CN111268913B - Microcrystalline glass product for electronic device cover plate and microcrystalline glass - Google Patents
Microcrystalline glass product for electronic device cover plate and microcrystalline glass Download PDFInfo
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- CN111268913B CN111268913B CN202010198684.6A CN202010198684A CN111268913B CN 111268913 B CN111268913 B CN 111268913B CN 202010198684 A CN202010198684 A CN 202010198684A CN 111268913 B CN111268913 B CN 111268913B
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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
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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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K5/00—Casings, cabinets or drawers for electric apparatus
- H05K5/02—Details
- H05K5/03—Covers
Abstract
The invention discloses a microcrystalline glass product and microcrystalline glass for an electronic equipment cover plate, wherein the main crystalline phase of the microcrystalline glass contains lithium silicate and quartz crystalline phase, and the microcrystalline glass comprises the following components in percentage by weight: SiO 2: 65-85%, Al2O 3: 1-15%, Li 2O: 5-15%, ZrO 2: 0.1-10%, P2O 5: 0.1-10%, K2O: 0-10%, MgO: 0-10%, ZnO: 0-10%, Na 2O: 0 to 5%, wherein (SiO2+ Al2O3+ Li2O + ZrO2)/P2O5 is 40 to 90%, and the ball drop test height is more than 700 mm. Through reasonable component design, the microcrystalline glass and the microcrystalline glass product have excellent mechanical properties, and the microcrystalline glass or the microcrystalline glass product suitable for electronic equipment is obtained at lower cost.
Description
The present application is a divisional application of an invention patent application having an application number of 201811264671.3, an application date of 2018, 10 and 26, and a name of "a microcrystalline glass product and a microcrystalline glass for an electronic device cover plate".
Technical Field
The present invention relates to a glass-ceramic product and a glass-ceramic, and in particular, to a glass-ceramic product for a cover plate of an electronic device, a glass-ceramic, a glass cover plate for an electronic device, and an electronic device.
Background
Since electronic devices have many precise electronic components inside, a cover plate or a housing is required to protect the internal electronic components. In the content disclosed in the prior literature, metal is used as a cover plate material, but the metal has the defects of easy oxidation, shielding of electromagnetic signals and the like; for example, chinese patent CN101508524A discloses a chemically strengthened glass, which has properties such as drop resistance and fracture toughness that are difficult to meet.
A glass ceramics is a material in which crystals are precipitated inside the glass by heat treatment of the glass. The crystallized glass can have physical properties that cannot be obtained in glass due to crystals dispersed therein. For example, the mechanical strength such as Young's modulus and fracture toughness, the etching characteristics with an acidic or alkaline chemical solution, the thermal properties such as the thermal expansion coefficient, and the increase and decrease of the glass transition temperature. The microcrystalline glass has higher mechanical properties, and because the microcrystalline is formed in the glass, the bending resistance, the wear resistance and the like of the microcrystalline glass have obvious advantages compared with the common glass.
Based on the above factors, the present inventors have intended to develop a glass-ceramic having excellent mechanical properties suitable for electronic devices through a large number of experimental studies.
Disclosure of Invention
The invention aims to provide a microcrystalline glass product for an electronic equipment cover plate, which has excellent mechanical properties.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) a crystallized glass article for electronic device cover plates, the crystallized glass article having a main crystal phase containing lithium silicate and a quartz crystal phase, and having a composition, expressed in weight percent, comprising: SiO 2 2 ：65～85％、Al 2 O 3 ：1～15％、Li 2 O：5～15％、ZrO 2 ：0.1～10％、P 2 O 5 ：0.1～10％、K 2 O：0～10％、MgO：0～10％、ZnO：0～10％、Na 2 O: 0 to 5% of (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 40-90, and the height of ball drop test is above 700 mm.
(2) The microcrystalline glass product for the electronic equipment cover plate comprises the following components in percentage by weight: SiO 2 2 ：65～85％、Al 2 O 3 ：1～15％、Li 2 O：5～15％、ZrO 2 ：0.1～10％、P 2 O 5 ：0.1～10％、K 2 O：0～10％、MgO：0～10％、ZnO：0～10％、Na 2 O：0～5％。
(3) The crystallized glass product for an electronic device cover plate according to any one of (1) to (2), which further comprises, in terms of weight percent: SrO: 0-5%, and/or BaO: 0 to 5%, and/or TiO 2 : 0 to 5%, and/or Y 2 O 3 : 0 to 5%, and/or B 2 O 3 : 0-3%, and/or a clarifying agent: 0 to 2 percent.
(4) The method according to any one of (1) to (3)A crystallized glass article for electronic device cover plates, wherein: (SiO) 2 +Li 2 O)/Al 2 O 3 6 to 15, and/or (Al) 2 O 3 +Li 2 O)/P 2 O 5 5 to 20, and/or (SiO) 2 +Li 2 O)/P 2 O 5 40 to 80, and/or (K) 2 O+MgO)/ZrO 2 0.6 to 1.2, and/or Li 2 O/(K 2 O+ZrO 2 ) 2.3 to 4.0.
(5) The crystallized glass product for an electronic device cover plate according to any one of (1) to (4), wherein: (SiO) 2 +Li 2 O)/Al 2 O 3 8 to 13, and/or (Al) 2 O 3 +Li 2 O)/P 2 O 5 6 to 14, and/or (SiO) 2 +Li 2 O)/P 2 O 5 40 to 70, and/or (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 45 to 85, and/or (K) 2 O+MgO)/ZrO 2 0.7 to 1.1, and/or Li 2 O/(K 2 O+ZrO 2 ) 2.5 to 3.5.
(6) The crystallized glass product for an electronic device cover plate according to any one of (1) to (5), which comprises, in terms of weight percent: SiO 2 2 : 70 to 76%, and/or Al 2 O 3 : 4 to 10%, and/or Li 2 O: 8 to 12.5%, and/or ZrO 2 : 1 to 5%, and/or P 2 O 5 : 1 to 3%, and/or K 2 O: 0-3%, and/or MgO: 0.3-2%, and/or ZnO: 0 to 3%, and/or Na 2 O: 0 to 1%, and/or Sb 2 O 3 : 0 to 1%, and/or SnO 2 : 0-1%, and/or SnO: 0 to 1%, and/or CeO 2 ：0～1％。
(7) The crystallized glass product for an electronic device cover plate according to any one of (1) to (6), wherein: (Al) 2 O 3 +Li 2 O)/P 2 O 5 8.5 to 14, and/or (SiO) 2 +Li 2 O)/P 2 O 5 45 to 60, and/or (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 Is 48 to 80, and/or (SiO) 2 +Li 2 O)/Al 2 O 3 8.5 to 12.
(8) The crystallized glass product for an electronic device cover plate according to any one of (1) to (7), wherein: (K) 2 O+MgO)/ZrO 2 0.8 to 1.0, and/or Li 2 O/(K 2 O+ZrO 2 ) 2.8 to 3.3.
(9) The crystallized glass product for an electronic device cover plate according to any one of (1) to (8), which comprises, in terms of weight percent: li 2 O: 8 to less than 10 percent, and/or does not contain SrO, and/or does not contain BaO, and/or does not contain TiO 2 And/or does not contain Y 2 O 3 And/or does not contain GeO 2 And/or do not contain CaO, and/or do not contain Cs 2 O, and/or does not contain PbO, and/or does not contain B 2 O 3 And/or does not contain As 2 O 3 And/or do not contain La 2 O 3 And/or and does not contain Tb 2 O 3 。
(10) The crystallized glass product for an electronic device cover plate according to any one of (1) to (9), wherein the crystallinity is 70% or more.
(11) The crystallized glass product for an electronic device cover plate according to any one of (1) to (10), wherein the falling ball test height is 1000mm or more; and/or the four-point bending strength is above 650 MPa; and/or a haze of 0.5% or less at a thickness of 0.55 mm; and/or a temperature coefficient of refractive index of-0.8X 10 -6 Below/° c; and/or a light transmittance at a wavelength of 550nm with a thickness of 0.55mm of 88% or more.
The invention also provides the microcrystalline glass which has excellent mechanical properties.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(12) microcrystalline glass, the main crystalline phase of which contains lithium silicate and quartz crystalline phases, the composition of which is expressed in weight percent: SiO 2 2 ：65～85％、Al 2 O 3 ：1～15％、Li 2 O：5～15％、ZrO 2 ：0.1～10％、P 2 O 5 ：0.1～10％、K 2 O：0～10％、MgO：0～10％、ZnO：0～10％、Na 2 O：0～3％，Sb 2 O 3 ：0～1％、SnO 2 ：0～1％、SnO：0～1％、CeO 2 : 0 to 1% of (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 Is 40 to 90, (K) 2 O+MgO)/ZrO 2 0.6 to 1.2, and 0.5% or less of haze in a thickness of 0.55 mm.
(13) Microcrystalline glass, the main crystalline phase of which comprises lithium silicate and a crystalline quartz phase, the composition of which, expressed in percentages by weight, comprises: SiO 2 2 ：65～85％、Al 2 O 3 ：1～15％、Li 2 O：5～15％、ZrO 2 ：0.1～10％、P 2 O 5 ：0.1～10％、K 2 O: 0-10%, MgO: 0-10%, ZnO: 0 to 10% of (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 Is 40 to 90.
(14) The microcrystalline glass comprises the following components in percentage by weight: SiO 2 2 ：65～85％、Al 2 O 3 ：1～15％、Li 2 O：5～15％、ZrO 2 ：0.1～10％、P 2 O 5 ：0.1～10％、K 2 O：0～10％、MgO：0～10％、ZnO：0～10％。
(15) The crystallized glass according to any one of (12) to (14), wherein: (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 45 to 85, and/or (SiO) 2 +Li 2 O)/Al 2 O 3 8 to 13, and/or (Al) 2 O 3 +Li 2 O)/P 2 O 5 6 to 14, and/or (SiO) 2 +Li 2 O)/P 2 O 5 40 to 70, and/or Li 2 O/(K 2 O+ZrO 2 ) 2.5 to 3.5.
(16) The crystallized glass of any one of (12) to (15), wherein SiO is 2 : 70 to 76%, and/or Al 2 O 3 : 4 to 10%, and/or Li 2 O: 8 to 12.5%, and/or ZrO 2 : 1 to 5%, and/or P 2 O 5 : 1 to 3%, and/or K 2 O: 0-3%, and/or MgO: 0.3-2%, and/or ZnO: 0 to 3%, and/or Na 2 O：0～1％。
(17) The crystallized glass of any one of (12) to (16), wherein: (K) 2 O+MgO)/ZrO 2 0.8 to 1.0, and/or Li 2 O/(K 2 O+ZrO 2 ) 2.8 to 3.3.
(18) The microcrystalline glass according to any one of (12) to (17), wherein the degree of crystallinity is 70% or more; and/or the grain size is 80nm or less; and/or a temperature coefficient of refractive index of-0.8X 10 -6 Below/° c; and/or the average light transmittance of the film with a thickness of 1mm and a wavelength of 400-800 nm is more than 85%.
The invention also provides a glass cover plate for electronic equipment, which comprises:
(19) a glass cover for electronic devices, comprising the crystallized glass product for electronic device cover according to any one of (1) to (11) and/or the crystallized glass according to any one of (12) to (18).
The present invention also provides an electronic device:
(20) an electronic device comprising the crystallized glass product for an electronic device cover plate according to any one of (1) to (11), and/or the crystallized glass according to any one of (12) to (18), and/or the glass cover plate for an electronic device according to (19).
The beneficial effects of the invention are: through reasonable component design, the microcrystalline glass and the microcrystalline glass product have excellent mechanical properties and are suitable for electronic equipment.
Detailed Description
The glass ceramics for electronic device cover plates is simply referred to as "glass ceramics" hereinafter.
The crystallized glass and the crystallized glass article of the present invention are materials having a crystal phase and a glass phase, which are different from amorphous solids. The crystalline phases of the glass-ceramic and the glass-ceramic article can be distinguished by the angle of the peak appearing in the X-ray diffraction pattern of the X-ray diffraction analysis and by TEMEDX, the predominant crystalline phase being determined by X-ray diffraction.
The inventors of the present invention have made extensive experiments and studies, and have obtained a crystallized glass or a crystallized glass product of the present invention at a low cost by specifying the content and content ratio of specific components constituting a crystallized glass or a crystallized glass product to specific values and precipitating specific crystal phases.
The compositional ranges of the respective components of the glass composition, the glass ceramics or the glass ceramics product of the present invention will be explained below. In the present specification, the contents of the respective components are all expressed in terms of weight percentage with respect to the total amount of glass matter converted into the composition of oxides, if not specifically stated. Here, the "composition in terms of oxide" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the glass composition, the crystallized glass, or the crystallized glass product composition of the present invention are decomposed at melting and converted into oxides, the total amount of the oxides is 100%. In the present specification, the term "glass" refers to a glass composition before crystallization, a glass composition after crystallization is referred to as "glass ceramics", and a glass ceramic product refers to glass ceramics after chemical tempering.
Unless otherwise indicated in a specific context, numerical ranges set forth herein include upper and lower values, and "above" and "below" include endpoints, all integers and fractions within the range, and are not limited to the specific values listed in the defined range. The term "about" as used herein means that the formulations, parameters, and other quantities and characteristics are not, and need not be, exact, and can be approximate and/or larger or smaller, if desired, reflecting tolerances, conversion factors, measurement error and the like. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.
The glasses, devitrified glasses and devitrified glass articles of the present invention can be broadly described as lithium-containing aluminosilicate glasses, devitrified glasses and devitrified glass articles comprising SiO 2 、Al 2 O 3 And Li 2 O, in addition to, ZrO 2 、P 2 O 5 And the like. In some embodiments, depending on the composition of the glass, the first of the microcrystalline glass and the microcrystalline glass articleThe predominant crystalline phase is lithium silicate; in some embodiments, the first predominant crystalline phase is petalite; in some embodiments, the first predominant crystalline phase is a crystalline quartz phase (including both quartz, and quartz solid solutions). In some embodiments, the primary crystalline phases include lithium silicate and quartz crystalline phases. In some embodiments, the predominant crystalline phases include lithium silicate and petalite. In some embodiments, the first crystalline phase is lithium silicate and the second predominant crystalline phase is a quartz crystalline phase; in some embodiments, the first crystalline phase is a quartz crystalline phase and the second predominant crystalline phase is lithium silicate; in some embodiments, the first crystalline phase is lithium silicate and the second predominant crystalline phase is petalite; in some embodiments, the first crystalline phase is petalite and the second predominant crystalline phase is lithium silicate. In some embodiments, the predominant crystalline phases include lithium silicate, petalite, and quartz crystalline phases; in some embodiments, the first crystalline phase is lithium silicate, the second predominant crystalline phase is petalite, and the third predominant crystalline phase is a quartz crystalline phase; in some embodiments, the first crystalline phase is lithium silicate, the second predominant crystalline phase is a quartz crystalline phase, and the third predominant crystalline phase is petalite; in some embodiments, the first predominant crystalline phase is petalite, the second predominant crystalline phase is lithium silicate, and the third predominant crystalline phase is a quartz crystalline phase; in some embodiments, the first crystalline phase is a quartz crystalline phase, the second predominant crystalline phase is lithium silicate, and the third predominant crystalline phase is petalite. In some embodiments, the quartz crystal phase is an alpha-hexagonal quartz crystal phase; in some embodiments, the lithium silicate is lithium disilicate; beta-spodumene ss, lithium phosphate, etc. may also be present as secondary crystalline phases. It should be noted that the crystal phase of quartz referred to herein includes both the case where quartz crystal is contained only, the case where quartz is contained, and the case where a solid solution of quartz is contained.
In some embodiments, the weight percentage of the residual glass phase in the glass ceramic and the glass ceramic product is 8-45%; in some embodiments, 10 to 40%; in some embodiments, 12-40%; in some embodiments, 15-40%; in some embodiments, 15 to 35%; in some embodiments, 15-32%; in some embodiments, 20 to 45%; in some embodiments, 20-40%; in some embodiments, 32-45%; in some embodiments, 32-40%; in some embodiments, 35 ~ 45%.
When the main crystal phase of the microcrystalline glass is one or the combination of quartz crystal phase, lithium silicate and petalite, the fracture toughness of the microcrystalline glass is high. When the main crystal phase of the microcrystalline glass is quartz crystal phase and lithium disilicate, the temperature coefficient of the refractive index of the microcrystalline glass is low, and the fracture toughness is high; the height of the microcrystalline glass product in the falling ball test is increased, and the four-point bending strength is increased.
The main crystal phase accounts for 50-92% of the weight of the microcrystalline glass or the microcrystalline glass product; in some embodiments, the weight percent is up to 60-90%; in some embodiments, the weight percent is 65-85%; in some embodiments, the weight percent is up to 70-80%; in some embodiments, the weight percentage is 80 to 92%. The primary crystalline phase, as referred to herein, refers to a crystalline phase having a higher weight percentage than other crystalline phases present in the microcrystalline glass or microcrystalline glass article.
In some embodiments, the microcrystalline glass or microcrystalline glass article has a weight percent quartz crystalline phase below 70%; in some embodiments, the microcrystalline glass or microcrystalline glass article has a weight percent quartz crystalline phase of less than 65%; in some embodiments, the weight percent of the crystalline quartz phase of the microcrystalline glass or microcrystalline glass article is less than 60%; in some embodiments, the microcrystalline glass or microcrystalline glass article has a weight percent quartz crystalline phase below 55%; in some embodiments, the weight percent of the crystalline quartz phase of the microcrystalline glass or microcrystalline glass article is less than 50%; in some embodiments, the weight percent of the crystalline quartz phase of the microcrystalline glass or microcrystalline glass article is less than 45%.
In some embodiments, the microcrystalline glass or microcrystalline glass article has a weight percent lithium silicate crystalline phase of less than 55%; in some embodiments, the microcrystalline glass or microcrystalline glass article has a weight percent lithium silicate crystalline phase below 50%; in some embodiments, the microcrystalline glass or microcrystalline glass article has a weight percent lithium silicate crystalline phase below 45%; in some embodiments, the microcrystalline glass or microcrystalline glass article has a weight percent lithium silicate crystalline phase of less than 40%.
In some embodiments, the weight percent petalite crystalline phase of the glass-ceramic or glass-ceramic article is less than 40%; in some embodiments, the weight percent petalite crystalline phase of the glass-ceramic or glass-ceramic article is less than 35%; in some embodiments, the glass-ceramic or glass-ceramic article has a petalite crystalline phase weight percent of less than 30%; in some embodiments, the glass-ceramic or glass-ceramic article has a petalite crystalline phase weight percent of less than 25%; in some embodiments, the glass-ceramic or glass-ceramic article has a petalite crystalline phase weight percent of less than 20%; in some embodiments, the glass-ceramic or glass-ceramic article has a petalite crystalline phase weight percent of less than 15%.
SiO 2 Is the basic component of the glass composition of the invention and is useful for stabilizing the network structure of glass and glass-ceramics, which is one of the components forming lithium silicate, quartz crystal phase and petalite after crystallization, if SiO 2 The content of (A) is 65% or less, and since the formation of crystals in the glass ceramics is reduced and the crystals are easily coarsened, the haze of the glass ceramics and the properties such as the falling ball test height of the glass ceramics are affected, SiO 2 The lower limit of the content is preferably 65%, preferably 70%; if SiO 2 The content is more than 85 percent, the melting temperature of the glass is high, the melting is difficult, the forming is difficult, and the consistency of the glass is influenced, therefore, the SiO 2 The upper limit of the content is preferably 85%, preferably 80%, and more preferably 76%. In some embodiments, about 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84% SiO may be included 2 。
Al 2 O 3 Is a component for forming a glass network structure, is an important component which is helpful for stabilizing glass forming and improving chemical stability, can also improve the mechanical property of glass and increase an ion exchange layer of a microcrystalline glass productDepth and surface stress, but if the content is less than 1%, the effect is not good, and therefore, Al 2 O 3 The lower limit of the content is 1%, preferably 4%. On the other hand, if Al 2 O 3 When the content of (b) exceeds 15%, the glass tends to have a low melting property and a low devitrification resistance, to have large crystals during crystallization, and to have a low strength of the glass ceramics and glass ceramics products, and therefore, Al is contained in the glass ceramics and glass ceramics products 2 O 3 The upper limit of the content is 15%, preferably 12%, more preferably 10%. In some embodiments, about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% Al may be included 2 O 3 。
Li 2 O is an essential component which becomes a crystal phase composition by crystallization, contributes to formation of a lithium-containing crystal phase such as lithium silicate and petalite, and is also an essential component for chemical strengthening. However, if the content is less than 5%, the effect is not good, and therefore, Li 2 The lower limit of the O content is 5%, preferably 7%, more preferably 8%, and in some embodiments, still more preferably 9%; on the other hand, if Li is contained excessively 2 O is liable to lower the chemical stability of the glass and deteriorate the light transmittance of the glass-ceramic and the glass-ceramic product, and therefore Li 2 The upper limit of the O content is preferably 15%, more preferably 12.5%, and in some embodiments, more preferably less than 10%. In some embodiments, about 5%, 6%, 7%, 8%, 9%, 9.8%, 10%, 11%, 12%, 13%, 14%, 15% Li may be included 2 O。
The inventor of the present invention has found that through the control of SiO 2 、Li 2 O and Al 2 O 3 Introduced in a certain proportion, can influence the thermal expansion coefficient of the glass, the haze and the grain size of the microcrystalline glass and the microcrystalline glass products, especially (SiO) 2 +Li 2 O)/Al 2 O 3 In the range of 6 to 15, the glass has a low thermal expansion coefficient, and after crystallization, small crystal grains are obtained, and the mechanical strength of the glass ceramics and glass ceramics products is improved, and in some embodiments, (SiO) is preferable 2 +Li 2 O)/Al 2 O 3 8 to 13, more preferably 8 to 12.5, and can obtain lower haze, so that the microcrystalline glass and the microcrystalline glass product have excellent light transmittance; further preferred is (SiO) 2 +Li 2 O)/Al 2 O 3 The content is 8.5-12, and the effect is particularly obvious. In some embodiments, (SiO) 2 +Li 2 O)/Al 2 O 3 The value of (b) may be 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15.
P 2 O 5 Is an optional component which is helpful for improving the low-temperature melting property of the glass, can carry out phase separation in the glass to form crystal nucleus and improve the thermal expansion stability, P, of the glass in the crystallization process 2 O 5 The lower limit of the content is preferably 0.1, more preferably 0.5%, and further preferably 1%; but if it contains P excessively 2 O 5 The glass tends to have a reduced devitrification resistance and phase separation, and the mechanical properties of the glass tend to deteriorate. Thus, P 2 O 5 The upper limit of the content is 10%, preferably 5%, more preferably 3%. In some embodiments, about 0%, 0.1%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% P may be included 2 O 5 。
By controlling (SiO) in the present invention 2 +Li 2 O)/P 2 O 5 The value of (A) is in the range of 40 to 80, and the depth of an ion exchange layer of the microcrystalline glass product, especially (SiO) 2 +Li 2 O)/P 2 O 5 The value of (b) is in the range of 40 to 70, more preferably (SiO) 2 +Li 2 O)/P 2 O 5 The value of (b) is 42 to 60, preferably 45 to 60, and the microcrystalline glass product can obtain a deeper ion exchange layer; in some embodiments, the (SiO) 2 +Li 2 O)/P 2 O 5 The value of (B) is in the range of 40 to 70, more preferably (SiO) 2 +Li 2 O)/P 2 O 5 When the value of (A) is 42 to 60, more preferably 45 to 60, the crystallization process is advantageous for forming a quartz crystal phase and lithium disilicate, and further, a microcrystalline glass and a microcrystalline glass product can have excellent fracture propertiesTemperature coefficient of refractive index of-0.5 x 10 -6 Below/° C, preferably-0.8X 10 -6 Below/° C, more preferably-1.1X 10 -6 Below/° c, the refractive index change difference between the glass phase and each crystalline phase in the glass ceramics and the glass ceramic products caused by the temperature difference is reduced, and the decrease of the light transmittance of the glass ceramics or the glass ceramic products caused by the temperature difference is avoided. In some embodiments, (SiO) 2 +Li 2 O)/P 2 O 5 May be 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70.
Through a great deal of experimental research of the inventor, Al is found 2 O 3 、Li 2 O and P 2 O 5 The proportion of the glass to be incorporated has a significant influence on the surface stress and the four-point bending strength of the glass-ceramic and glass-ceramic articles, in particular of (Al) 2 O 3 +Li 2 O)/P 2 O 5 In the range of 5 to 20, the surface stress of the glass ceramics and the glass ceramics product can be increased, and (Al) is preferable 2 O 3 +Li 2 O)/P 2 O 5 In the range of 6 to 14, (Al) is more preferable in some embodiments 2 O 3 +Li 2 O)/P 2 O 5 Is 8 to 14, more preferably (Al) 2 O 3 +Li 2 O)/P 2 O 5 8.5 to 14, and the four-point bending strength of the microcrystalline glass and the microcrystalline glass product is significantly improved, and in some embodiments, the four-point bending strength of the microcrystalline glass and the microcrystalline glass product is 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or more. In some embodiments, (Al) 2 O 3 +Li 2 O)/P 2 O 5 The value of (a) may be 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20.
ZrO 2 Having the effect of precipitating crystals to form nuclei and simultaneously contributing to an increase in the chemical stability of the glassOptional components, found by research, ZrO 2 Li can also be increased by significantly reducing glass devitrification and lowering liquidus temperature during formation 2 O-Al 2 O 3 -SiO 2 -P 2 O 5 Stability of the glass. ZrO in the invention 2 The lower limit of the content is preferably 0.1, more preferably 0.5%, and further preferably 1%; but if it contains ZrO excessively 2 The devitrification resistance of the glass is easily lowered and at the same time the difficulty of controlling the crystallization process of the glass is increased, and therefore, ZrO 2 The upper limit of the content is 10%, preferably 6%, more preferably 5%. In some embodiments, ZrO may be included at about 0%, 0.1%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% 2 。
In the course of a large number of experimental studies, the inventors have found that SiO can be controlled by controlling the SiO 2 、Al 2 O 3 、Li 2 O and ZrO 2 Total content of (2) and P 2 O 5 Ratio of introduced amounts (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 In the range of 40-90, the microcrystalline glass product can be subjected to falling ball impact of more than 700mm, preferably (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 45-85; in some embodiments, among others, (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 In the range of 46 to 80, lithium disilicate and quartz crystal phase are easily formed, and the microcrystalline glass product easily obtains excellent fracture toughness which can be 1 MPa.m 1/2 Above, preferably 1.3MPa · m 1 /2 More preferably 1.5MPa · m or more 1/2 The above; simultaneously, the bearing capacity of the falling ball test height is further optimized, and (SiO) is further optimized 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 48 to 80, and a ball drop test height of 700mm or more, preferably 800mm or more, more preferably 1000mm or more, and further preferably 1200mm or more. In some embodiments, (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 May be 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90.
K 2 O is an optional component for improving the low-temperature melting property and the formability of the glass, but if K is excessively contained, K is excessively contained 2 O, a decrease in the chemical stability of the glass and an increase in the average linear expansion coefficient are easily caused. Thus, K 2 The content of O is 0 to 10%, preferably 0 to 5%, more preferably 0 to 3%. In some embodiments, K may be included at about 0%, greater than 0%, 0.1%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% 2 O。
In the present invention, when Li is controlled 2 O and K 2 O and ZrO 2 Total content (K) of 2 O+ZrO 2 ) Introduction amount ratio of Li 2 O/(K 2 O+ZrO 2 ) When the crystallization temperature is within the range of 2.3-4.0, the crystallization performance of the microcrystalline glass can be optimized, and the microcrystalline glass product have proper crystallinity, so that the microcrystalline glass and the microcrystalline glass product have excellent performance; preferably Li 2 O/(K 2 O+ZrO 2 ) 2.5 to 3.5, more preferably 2.8 to 3.3, and the crystallized glass product have a large ball drop test height, and in some embodiments, the ball drop test height is preferably 800mm or more, more preferably 1000mm or more, and further preferably 1200mm or more. In some embodiments, Li 2 O/(K 2 O+ZrO 2 ) The value of (a) may be 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0.
The ZnO can improve the melting property of the glass, improve the chemical stability of the glass, refine crystal grains during crystallization, and suppress the deterioration of devitrification property by controlling the upper limit of the ZnO content to 10% or less, and therefore, the upper limit of the ZnO content is 10%, preferably 5%, more preferably 3%. In some embodiments, about 0%, greater than 0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% ZnO may be included.
MgO contributes to lowering the viscosity of glass, inhibiting glass crystallization during molding and refining crystal grains during crystallization, and also has the effect of improving low-temperature melting property, and MgO is an optional component in the invention, and the preferable content is more than 0.3%; however, if the content of MgO is too high, devitrification resistance may be lowered, and undesirable crystals are obtained after crystallization, resulting in deterioration of the performance of the crystallized glass or crystallized glass product, and therefore, the upper limit of the content of MgO is 10%, preferably 5%, more preferably 2%. In some embodiments, MgO may be included at about 0%, greater than 0%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.
Through a great deal of experimental research of the inventor, the inventor finds that when K is controlled 2 Total content K of O and MgO 2 O + MgO and ZrO 2 Introduced amount ratio (K) 2 O+MgO)/ZrO 2 In the range of 0.6 to 1.2, it can be reacted with Li 2 The O generates a synergistic effect to promote the microcrystalline glass and the microcrystalline glass product to have proper crystallinity, so that the microcrystalline glass and the microcrystalline glass product have excellent performance; it was also found that (K) is controlled by preference 2 O+MgO)/ZrO 2 0.7 to 1.1, and (K) is more preferable because crystal grains can be refined and the light transmittance and mechanical strength are more excellent 2 O+MgO)/ZrO 2 In the range of 0.8 to 1.0, the four-point bending strength of the crystallized glass and the crystallized glass product becomes large in some embodiments, and the four-point bending strength is preferably 650MPa or more, more preferably 700MPa or more. In some embodiments, (K) 2 O+MgO)/ZrO 2 Can be 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2.
SrO is an optional component for improving the low-temperature melting property of the glass and inhibiting the formation crystallization, and in the invention, the SrO is preferably controlled to be less than 5%, so that the microcrystalline glass and the microcrystalline glass product can easily obtain excellent grain size, the content of the SrO is preferably less than 1%, and in some embodiments, the SrO is preferably not introduced. In some embodiments, about 0%, greater than 0%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5% SrO may be included.
BaO is an optional ingredient contributing to improvement of glass forming property of the glass, and when the content thereof exceeds 5%, devitrification resistance of the glass is lowered, so that the BaO content is preferably controlled to 5% or less, more preferably 1% or less, and in some embodiments, is preferably not incorporated. In some embodiments, BaO may be included at about 0%, greater than 0%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%.
TiO 2 Is an optional component which helps to lower the melting temperature of the glass and improve chemical stability, and the incorporation of 5% or less in the present invention makes it easier to control the glass crystallization process, preferably 1% or less, and in some embodiments, preferably none. In some embodiments, about 0%, greater than 0%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5% TiO may be included 2 。
Y 2 O 3 Is an optional component for improving the hardness and chemical stability of the glass, but if the content is too large, devitrification of the glass is likely to occur, and the content is 5% or less, preferably 1% or less, and in some embodiments, it is preferable not to incorporate the glass. In some embodiments, about 0%, greater than 0%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5% Y may be included 2 O 3 。
Na 2 O is an optional component for improving the melting property of the glass, and if it is contained in a high content, it is likely to cause increase in the precipitated crystal phase or phase change in the precipitated crystal phase during crystallization, so that it is preferable that Na is contained in an amount of 5% or less in the glass ceramics product without impairing the performance of the glass ceramics and glass ceramics product of the present invention 2 O, more preferably 3% or less of Na 2 O, more preferably 1% or less of Na 2 O; the glass or glass ceramics may preferably contain 3% or less of Na 2 O, more preferably 1% or less of Na 2 O, in some embodiments, preferably does not contain Na 2 And O. In some embodiments, about 0%, greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1% may be included1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%. 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0% Na 2 O。
B 2 O 3 It is useful to provide a glass having a low melting temperature, and when the content thereof is high, the chemical stability of the glass is lowered, so that B 2 O 3 The content is 3% or less, preferably 0.1 to 2% in some embodiments, and preferably B is not introduced in some embodiments 2 O 3 . In some embodiments, about 0%, greater than 0%, 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%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0% B may be included 2 O 3 。
Sb 2 O 3 、SnO 2 、SnO、CeO 2 One or more of Sb is added as a clarifying agent 2 O 3 The upper limit of the content is 2%, preferably 1%, more preferably 0.5%. SnO 2 、SnO、CeO 2 The upper limit of the content of each is 2%, preferably 1%, and more preferably 0.5%. In some embodiments, one or more of the above 4 fining agents are present in an amount of about 0%, greater than 0%, 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%.
In some embodiments, As may also be used 2 O 3 The content of each of the clarifying agents is 2% or less, preferably 1% or less, and more preferably 0.5% or less.
In the present invention, to obtain a suitable crystal grain size and crystal phase type, thereforeIn some embodiments it is preferred not to introduce La 2 O 3 、Cs 2 O、Tb 2 O 3 、GeO 2 And CaO and the like; PbO and As 2 O 3 Are toxic substances and do not meet the environmental requirements even when added in small amounts, and therefore the present invention does not contain PbO and As in some embodiments 2 O 3 。
The term "not introduced", "not containing" or "0%" as used herein means that the compound, molecule, element or the like is not intentionally added as a raw material to the glass, glass ceramic or glass ceramic product of the present invention; it is within the scope of the present invention that certain impurities or components, which are not intentionally added, may be present as raw materials and/or equipment for the production of glass, glass-ceramic and glass-ceramic articles, and may be present in small or trace amounts in the final glass composition, glass-ceramic and glass-ceramic articles.
In some embodiments of the present invention, the predominant crystalline phases in the microcrystalline glass and microcrystalline glass articles comprise lithium silicate and the crystalline phase quartz, the lithium silicate being lithium disilicate (Li) 2 Si 2 O 5 ) And lithium metasilicate (Li) 2 SiO 3 ) In some embodiments, it is preferred to use lithium disilicate and quartz crystal phase and/or petalite as the main crystal phases, in some embodiments, it is preferred to use lithium disilicate and quartz crystal phase as the main crystal phases, and in some preferred embodiments, it is preferred to use lithium disilicate and α -quartz crystal phase as the main crystal phases, thereby achieving superior performance in the present invention.
The microcrystalline glass of the present invention is provided with excellent mechanical properties, and at the same time, ion exchange can be performed to obtain additional mechanical strength. The invention can lead the microcrystalline glass and the microcrystalline glass product to obtain proper grain size through reasonable component design; meanwhile, the microcrystalline glass and the microcrystalline glass product have good crystallinity, so that the microcrystalline glass and the microcrystalline glass product have excellent mechanical properties. The crystallinity is the complete degree of crystallization, the arrangement of mass points in the complete crystal is regular, the diffraction line is strong, sharp and symmetrical, and the half-height width of a diffraction peak is close to the width measured by an instrument; the crystals with poor crystallinity have defects such as dislocation and the like, so that diffraction line peaks are wide and diffuse. The poorer the crystallinity, the weaker the diffraction power, the wider the diffraction peak until it disappears in the background.
The grain size and haze of the microcrystalline glass or microcrystalline glass article of the present invention affect the transparency of the microcrystalline glass or microcrystalline glass article, i.e., affect the light transmission, with smaller grains giving higher transparency and smaller haze giving higher transparency. In some embodiments, the haze is 0.6% or less, preferably 0.5% or less, more preferably 0.4% or less for a thickness of 0.55 mm. In some embodiments, the crystal grain size is 100nm or less, preferably 80nm or less, more preferably 60nm or less, further preferably 50nm or less, and still further preferably 40nm or less. On the other hand, it is found through research that the smaller the difference between the refractive indexes of the crystal phase and the glass phase in the microcrystalline glass, the higher the transparency of the microcrystalline glass or the microcrystalline glass product.
In some embodiments, the microcrystalline glass or microcrystalline glass article exhibits high transparency in the visible range (i.e., the microcrystalline glass or microcrystalline glass article is transparent). In some embodiments, the average light transmittance of 400 to 800nm at a thickness of 1mm is 80% or more, preferably 85% or more, and more preferably 88% or more. In some preferred embodiments, the 0.55mm thick 550nm light transmittance is 80% or more, preferably 85% or more, more preferably 88% or more, and still more preferably 91% or more.
In some embodiments, an antimicrobial component may be added to the glass, microcrystalline glass, or microcrystalline glass article.
The glass composition, the glass-ceramic and the glass-ceramic product of the invention can be produced and manufactured by the following methods:
forming a glass composition: the raw materials are uniformly mixed according to the composition proportion range, the uniform mixture is put into a crucible made of platinum or quartz, the melting is carried out for 5 to 24 hours in an electric furnace or a gas furnace within the temperature range of 1250 to 1650 ℃ according to the melting difficulty of the glass composition, the mixture is stirred to be uniform, then the temperature is reduced to a proper temperature and the mixture is cast into a mould, and the glass is slowly cooled to obtain the glass.
The glass composition of the present invention can be shaped by a well-known method. In some embodiments, the glass composition of the present invention has a refractive index (nd) of 1.500 to 1.530, preferably 1.510 to 1.525.
The glass composition of the present invention is crystallized by a crystallization process after molding or after molding processing, and crystals are uniformly precipitated inside the glass. The crystallization treatment may be performed in 1 stage or 2 stages, but it is preferable to perform the crystallization treatment in 2 stages. The treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature. The crystallization process performed at the 1 st temperature is referred to as a 1 st crystallization process, and the crystallization process performed at the 2 nd temperature is referred to as a 2 nd crystallization process.
In order to obtain desired physical properties of the glass ceramics, the preferred crystallization process is:
the above-described crystallization process is performed in 1 stage, and thus the nucleus formation process and the crystal growth process can be continuously performed. That is, the temperature is raised to a predetermined crystallization temperature, and after reaching the heat treatment temperature, the temperature is maintained for a certain period of time, and then the temperature is lowered. The temperature of the crystallization treatment is preferably 490 to 800 ℃, and the holding time at the crystallization treatment temperature is preferably 0 to 8 hours, and more preferably 1 to 6 hours, in order to precipitate a desired crystal phase, more preferably 550 to 750 ℃.
When the crystallization is performed in 2 stages, the temperature 1 is preferably 490 to 650 ℃, and the temperature 2 is preferably 600 to 850 ℃. The holding time at the 1 st temperature is preferably 0 to 24 hours, more preferably 2 to 15 hours. The holding time at the 2 nd temperature is preferably 0 to 10 hours, more preferably 0.5 to 6 hours.
The above-mentioned holding time of 0 hour means that the temperature is lowered or raised less than 1 minute after the temperature is reached.
In some embodiments, the microcrystalline glass obtained by the crystallization process has a refractive index (nd) of 1.520 to 1.550, preferably 1.530 to 1.545.
In some embodiments, the glass compositions or glass-ceramics described herein can be fabricated into shaped bodies including, but not limited to, sheets by various processes including, but not limited to, slot draw, float, roll, and other sheet forming processes known in the art. Alternatively, the glass composition or glass ceramic may be formed by a float or roll process as is well known in the art.
The glass composition or glass ceramics of the present invention can be used for producing a sheet glass shaped article by a method such as grinding or polishing, but the method for producing a glass shaped article is not limited to these methods.
The glass or glass-ceramic molded article of the present invention can be produced into various shapes at a certain temperature by a method such as hot bending or press molding, and is not limited to these methods.
The glass compositions, devitrified glasses, and devitrified glass articles of the present invention can have any thickness that is reasonably useful.
The crystallized glass of the present invention can be produced into a crystallized glass product by forming a compressive stress layer to obtain higher strength in addition to improving mechanical properties by precipitation crystallization.
In some embodiments, the glass composition or glass ceramic may be formed into a sheet and/or shaped (e.g., perforated, hot bent, etc.), shaped, polished and/or polished, and chemically tempered via a chemical tempering process.
The chemical toughening method is an ion exchange method. The glass and glass ceramics of the present invention can be ion-exchanged by a method known in the art. In the ion exchange process, smaller metal ions in the glass or glass-ceramic are replaced or "exchanged" by larger metal ions having the same valence state that are adjacent to the glass or glass-ceramic. And replacing smaller ions with larger ions to build a compressive stress in the glass or the glass ceramics to form a compressive stress layer.
In some embodiments, the metal ion is a monovalent alkali metal ion (e.g., Na) + 、K + 、Rb + 、Cs + Etc.), ion exchange by immersing the glass or glass-ceramic in a solution containing a larger metal ionAt least one molten salt bath, the larger metal ions being used to displace the smaller metal ions in the glass. Alternatively, other monovalent metal ions such as Ag + 、Tl + 、Cu + Etc. may also be used to exchange monovalent ions. One or more ion exchange processes used to chemically temper glass or glass ceramics may include, but are not limited to: it is immersed in a single salt bath or in a plurality of salt baths of the same or different composition with washing and/or annealing steps between the immersions.
In some embodiments, the glass or glass-ceramic may be formed by melting a Na salt (e.g., NaNO) by immersion at a temperature of about 430 ℃ to 470 ℃ 3 ) The salt bath is subjected to ion exchange for about 6 to 20 hours, preferably at a temperature of between 435 and 460 ℃ for 8 to 13 hours. In this embodiment, Na ions replace part of Li ions in the glass or glass ceramics, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the glass or glass-ceramic may be formed by melting a K salt (e.g., KNO) by immersion at a temperature of about 400 ℃ to 450 ℃ 3 ) The salt bath is subjected to ion exchange for 1 to 8 hours, and the preferable time range is 2 to 4 hours.
In some preferred embodiments, the Na salt (e.g., NaNO) is melted at 450 deg.C 3 ) The salt bath of (2) has an ion exchange layer depth of 80 μm or more, preferably 85 μm or more, for about 8 hours.
In some embodiments, there are also an ion implantation method of implanting ions into a surface layer of glass or glass ceramics, and a thermal tempering method of heating glass or glass ceramics and then rapidly cooling the same.
The glass composition, the microcrystalline glass and/or the microcrystalline glass product disclosed by the invention are tested by adopting the following methods:
[ coefficient of thermal expansion ]
Coefficient of thermal expansion (alpha) 20℃-120℃ ) The test was carried out according to the test method GB/T7962.16-2010.
[ refractive index ]
The refractive index (nd) was measured according to GB/T7962.1-2010 method.
[ haze ]
A haze tester EEL57D was used, prepared from 0.55mm thick glass samples and tested according to GB 2410-80.
[ grain size ]
And (3) determining by using an SEM (scanning electron microscope), carrying out surface treatment on the microcrystalline glass in HF (hydrofluoric acid), carrying out gold spraying on the surface of the microcrystalline glass, and carrying out surface scanning under the SEM, so as to determine the size of the crystal grains.
[ light transmittance ]
A sample is processed to a thickness of 1mm, and the opposite surfaces are polished in parallel, and the average light transmittance of 400 to 800nm is measured by a Hitachi U-41000 spectrophotometer.
The sample was processed to a thickness of 0.55mm and polished in parallel with the opposite surfaces, and the light transmittance at 550nm was measured by means of a Hitachi U-41000 spectrophotometer.
[ temperature coefficient of refractive index ]
The temperature coefficient of the refractive index is tested according to the method specified in GB/T7962.4-2010, and the temperature coefficient of the refractive index at 20-40 ℃ is measured.
[ degree of crystallinity ]
The XRD diffraction peaks were compared with the database pattern, and the crystallinity was obtained by calculating the proportion of the diffraction intensity of the crystalline phase in the intensity of the entire pattern, and internal calibration was performed by using a pure quartz crystal.
[ surface stress ] and [ depth of ion exchange layer ]
And (4) carrying out surface stress measurement by using a glass surface stress meter FSM-6000 LEUV.
Ion exchange layer depth was measured using a glass surface stress meter SLP-2000.
The refractive index of the sample was 1.54 and the optical elastic constant was 25.3[ (nm/cm)/MPa, which were used as the measurement conditions.
[ falling ball test height ]
The samples of 150X 57X 0.55mm were polished on both surfaces and placed on a rubber sheet, and 132g of steel balls were dropped from a predetermined height to obtain a maximum ball drop test height at which the samples could withstand an impact without breaking. Specifically, the test was conducted from a ball drop test height of 650mm, and the heights were changed in the order of 700mm, 750mm, 800mm, 850mm, and 900mm and above without breaking. For the examples having the "falling ball test height", a crystallized glass article was used as a test object. The test data recorded as 900mm in the examples shows that the crystallized glass product was not broken and received an impact even when the steel ball was dropped from the height of 900 mm.
[ fracture toughness ]
The method for directly measuring the size of the indentation propagation crack is used, the specification of a sample is 2mm multiplied by 4mm multiplied by 20mm, after the sample is chamfered, ground and polished, a Vickers hardness indenter is used for applying 49N force on the sample and maintaining the force for 30s, after the indentation is made, the fracture strength is measured by a three-point bending method.
[ four-point bending Strength ]
The test is carried out by adopting a microcomputer control electronic universal tester CMT6502, the glass specification is 150 multiplied by 57 multiplied by 0.55mm and the ASTM C158-2002 is taken as a standard.
The glass composition of the present invention has the following properties:
1) in some embodiments, the coefficient of thermal expansion (α) 20℃-120℃ ) Is 45 x 10 -7 /K～70×10 -7 Preferably 50X 10,/K -7 /K～70×10 -7 /K。
2) In some embodiments, the refractive index (nd) is 1.500 to 1.530, preferably 1.510 to 1.525.
The microcrystalline glass has the following properties:
1) in some embodiments, the haze is 0.6% or less, preferably 0.5% or less, more preferably 0.4% or less for a thickness of 0.55 mm.
2) In some embodiments, the crystal grain size is 100nm or less, preferably 80nm or less, more preferably 60nm or less, further preferably 50nm or less, and still further preferably 40nm or less.
3) In some embodiments, the temperature coefficient of refractive index of the microcrystalline glass of the present invention is-0.5X 10 -6 Below/° C, preferably-0.8X 10 -6 Below/° C, more preferably-1.1X 10 -6 Below/° c. 4) In some embodiments, the degree of crystallinity is50% or more, preferably 65% or more, more preferably 70% or more, and further preferably 75% or more.
5) In some embodiments, the refractive index (nd) is 1.520 to 1.550, preferably 1.530 to 1.545.
6) In some embodiments, the average light transmittance of 400 to 800nm at a thickness of 1mm is 80% or more, preferably 85% or more, and more preferably 88% or more.
7) In some embodiments, the 0.55mm thickness 550nm light transmittance is 80% or more, preferably 85% or more, more preferably 88% or more, and even more preferably 91% or more.
The microcrystalline glass product of the invention has the following properties besides the properties of the microcrystalline glass:
1) in some embodiments, the surface stress is 200MPa or greater, preferably 250MPa or greater, more preferably 300MPa or greater;
2) in some embodiments, the four-point bending strength is 600MPa or greater, preferably 650MPa or greater, more preferably 700MPa or greater;
3) in some embodiments, the depth of the ion exchange layer is 30 μm or more, preferably 50 μm or more, more preferably 60 μm or more, and further preferably 80 μm or more;
4) In some embodiments, the ball drop test height is 700mm or more, preferably 800mm or more, more preferably 1000mm or more, and even more preferably 1200mm or more;
5) in some embodiments, the fracture toughness is 1 MPa-m 1/2 Above, preferably 1.3MPa · m 1/2 More preferably 1.5MPa · m or more 1/2 The above.
6) In some embodiments, the average light transmittance of 400 to 800nm at a thickness of 1mm is 80% or more, preferably 85% or more, and more preferably 88% or more.
7) In some embodiments, the 0.55mm thickness 550nm light transmittance is 80% or more, preferably 85% or more, more preferably 88% or more, and even more preferably 91% or more.
The microcrystalline glass and the microcrystalline glass product have the excellent performance, so that the microcrystalline glass and the microcrystalline glass product can be widely made into glass cover plates or glass components; meanwhile, the glass ceramics products, and the glass cover plates or glass components made of the glass ceramics can also be applied to electronic equipment or display equipment, such as mobile phones, watches, computers, touch display screens and the like.
Examples
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided. Many efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. The composition is itself given in weight% on oxide basis and has been standardized to 100%.
The following tables 1 to 3 show examples of glass compositions
Table 1.
Table 2.
Table 3.
Examples of the microcrystalline glass are shown in tables 4 to 6 below
Table 4.
Table 5.
Table 6.
Examples of the glass-ceramic product are shown in tables 7 to 9 below
Table 7.
Table 8.
Table 9.
Claims (20)
1. A crystallized glass product for electronic device cover plates, characterized in that the main crystal phase thereof contains lithium silicate and quartz crystal phases, and the composition thereof, expressed in weight percent, contains: SiO 2 2 ：65～85%、Al 2 O 3 ：1～15%、Li 2 O：5～15%、ZrO 2 ：0.1～10%、P 2 O 5 ：0.1～10%、K 2 O：0～10%、MgO：0～10%、ZnO：0～10%、Na 2 O: 0 to 3% of (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 40 to 90, and does not contain La 2 O 3 The height of a ball drop test of 132g of steel balls is more than 700mm, and the weight percentage of the main crystal phase in the microcrystalline glass product is 50-92%.
2. The microcrystalline glass product for the electronic equipment cover plate is characterized by comprising the following components in percentage by weight: SiO 2 2 ：65～85%、Al 2 O 3 ：1～15%、Li 2 O：5～15%、ZrO 2 ：0.1～10%、P 2 O 5 ：0.1～10%、K 2 O：0～10%、MgO：0～10%、ZnO：0～10%、Na 2 O: 0 to 3% of (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 40 to 90, and does not contain La 2 O 3 132g of steel balls having a ball drop test height ofMore than 700mm, and the weight percentage of the main crystal phase in the microcrystalline glass product is 50-92%.
3. The crystallized glass product for electronic device cover plates according to claim 1, which further comprises, in terms of composition by weight: SrO: 0-5%, and/or BaO: 0 to 5%, and/or TiO 2 : 0 to 5%, and/or Y 2 O 3 : 0 to 5%, and/or B 2 O 3 : 0-3%, and/or a clarifying agent: 0 to 2 percent.
4. The crystallized glass product for electronic device cover plates according to claim 2, which further comprises, in terms of composition by weight: SrO: 0-5%, and/or BaO: 0 to 5%, and/or TiO 2 : 0 to 5%, and/or Y 2 O 3 : 0 to 5%, and/or B 2 O 3 : 0-3%, and/or a clarifying agent: 0 to 2 percent.
5. The crystallized glass product for a cover plate of an electronic device according to any one of claims 1 to 4, wherein: (SiO) 2 +Li 2 O)/Al 2 O 3 6 to 15, and/or (Al) 2 O 3 +Li 2 O)/P 2 O 5 5 to 20, and/or (SiO) 2 +Li 2 O)/P 2 O 5 40 to 80, and/or (K) 2 O+MgO）/ZrO 2 0.6 to 1.2, and/or Li 2 O/（K 2 O+ZrO 2 ) 2.3 to 4.0.
6. The crystallized glass product for a cover plate of an electronic device according to any one of claims 1 to 4, wherein: (SiO) 2 +Li 2 O)/Al 2 O 3 8 to 13, and/or (Al) 2 O 3 +Li 2 O)/P 2 O 5 6 to 14, and/or (SiO) 2 +Li 2 O)/P 2 O 5 40 to 70, and/or (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 45 to 85, and/or (K) 2 O+MgO）/ZrO 2 0.7 to 1.1, and/or Li 2 O/（K 2 O+ZrO 2 ) 2.5 to 3.5.
7. The crystallized glass product for a cover plate of an electronic device according to any one of claims 1 to 4, which comprises, in terms of weight percent: SiO 2 2 : 70 to 76%, and/or Al 2 O 3 : 4 to 10%, and/or Li 2 O: 8 to 12.5%, and/or ZrO 2 : 1 to 5%, and/or P 2 O 5 : 1 to 3%, and/or K 2 O: 0-3%, and/or MgO: 0.3-2%, and/or ZnO: 0 to 3%, and/or Na 2 O: 0 to 1%, and/or Sb 2 O 3 : 0 to 1%, and/or SnO 2 : 0-1%, and/or SnO: 0 to 1%, and/or CeO 2 ：0～1%。
8. The crystallized glass product for a cover plate of an electronic device according to any one of claims 1 to 4, wherein: (Al) 2 O 3 +Li 2 O)/P 2 O 5 8.5 to 14, and/or (SiO) 2 +Li 2 O)/P 2 O 5 45 to 60, and/or (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 48 to 80, and/or (SiO) 2 +Li 2 O)/Al 2 O 3 8.5 to 12.
9. The crystallized glass product for a cover plate of an electronic device according to any one of claims 1 to 4, wherein: (K) 2 O+MgO）/ZrO 2 0.8 to 1.0, and/or Li 2 O/（K 2 O+ZrO 2 ) 2.8 to 3.3.
10. The crystallized glass product for a cover plate of an electronic device according to any one of claims 1 to 4, which comprises, in terms of weight percent: li 2 O: 8 to less than 10 percent, and/or does not contain SrO, and/or does not contain BaO, and/or does not contain TiO 2 And/or does not contain Y 2 O 3 And/or does not contain GeO 2 And/or do not contain CaO, and/or do not contain Cs 2 O, and/or does not contain PbO, and/or does not contain B 2 O 3 And/or does not contain As 2 O 3 And/or does not contain Tb 2 O 3 。
11. The crystallized glass product for electronic device cover plates according to any one of claims 1 to 4, wherein the degree of crystallinity is 70% or more.
12. The crystallized glass product for a cover plate of an electronic device according to any one of claims 1 to 4, wherein a ball drop test height of a 132g steel ball is 1000mm or more; and/or the four-point bending strength is above 650 MPa; and/or a haze of 0.5% or less at a thickness of 0.55 mm; and/or a temperature coefficient of refractive index of-0.8X 10 -6 Below/° c; and/or a light transmittance at a wavelength of 550nm with a thickness of 0.55mm of 88% or more.
13. Microcrystalline glass, characterized in that its main crystalline phase contains lithium silicate and quartz crystalline phases, the composition of which, expressed in weight percentages, is: SiO 2 2 ：65～85%、Al 2 O 3 ：1～15%、Li 2 O：5～15%、ZrO 2 ：0.1～10%、P 2 O 5 ：0.1～10%、K 2 O：0～10%、MgO：0～10%、ZnO：0～10%、Na 2 O：0～3%，Sb 2 O 3 ：0～1%、SnO 2 ：0～1%、SnO：0～1%、CeO 2 : 0 to 1% of (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 Is 40 to 90, (K) 2 O+MgO）/ZrO 2 0.6-1.2, haze of 0.55mm thickness is below 0.5%, and the weight percentage of the main crystal phase in the microcrystalline glass is 50-92%.
14. The microcrystalline glass is characterized by comprising the following components in percentage by weight: SiO 2 2 ：65～85%、Al 2 O 3 ：1～15%、Li 2 O：5～15%、ZrO 2 ：0.1～10%、P 2 O 5 ：0.1～10%、K 2 O：0～10%、MgO：0～10%、ZnO：0～10%、Na 2 O：0～3%，Sb 2 O 3 ：0～1%、SnO 2 ：0～1%、SnO：0～1%、CeO 2 : 0 to 1% of (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 40-90, haze of 0.55mm thickness is below 0.5%, and the weight percentage of the main crystal phase in the microcrystalline glass is 50-92%.
15. The glass-ceramic according to claim 13 or 14, wherein: (SiO) 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 45 to 85, and/or (SiO) 2 +Li 2 O)/Al 2 O 3 8 to 13, and/or (Al) 2 O 3 +Li 2 O)/P 2 O 5 6 to 14, and/or (SiO) 2 +Li 2 O)/P 2 O 5 40 to 70, and/or Li 2 O/（K 2 O+ZrO 2 ) 2.5 to 3.5.
16. A glass-ceramic according to claim 13 or 14, wherein SiO is present 2 : 70 to 76%, and/or Al 2 O 3 : 4 to 10%, and/or Li 2 O: 8 to 12.5%, and/or ZrO 2 : 1 to 5%, and/or P 2 O 5 : 1 to 3%, and/or K 2 O: 0-3%, and/or MgO: 0.3-2%, and/or ZnO: 0 to 3%, and/or Na 2 O：0～1%。
17. The glass-ceramic according to claim 13 or 14, wherein: (K) 2 O+MgO）/ZrO 2 0.8 to 1.0, and/or Li 2 O/（K 2 O+ZrO 2 ) 2.8 to 3.3.
18. The microcrystalline glass according to claim 13 or 14, wherein a crystallinity is 70% or more; and/or the grain size is 80nm or less; and/or temperature system of refractive indexThe number is-0.8X 10 -6 Below/° c; and/or the average light transmittance of the film with a thickness of 1mm and a wavelength of 400-800 nm is more than 85%.
19. A glass cover plate for electronic equipment, characterized by comprising the crystallized glass product for an electronic equipment cover plate according to any one of claims 1 to 12 and/or the crystallized glass according to any one of claims 13 to 18.
20. An electronic device comprising the crystallized glass product for an electronic device cover plate according to any one of claims 1 to 12, and/or the crystallized glass according to any one of claims 13 to 18, and/or the glass cover plate for an electronic device according to claim 19.
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| CN201811264671.3A CN109320091A (en) | 2018-10-26 | 2018-10-26 | Electronic equipment cover board crystallized glass article and devitrified glass |
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| CN112608032B (en) * | 2018-10-26 | 2022-04-22 | 成都光明光电股份有限公司 | Glass ceramics, glass ceramics product and manufacturing method thereof |
| KR102438534B1 (en) * | 2019-03-06 | 2022-08-30 | 가부시키가이샤 오하라 | Inorganic composition articles and crystallized glass |
| US20220033298A1 (en) * | 2019-03-22 | 2022-02-03 | Nippon Electric Glass Co., Ltd. | Li2o-al2o3-sio2-based crystallized glass |
| CN109851226A (en) * | 2019-03-27 | 2019-06-07 | 苏州新吴光电科技有限公司 | A kind of devitrified glass and preparation method thereof |
| WO2020243123A1 (en) * | 2019-05-29 | 2020-12-03 | Corning Incorporated | Colored glass-ceramics having petalite and lithium silicate structures |
| CN110482855B (en) * | 2019-06-11 | 2022-07-05 | 中国南玻集团股份有限公司 | Aluminosilicate glass and preparation method thereof |
| CN110734226B (en) * | 2019-12-03 | 2021-12-17 | 重庆鑫景特种玻璃有限公司 | Microcrystalline glass with ultrahigh bifurcation threshold |
| CN110981206B (en) * | 2019-12-20 | 2022-04-05 | 重庆鑫景特种玻璃有限公司 | Polycrystalline core composite transparent glass ceramic and preparation method thereof |
| CN111018356B (en) * | 2019-12-30 | 2022-05-10 | 重庆鑫景特种玻璃有限公司 | Microcrystalline glass with high crystal content and preparation method thereof |
| CN111362579A (en) * | 2020-04-07 | 2020-07-03 | 科立视材料科技有限公司 | Glass ceramic, strengthened glass ceramic and preparation method thereof |
| CN111807706B (en) * | 2020-06-29 | 2022-04-08 | 成都光明光电股份有限公司 | Glass ceramics and glass ceramics product |
| CN112679095B (en) * | 2020-12-25 | 2022-03-11 | 醴陵旗滨电子玻璃有限公司 | Microcrystalline glass, preparation method thereof, intelligent terminal and display |
| CN114014550A (en) * | 2020-12-31 | 2022-02-08 | 成都光明光电股份有限公司 | Glass ceramics, glass ceramics product and manufacturing method thereof |
| CN112919810B (en) * | 2021-03-23 | 2022-02-18 | 成都光明光电股份有限公司 | Glass-ceramic, glass-ceramic article and method for producing same |
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