%, 0.15%, 0.25%, 0.3%, 0.5%, or 1% BiO. In some embodiments, the glass composition may include BiO in the following content ranges: greater than or equal to 0% and less than or equal to 1%, greater than or equal to 0.15% and less than or equal to 0.5%, and greater than or equal to 0.2% and less than or equal to 0.3%.

[0141] In an optional implementation manner of this embodiment, the components of the glass-ceramics, measured in molar percentage, include: Li2O greater than or equal to 22.2% and less than or equal to 25.8%, Na2O greater than or equal to 0 and less than or equal to 3.1%, and K2O greater than or equal to 0 and less than or equal to 1.2%. Furthermore, the components of the glass-ceramics, measured in molar percentage, satisfy the following relationship: Li2O / (Na2O+K2O)=0.8~20. Based on this content design, the mixed alkali effect can be fully utilized to improve the chemical stability of the glass-ceramics, such as acid and alkali resistance, water resistance, etc. Its values ​​can be 0.8, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 for example. In an optional embodiment, its value range can be 1-19, 2-18, 3-17, 4-16, 5-15, 6-14, 7-13, 8-12, 9-11.

[0142] In an optional embodiment, the crystallization lower limit temperature of the glass-ceramics of this embodiment is 553-639°C, and the crystallization upper limit temperature is 989-1123°C. The glass-ceramics meets at least one of the following performance indicators: elastic modulus greater than or equal to 99.87 GPa, shear modulus greater than or equal to 40.23 GPa, fracture toughness greater than or equal to 1.01 MPa·m 1 / 2 , Poisson's ratio is greater than or equal to 0.20.

[0143] In addition, the crystalline phase of the glass-ceramics is lithium disilicate, and the lithium disilicate crystalline phase meets the following indicators: an average grain size of less than or equal to 38 to 45.7 nm, and a crystallinity greater than or equal to 56.38%. Furthermore, the lithium disilicate crystalline phase meets the following indicators: 98% of the grains in the entire crystalline phase have a size of less than or equal to 60 nm, 95% of the grains in the entire crystalline phase have a size of less than or equal to 55 nm, and 80% of the grains in the entire crystalline phase have a size of less than or equal to 50 nm; and the crystallinity is greater than or equal to 61.22%.

[0144] Next, an embodiment of the present application further provides a chemically strengthened glass-ceramics, which is obtained by ion exchange treatment based on the glass-ceramics provided by the aforementioned embodiment.

[0145] In an optional implementation manner of this embodiment, the chemically strengthened microcrystalline glass meets the following mechanical performance indicators: surface compressive stress value is 240~276MPa, the compressive stress value at a depth of 50μm from the surface is 102~125MPa, the compressive stress value at a depth of 80μm from the surface is 65~75MPa, the depth of the compressive stress layer is 113~130μm, the absolute value of the maximum tensile stress is 105~108MPa, and the absolute value of the average tensile stress is 58~63MPa; when the thickness is 0.55mm, the drop test height of the whole machine based on 80-mesh sandpaper is greater than 1100mm; when the thickness is 0.55mm, the drop test height of the whole machine based on 180-mesh sandpaper is greater than 1500mm, the four-point bending test strength is greater than 1120MPa, and the nine-point drop ball test height based on a 32g steel ball is greater than 1300mm.

[0146] In an optional implementation manner of this embodiment, the chemically strengthened microcrystalline glass meets the following optical performance indicators: the transmittance of visible light with a wavelength of 550nm when the thickness is 0.55mm is greater than or equal to 91.05%, the |B| value is less than or equal to 0.57%, and the haze is less than or equal to 0.14%; and the chemically strengthened microcrystalline glass with a thickness of 0.55mm meets the following performance indicators after 120 hours of double 85 test: the transmittance of visible light with a wavelength of 550nm is greater than or equal to 91.04%, the |B| value is less than or equal to 0.55%, and the haze is less than or equal to 0.15%.

[0147] In this embodiment, when chemically strengthening the microcrystalline glass, the chemical strengthening salt bath includes, by mass percentage: KNO3 greater than or equal to 9.99% and less than or equal to 39.99%, NaNO3 greater than or equal to 59.99 and less than or equal to 89.99%, and LiNO3 greater than or equal to 0.03% and less than or equal to 0.1%. The temperature of the chemical strengthening salt bath is 460-490°C, and the duration of the ion exchange treatment is 4-10 hours.

[0148] Chemical strengthening refers to placing the microcrystalline glass in a salt bath for ion exchange treatment, so that the microcrystalline glass forms a compressive stress layer and a tensile stress layer. The salt bath in this embodiment is a mixed salt bath. Compared with the traditional multiple strengthening, this embodiment can simultaneously complete multiple ion exchange behaviors between the salt bath and the microcrystalline glass through a single strengthening process, thereby improving the chemical strengthening efficiency and reducing the amount of salt bath used. After chemical strengthening treatment, the chemically strengthened microcrystalline glass obtained has a deeper compressive stress layer depth and a higher surface compressive stress. In an optional implementation manner of this embodiment, the ratio of the surface compressive stress value to the compressive stress layer depth is greater than or equal to 7.5.

[0149] Accordingly, an embodiment of the present application further provides a glass preparation method, which specifically includes:

[0150] Step A: Mix the raw materials uniformly according to the glass formula, melt them at a preset melting temperature and melting time, and then form and anneal them to obtain a precursor glass;

[0151] Step B: heat-treating the precursor glass to obtain glass-ceramics.

[0152] The glass-ceramics includes a glass phase and a crystalline phase. The proportion of the glass phase in the glass-ceramics is 10-50% by mass. The composition of the glass phase satisfies the following relationship:

[0153] t=(19.8*F+16.7*I) / (0.43*M),

[0154] 130<t<380;

[0155] Wherein, F represents the mass percentage content of the network former in the glass phase, I represents the mass percentage content of the network intermediate in the glass phase, M represents the mass percentage content of the network exosome in the glass phase, and F = 22% to 48%, I = 1% to 12%, and M = 2% to 10%.

[0156] Furthermore, the glass formula comprises, in mole percentage, the following: SiO2 greater than or equal to 60% and less than or equal to 78%; Al2O3 greater than or equal to 1.5% and less than or equal to 5.5%; Li2O greater than or equal to 18% and less than or equal to 26.8%; P2O5 greater than or equal to 0.1% and less than or equal to 2.5%; ZrO2 greater than or equal to 0 and less than or equal to 5%; RO greater than or equal to 0 and less than or equal to 3.4%, and RO comprises at least one of CaO, MgO, ZnO, and BaO; Na2O greater than or equal to 0 and less than or equal to 6.5%; K2O greater than or equal to 0 and less than or equal to 4%; and fining agent greater than or equal to 0 and less than or equal to 1%.

[0157] In actual applications, glass raw materials are first prepared according to the glass components and contents provided in the aforementioned embodiments, and the glass raw materials are evenly mixed and melted at 1350-1550°C. The precursor glass is then obtained after clarification, homogenization, forming, and annealing. Then, the precursor glass is crystallized using a two-stage heat treatment method. The first step of the heat treatment is a nucleation treatment, and the second step of the heat treatment is a crystallization treatment. The glass is then cooled to room temperature to obtain microcrystalline glass that meets the expected crystallinity, grain size, and crystal phase ratio.

[0158] In addition, the above-mentioned heat treatment process may include: placing the precursor glass in a crystallization furnace, heating it to 560-590°C at a heating rate of 8-12°C / min and then keeping it warm for 220-250 minutes, then heating it to 750-790°C at a heating rate of 8-12°C / min and then keeping it warm for 70-90 minutes, and finally cooling it at a cooling rate less than or equal to 2°C / min.

[0159] It is worth mentioning that the microcrystalline glass obtained in the above step B can be further cold-processed, that is, through shaping, multi-wire cutting, CNC, grinding, rough grinding, fine polishing, cleaning and other processes, to obtain microcrystalline glass with a thickness of 0.35 to 0.7 mm. The preferred thickness of this embodiment can be 0.55 mm.

[0160] In an optional implementation manner of this embodiment, the above-mentioned glass preparation method further includes: step C, immersing the microcrystalline glass in a chemical strengthening salt bath for ion exchange treatment to obtain chemically strengthened microcrystalline glass.

[0161] In this embodiment, when chemically strengthening the microcrystalline glass, the chemical strengthening salt bath includes, by mass percentage: KNO3 greater than or equal to 9.99% and less than or equal to 39.99%, NaNO3 greater than or equal to 59.99 and less than or equal to 89.99%, and LiNO3 greater than or equal to 0.03% and less than or equal to 0.1%. The temperature of the chemical strengthening salt bath is 460-490°C, and the duration of the ion exchange treatment is 4-10 hours.

[0162] Chemical strengthening involves placing glass-ceramics in a salt bath for ion exchange, which results in the formation of compressive and tensile stress layers. The salt bath in this embodiment is a mixed salt bath. Compared to traditional multiple strengthening processes, this embodiment achieves multiple ion exchange events between the salt bath and the glass-ceramics in a single strengthening step, improving chemical strengthening efficiency and reducing salt bath usage. The resulting chemically strengthened glass-ceramics exhibit a deeper compressive stress layer and higher surface compressive stress.

[0163] It is worth mentioning that for chemically strengthened glass-ceramics, after being taken out of the salt bath, the surface residual substances can be cleaned first, and then the surface can be re-grinded using a flat grinder. The relevant parameters of the re-grinding process are set as follows: the surface is white, the hardness is 75, the upper and lower grinding discs are both 10 rpm, and the grinding powder concentration is 1.13 g / cm 3 , pressure 150-250kg, re-grinding number of 100-300 laps. Finally, the chemically strengthened micro-ceramic glass can be cleaned with a neutral cleaning agent with a pH of 7-9 to obtain chemically strengthened micro-ceramic glass products.

[0164] In an optional implementation manner of this embodiment, the above-mentioned glass preparation method also includes: hot bending the microcrystalline glass through a hot bending workstation; wherein the pressure of the hot bending workstation is 0.7~1.1MPa, and the operating time of a single workstation is 70~110s.

[0165] In an optional implementation manner of this embodiment, the hot bending treatment needs to go through four preheating workstations, three hot pressing workstations and two cooling workstations; among them, the operating temperature of the first preheating workstation is 430~470℃, the operating temperature of the second preheating workstation is 530~570℃, the operating temperature of the third preheating workstation is 630~670℃, the operating temperature of the fourth preheating workstation is 710~730℃, the operating temperature of the first hot pressing workstation is 740~760℃, the operating temperature of the second hot pressing workstation is 740~760℃, the operating temperature of the third hot pressing workstation is 580~620℃, the operating temperature of the first cooling workstation is 430~470℃, and the operating temperature of the second cooling workstation is 280~320℃.

[0166] Next, in order to illustrate the technical effects of the highly reliable microcrystalline glass and chemically strengthened microcrystalline glass of the embodiments of the present application, the present application conducted tests on glass products with different component contents to determine their properties. The comparative examples and Examples 1 to 8 in Table 1 show the relevant test conditions and test data of the microcrystalline glass with different component contents of the present application.

[0167] Table 1

[0168]

[0169]

[0170]

[0171]

[0172] like Figure 1 The DSC test curve of the glass-ceramics of Example 4 is shown. In the DSC test spectrum of the corresponding prepared glass-ceramics, the temperature of the first endothermic peak is 511.4°C, and the temperature of the first exothermic peak is 620°C. Figure 2 The figure shows the XRD test curve of the glass-ceramics corresponding to Example 4. It can be seen from the figure that the glass-ceramics provided by the present application has a lithium disilicate crystal phase. Figure 3 The figure shows a scanning electron microscope image of the glass-ceramics corresponding to Example 4. It can be seen from the figure that the grain size of the lithium disilicate crystal phase provided by the present application is less than 60nm; Figure 4 Shown is a viscosity-temperature characteristic diagram of the microcrystalline glass corresponding to Example 4, which is used to characterize the viscosity-temperature characteristics of the product.

[0173] With reference to the mechanical property data (i.e., Vickers hardness, fracture toughness, Young's modulus, shear modulus, Poisson's ratio) and optical property data (i.e., refractive index, |B| value, haze, transmittance) provided in the comparative examples and examples in Table 1 above, it can be seen that after optimizing the glass component content with reference to the aforementioned t calculation formula, τ calculation formula, and X calculation formula, the mechanical properties (i.e., elastic modulus, shear modulus, fracture toughness, surface compressive stress, drop ball impact height, etc.) and optical properties (i.e., transmittance, haze, B value, etc.) of the microcrystalline glass products obtained in the examples of the present application are improved compared to traditional glass. Effectively improved. For the chemically strengthened glass provided in the embodiments of the present application, typically, the transmittance decrease ratio after passing the double 85 test is less than or equal to 1%, which shows relatively excellent chemical resistance. In addition, the drop height of the 80-grit sandpaper is greater than or equal to 1100mm, which shows relatively excellent drop resistance. In addition, the four-point bending test strength is greater than 1120MPa, which shows relatively excellent bending resistance. In addition, the nine-point drop ball test height is greater than or equal to 1300mm, which shows relatively excellent impact resistance. It can be seen that the micro-ceramic glass product with the optimized design of the present application has good durability.

[0174] It is also worth mentioning that due to the above-mentioned performance advantages of the chemically strengthened microcrystalline glass provided in the embodiments of the present application, it can be widely used in the production of protective covers of electronic devices, optical elements, photovoltaic devices or windows of household appliances.

[0175] Finally, it should be noted that in the above embodiments, the description of each embodiment has its own focus. For parts that are not described in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0176] The above is a description of the microcrystalline glass with high reliability and durability, chemically strengthened microcrystalline glass and glass preparation method provided by this application. For those skilled in the art, based on the ideas of the embodiments of this application, equivalent substitutions made in the specific implementation methods and application scopes should all be covered by the scope of the claims of this application. In summary, the content of this specification should not be understood as a limitation on the scheme of this application.

Claims

1. A glass-ceramic with high reliability, characterized in that: The glass-ceramics includes a glass phase and a crystalline phase. The proportion of the glass phase in the glass-ceramics is 10-50% by mass. The composition of the glass phase satisfies the following relationship: t=(19.8*F+16.7*I) / (0.43*M), 130＜t＜380； Wherein, F represents the mass percentage content of the network former in the glass phase, I represents the mass percentage content of the network intermediate in the glass phase, M represents the mass percentage content of the network exosome in the glass phase, and F = 22% to 48%, I = 1% to 12%, and M = 2% to 10%.

2. The glass-ceramic according to claim 1, characterized in that The network former includes at least one of the following: SiO2, Al2O3, B2O3, and P2O5.

3. The glass-ceramic according to claim 2, characterized in that: The calculation formula of the mass percentage content of the network former is expressed as: F=(A-68.9%*a-76.8%*b-63.8%*c-60.4%*de)+(B-12.7*a-36.1*d)+C+D; Among them, a represents the mass percentage of the petalite crystal phase in the entire microcrystalline glass, b represents the mass percentage of the lithium disilicate crystal phase in the entire microcrystalline glass, c represents the mass percentage of the lithium silicate crystal phase in the entire microcrystalline glass, d represents the mass percentage of the spodumene crystal phase in the entire microcrystalline glass, e represents the mass percentage of the quartz crystal phase in the entire microcrystalline glass, A represents the mass percentage of SiO2, B represents the mass percentage of Al2O3, C represents the mass percentage of B2O3, and D represents the mass percentage of P2O5.

4. The glass-ceramic according to claim 1, characterized in that The network intermediate includes at least one of the following: TiO2, ZrO2, Y2O3, and La2O3.

5. The glass-ceramic according to claim 1, characterized in that: The network outer body includes: Li2O, Na2O, K2O and RO, and RO includes at least one of CaO, MgO, ZnO and BaO.

6. The glass-ceramic according to claim 5, characterized in that: The calculation formula of the mass percentage content of the network exosome is expressed as: M=(O-4.9*a-19.9*b-33.2*c-8.0*d)+P+Q+R; Among them, a represents the mass percentage of the petalite crystal phase in the entire microcrystalline glass, b represents the mass percentage of the lithium disilicate crystal phase in the entire microcrystalline glass, c represents the mass percentage of the lithium silicate crystal phase in the entire microcrystalline glass, d represents the mass percentage of the spodumene crystal phase in the entire microcrystalline glass, O represents the mass percentage of Li2O, P represents the mass percentage of Na2O, Q represents the mass percentage of K2O, and R represents the mass percentage of RO.

7. The glass-ceramic according to claim 1, characterized in that: The crystalline phase includes at least one of the following: lithium disilicate, petalite, quartz and quartz solid solution, spodumene, lithium metasilicate, nautilus, spinel, wollastonite, and cordierite.

8. The glass-ceramic according to claim 1, characterized in that: The glass-ceramics satisfies the following relationship: τ=(A-78.5*a-80.1*b-66.8*c-64.6*de)+(B-16.7*a-27.4*d)+(w*F+x*I+y*M) / (O-4.9*a-19.9*b-33.2*c-8.0*d); 17<τ<98; Wherein, τ represents the reliability evaluation index, a represents the mass percentage of the petalite crystal phase in the entire glass-ceramics, b represents the mass percentage of the lithium disilicate crystal phase in the entire glass-ceramics, c represents the mass percentage of the lithium silicate crystal phase in the entire glass-ceramics, d represents the mass percentage of the spodumene crystal phase in the entire glass-ceramics, e represents the mass percentage of the quartz crystal phase in the entire glass-ceramics, A represents the mass percentage of SiO2, B represents the mass percentage of Al2O3, O represents the mass percentage of Li2O, M represents the mass percentage of the network former, N represents the mass percentage of the network intermediate, Z represents the mass percentage of the network outer body, w = 0.15 ~ 0.76, x = 12.7 ~ 38.5, y = 2.4 ~ 19.5; Furthermore, the mass percentage wt(i) of a certain oxide component in the glass-ceramics satisfies the following relationship: wt(i)=M(i)*n(i) / (∑M(x)*n(x)); Wherein, M(i) and n(i) are respectively the molar mass and molar percentage of a certain oxide component in the microcrystalline glass, and M(x) and n(x) are respectively the molar mass and molar percentage of any other oxide component in the microcrystalline glass.

9. The glass-ceramic according to claim 1, characterized in that: The glass-ceramics satisfies the following relationship: X=n[(Li2O)+9*n(Na2O)+13*n(K2O)] / 33*n(RO)]; 0＜X＜0.03； Wherein, X represents an ion exchange capacity evaluation index, n(Li2O) represents the molar percentage of the Li2O component, n(Na2O) represents the molar percentage of the Na2O component, n(K2O) represents the molar percentage of the K2O component, and n(RO) represents the molar percentage of the alkaline earth metal oxide component.

10. The glass-ceramic according to claim 1, characterized in that: Its components, expressed in mole percentage, include: SiO2 greater than or equal to 60% and less than or equal to 78%; 1.5% or more and 5.5% or less of Al2O3; 18% or more and 26.8% or less of Li2O; P2O5 greater than or equal to 0.1% and less than or equal to 2.5%; ZrO2 greater than or equal to 0 and less than or equal to 5%; RO is greater than or equal to 0 and less than or equal to 3.4%, and RO includes at least one of CaO, MgO, ZnO, and BaO; greater than or equal to 0 and less than or equal to 6.5% Na2O; K2O greater than or equal to 0 and less than or equal to 4%; Greater than or equal to 0 and less than or equal to 1% of clarifier.

11. The glass-ceramic according to claim 10, characterized in that: The components of the microcrystalline glass, expressed in molar percentage, also include: greater than or equal to 0 and less than or equal to 4.8% B2O3; and / or, greater than or equal to 0% and less than or equal to 4% TiO2; and / or, greater than or equal to 0 and less than or equal to 4% Y2O3; and / or, greater than or equal to 0 and less than or equal to 0.5% La2O3.

12. The glass-ceramic according to claim 10, characterized in that: The components of the microcrystalline glass include, by mole percentage, greater than or equal to 22.2% and less than or equal to 25.8% of Li2O, greater than or equal to 0 and less than or equal to 3.1% of Na2O, and greater than or equal to 0 and less than or equal to 1.2% of K2O.

13. The glass-ceramic according to claim 10, characterized in that: The composition of the glass phase, expressed in molar percentage, satisfies the following relationship: Li2O / (Na2O+K2O)=0.8-20.

14. The glass-ceramic according to claim 1, characterized in that The crystal phase is lithium disilicate, and the lithium disilicate crystal phase meets the following indicators: an average grain size is less than or equal to 38 to 45.7 nm, and a crystallinity is greater than or equal to 56.38%.

15. The glass-ceramic according to claim 14, characterized in that: The lithium disilicate crystalline phase meets the following indicators: the size of 98% of the grains in the overall crystalline phase is less than or equal to 60 nm, the size of 95% of the grains in the overall crystalline phase is less than or equal to 55 nm, and the size of 80% of the grains in the overall crystalline phase is less than or equal to 50 nm; the crystallinity is greater than or equal to 61.22%.

16. The glass-ceramic according to any one of claims 1 to 15, characterized in that: The lower limit crystallization temperature of the microcrystalline glass is 553-639°C, and the upper limit crystallization temperature is 989-1123°C.

17. The glass-ceramic according to any one of claims 1 to 15, characterized in that: Meet the following performance indicators: elastic modulus greater than or equal to 99.87GPa, shear modulus greater than or equal to 40.23GPa, fracture toughness greater than or equal to 1.01Mpa·m 1 / 2 , Poisson's ratio is greater than or equal to 0.

20.

18. A chemically strengthened glass-ceramic with high reliability, characterized in that: The chemically strengthened glass-ceramics is obtained by subjecting the glass-ceramics according to any one of claims 1 to 17 to ion exchange treatment.

19. The chemically strengthened glass-ceramics according to claim 18, wherein The ratio of the surface compressive stress value to the depth of the compressive stress layer is greater than or equal to 7.

5.

20. The chemically strengthened glass-ceramics according to claim 18, wherein The surface compressive stress value is 240~276MPa, the compressive stress value at a depth of 50μm from the surface is 102~125MPa, the compressive stress value at a depth of 80μm from the surface is 65~75MPa, the depth of the compressive stress layer is 113~130μm, the absolute value of the maximum tensile stress is 105~108MPa, and the absolute value of the average tensile stress is 58~63MPa.

21. The chemically strengthened glass-ceramics according to claim 18, wherein Meets the following performance indicators: When the thickness is 0.55mm, the whole machine drop test height based on 80-grit sandpaper is greater than 1100mm; when the thickness is 0.55mm, the whole machine drop test height based on 180-grit sandpaper is greater than 1500mm; the four-point bending test strength is greater than 1120MPa; the nine-point drop ball test height based on a 32g steel ball is greater than 1300mm.

22. The chemically strengthened glass-ceramics according to claim 18, wherein Meet the following performance indicators: transmittance of visible light with a wavelength of 550nm at a thickness of 0.55mm is greater than or equal to 91.05%, |B| value is less than or equal to 0.57%, and haze is less than or equal to 0.14%; In addition, the chemically strengthened microcrystalline glass with a thickness of 0.55 mm meets the following performance indicators after 120 hours of double 85 test: the transmittance of visible light with a wavelength of 550 nm is greater than or equal to 91.04%, the |B| value is less than or equal to 0.55%, and the haze is less than or equal to 0.15%.

23. A method for preparing glass, characterized in that: include: The raw materials are mixed evenly according to the glass formula, melted at a preset melting temperature and melting time, and then formed and annealed to obtain a precursor glass; heat-treating the precursor glass to obtain glass-ceramics; The glass-ceramics includes a glass phase and a crystalline phase. The proportion of the glass phase in the glass-ceramics is 10-50% by mass. The composition of the glass phase satisfies the following relationship: t=(19.8*F+16.7*I) / (0.43*M), 130＜t＜380； Wherein, F represents the mass percentage content of the network former in the glass phase, I represents the mass percentage content of the network intermediate in the glass phase, M represents the mass percentage content of the network exosome in the glass phase, and F = 22% to 48%, I = 1% to 12%, and M = 2% to 10%.

24. The glass preparation method according to claim 23, characterized in that: The glass formulation comprises, in mole percentage: SiO2 greater than or equal to 60% and less than or equal to 78%; 1.5% or more and 5.5% or less of Al2O3; 18% or more and 26.8% or less of Li2O; P2O5 greater than or equal to 0.1% and less than or equal to 2.5%; ZrO2 greater than or equal to 0 and less than or equal to 5%; RO is greater than or equal to 0 and less than or equal to 3.4%, and RO includes at least one of CaO, MgO, ZnO, and BaO; greater than or equal to 0 and less than or equal to 6.5% Na2O; K2O greater than or equal to 0 and less than or equal to 4%; Greater than or equal to 0 and less than or equal to 1% of clarifier.

25. The glass preparation method according to claim 23, characterized in that: Also includes: immersing the glass-ceramics in a chemically strengthened salt bath for ion exchange treatment to obtain chemically strengthened glass-ceramics; The chemical strengthening salt bath comprises, by mass percentage, greater than or equal to 9.99% and less than or equal to 39.99% of KNO3, greater than or equal to 59.99% and less than or equal to 89.99% of NaNO3, and greater than or equal to 0.03% and less than or equal to 0.1% of LiNO3.

26. The glass preparation method according to claim 25, characterized in that: The temperature of the chemical strengthening salt bath is 460-490° C., and the duration of the ion exchange treatment is 4-10 hours.

27. The glass preparation method according to claim 23, characterized in that: The heat treatment of the precursor glass comprises: The precursor glass is placed in a crystallization furnace, heated to 560-590°C at a heating rate of 8-12°C / min, and then kept warm for 220-250 minutes. Then, it is heated to 750-790°C at a heating rate of 8-12°C / min, and then kept warm for 70-90 minutes. Finally, it is cooled at a cooling rate of less than or equal to 2°C / min.

28. The glass preparation method according to claim 23, characterized in that: Also includes: The glass-ceramics is subjected to heat bending treatment at a heat bending workstation; wherein the pressure of the heat bending workstation is 0.7 to 1.1 MPa, and the operation time of a single workstation is 70 to 110 seconds.

29. The glass preparation method according to claim 28, characterized in that: The hot bending treatment needs to go through four preheating workstations, three hot pressing workstations and two cooling workstations; among them, the operating temperature of the first preheating workstation is 430-470°C, the operating temperature of the second preheating workstation is 530-570°C, the operating temperature of the third preheating workstation is 630-670°C, the operating temperature of the fourth preheating workstation is 710-730°C, the operating temperature of the first hot pressing workstation is 740-760°C, the operating temperature of the second hot pressing workstation is 740-760°C, the operating temperature of the third hot pressing workstation is 580-620°C, the operating temperature of the first cooling workstation is 430-470°C, and the operating temperature of the second cooling workstation is 280-320°C.

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