CN117776535A - Transparent glass ceramics, base material glass, chemically strengthened glass ceramics and application thereof - Google Patents
Transparent glass ceramics, base material glass, chemically strengthened glass ceramics and application thereof Download PDFInfo
- Publication number
- CN117776535A CN117776535A CN202311800621.3A CN202311800621A CN117776535A CN 117776535 A CN117776535 A CN 117776535A CN 202311800621 A CN202311800621 A CN 202311800621A CN 117776535 A CN117776535 A CN 117776535A
- Authority
- CN
- China
- Prior art keywords
- glass
- ceramic
- transparent glass
- transparent
- chemically strengthened
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 367
- 239000011521 glass Substances 0.000 title claims abstract description 365
- 239000000919 ceramic Substances 0.000 title claims abstract description 75
- 239000005345 chemically strengthened glass Substances 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 65
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 42
- 239000013078 crystal Substances 0.000 claims description 137
- 239000000758 substrate Substances 0.000 claims description 130
- 238000012360 testing method Methods 0.000 claims description 97
- 238000001938 differential scanning calorimetry curve Methods 0.000 claims description 39
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 32
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims description 31
- 229910052670 petalite Inorganic materials 0.000 claims description 31
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 27
- 238000002834 transmittance Methods 0.000 claims description 27
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 239000010453 quartz Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 229910013553 LiNO Inorganic materials 0.000 claims description 7
- 244000137852 Petrea volubilis Species 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 5
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910052642 spodumene Inorganic materials 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 abstract description 55
- 238000004519 manufacturing process Methods 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 25
- 238000005336 cracking Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000011449 brick Substances 0.000 description 53
- 239000011734 sodium Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 36
- 239000000047 product Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 29
- 230000008569 process Effects 0.000 description 29
- 238000002425 crystallisation Methods 0.000 description 28
- 230000008025 crystallization Effects 0.000 description 28
- 239000006121 base glass Substances 0.000 description 25
- 230000009286 beneficial effect Effects 0.000 description 24
- 239000002585 base Substances 0.000 description 21
- 239000000126 substance Substances 0.000 description 21
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- 230000006911 nucleation Effects 0.000 description 13
- 238000010899 nucleation Methods 0.000 description 13
- 230000001965 increasing effect Effects 0.000 description 6
- 238000005482 strain hardening Methods 0.000 description 6
- 239000006058 strengthened glass Substances 0.000 description 6
- 238000004846 x-ray emission Methods 0.000 description 6
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 230000001360 synchronised effect Effects 0.000 description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- 201000005947 Carney Complex Diseases 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000002076 thermal analysis method Methods 0.000 description 3
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000005354 aluminosilicate glass Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010977 jade Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 229910010100 LiAlSi Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- YTZVWGRNMGHDJE-UHFFFAOYSA-N tetralithium;silicate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-][Si]([O-])([O-])[O-] YTZVWGRNMGHDJE-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000500 β-quartz Inorganic materials 0.000 description 1
- 229910052644 β-spodumene Inorganic materials 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
The application belongs to the technical field of glass ceramics, and in particular relates to transparent glass ceramics, base material glass, chemically strengthened glass ceramics and application thereof, wherein the composition of the transparent glass ceramics meets the following conditions: the content range of each specific oxide; 18.200 Li is less than or equal to 2 O/P 2 O 5 ≤25.500；14.000≤2×Li 2 O/(0.5×ZrO 2 +CaO). Ltoreq. 23.000. The transparent glass ceramic scheme is suitable for mass production of large-size glass ceramic and meets the requirement of cover platesThe microcrystalline glass product has the advantages of no cracking phenomenon in heat treatment, excellent and uniform optical performance, excellent strength performance and good display effect.
Description
Technical Field
The application belongs to the technical field of glass ceramics, and in particular relates to transparent glass ceramics, base material glass, chemically strengthened glass ceramics and application thereof.
Background
With the development of electronic display technology, glass has gradually replaced plastic materials and is applied to display devices as a protective cover plate material. Cover glass for protecting electronic products in the market at present mainly comprises two types: one is chemically strengthened glass prepared by taking common aluminosilicate glass as a base material, and the other is chemically strengthened glass prepared by carrying out chemical strengthening treatment on microcrystalline glass containing microcrystalline phases and glass phases. The microcrystalline glass contains a large number of nano-scale crystals, so that microcrack expansion can be prevented, and the overall strength performance of the microcrystalline glass is obviously improved compared with that of common aluminosilicate glass.
Since glass ceramics have strength properties superior to those of ordinary glass, industry attention has been paid. However, glass ceramics for display screens, which have high requirements on optical display effects and strength properties, are difficult to produce in large sizes, and are difficult to ensure uniformity of components and uniformity of temperature fields, and are prone to local optical unevenness or cracking of glass bricks.
It should be noted that this section of this application provides only the background art related to this application, and does not necessarily constitute prior art or known technology.
Disclosure of Invention
In order to improve the yield, when the glass ceramics are produced in mass production, a production line usually melts large-size substrate glass bricks first, then carries out heat treatment on the large-size substrate glass bricks to prepare large-size glass ceramics, and then carries out cold working treatment on the large-size glass ceramics to obtain a plurality of glass ceramics sheets with the required size specification.
In the prior art, when the microcrystalline glass with the main crystal phase of petalite crystal phase and lithium disilicate crystal phase is put into a production line for mass production, when large-size microcrystalline glass bricks are produced, such as microcrystalline glass bricks with the length-width-thickness specification of (200 mm-500 mm) x (100 mm-500 mm) x (10 mm-40 mm), the problems that the optical performance of the microcrystalline glass bricks is poor, the microcrystalline glass bricks are easy to crack and the like are very easy to occur. The optical performance of the glass ceramic brick is poor, b values of different areas of the whole brick are large in difference, and unexpected colors are locally displayed, so that the whole display effect of the glass ceramic cannot meet the application requirement of a display screen cover plate, and the product percent of pass is reduced. The cracking of the glass ceramic brick can directly reduce the yield and is unfavorable for realizing the mass production of glass ceramic products. The product with the optical performance meeting the requirement is extremely easy to have the problem of poor strength performance, especially the problem of poor anti-drop performance, and further has the problem of difficult meeting the requirement of using strength.
The purpose of the application is to overcome the defects that when the glass ceramics are produced in mass (especially large-size glass ceramics) in the prior art, the optical performance of the whole brick is uneven, the heat treatment is cracked and the strength cannot be considered easily, and to provide transparent glass ceramics, base material glass, chemically strengthened glass ceramics and application thereof.
The scheme provided by the application is suitable for mass production of large-size transparent glass ceramic tiles meeting the requirement of the cover plate, wherein the main crystal phase is petalite crystal phase and lithium disilicate crystal phase, and the large-size transparent glass ceramic tiles have no cracking phenomenon when being prepared by adopting large-size substrate glass tiles for heat treatment in the preparation process, and the prepared transparent glass ceramic tiles have excellent and uniform optical performance. And then, carrying out cold working treatment (comprising cutting, CNC, polishing and the like to obtain the required size specification) and chemical strengthening treatment on the prepared transparent glass ceramic tile, thus obtaining the transparent chemically strengthened glass ceramic product meeting the optical performance requirements, the strength performance requirements and the display effect requirements. The scheme provided by the application improves the production yield and economic benefit of the transparent glass ceramics with the main crystal phases of petalite crystal phase and lithium disilicate crystal phase, and is easy to realize the industrialized mass production of the transparent glass ceramics.
In order to achieve the above purpose, the present application provides the following technical solutions:
1. a transparent glass-ceramic, wherein the transparent glass-ceramic comprises petalite crystal phase and lithium disilicate crystal phase, wherein the petalite crystal phase and the lithium disilicate crystal phase have a higher weight percentage than other crystal phases present in the transparent glass-ceramic;
the transparent glass ceramics comprises the following components in percentage by mole of oxide:
SiO 2 ：60.90mol％-72.65mol％，Al 2 O 3 ：1.50mol％-5.00mol％，P 2 O 5 ：0.85mol％-1.50mol％，ZrO 2 ：2.00mol％-4.00mol％，Na 2 O：0.00mol％-1.00mol％，K 2 O：0.00mol％-0.50mol％，Li 2 O：20.00mol％-30.00mol％，CaO：0.00mol％-1.60mol％，B 2 O 3 ：0.00mol％-1.00mol％；
the composition of the transparent glass ceramics is expressed by the mol percent of each oxide in the composition of the transparent glass ceramics, and the composition of the transparent glass ceramics meets the following conditions:
18.200≤Li 2 O/P 2 O 5 ≤25.500；
14.000≤2×Li 2 O/(0.5×ZrO 2 +CaO). Ltoreq. 23.000. According to the technical scheme, the oxide content and the specific oxide content relation under specific conditions can ensure the generation of petalite and lithium disilicate serving as main crystal phases, and the problem that when a large-size base material glass brick is used for preparing a microcrystalline glass brick, the microcrystalline glass brick is blue, fogged and even cracked integrally is avoided under the condition that the good melting condition of the base material glass brick is ensured, so that the transparent microcrystalline glass is favorable to obtain excellent optical performance and strength, and the integral display effect of the transparent microcrystalline glass can meet the application requirement of a display screen cover plate. Meanwhile, after the transparent glass ceramics are subjected to chemical strengthening treatment, the chemically strengthened glass ceramics with high strength can be obtained.
2. The transparent glass-ceramic according to claim 1, wherein the composition of the transparent glass-ceramic, expressed as mole percent of each oxide in the composition of the transparent glass-ceramic, satisfies:
4.100≤(Li 2 O+Na 2 O+K 2 O+B 2 O 3 )/(P 2 O 5 +ZrO 2 +CaO) is less than or equal to 6.000; and/or the number of the groups of groups,
0.100≤P 2 O 5 ×(CaO+ZrO 2 +Li 2 O+Al 2 O 3 )/(Na 2 O+K 2 O+B 2 O 3 ) Less than or equal to 0.900, preferably, 0.190 less than or equal to P 2 O 5 ×(CaO+ZrO 2 +Li 2 O+Al 2 O 3 )/(Na 2 O+K 2 O+B 2 O 3 ) Less than or equal to 0.900. By making the composition satisfy at least one of the above-described relational expressions, it is advantageous to further improve the network structure and the crystal phase structure of the transparent glass-ceramic, and thus it is advantageous to form a transparent glass-ceramic satisfying a specific structure and having excellent properties (in particular, optical properties, strength properties, etc.).
It should be noted that, in the above formulas of the present application, the content percentages in terms of moles are substituted into the formulas, i.e., the mole units do not participate in the calculation of the formulas, and P is exemplary 2 O 5 If the molar content of (2) is 0.85%, 0.85% is substituted into the formula.
3. The transparent glass-ceramic according to claim 1 or 2, wherein the composition of the transparent glass-ceramic comprises, in mole percent of oxides:
SiO 2 ：67.50mol％-71.00mol％，Al 2 O 3 ：3.50mol％-5.00mol％，P 2 O 5 ：0.85mol％-1.50mol％，ZrO 2 ：2.50mol％-3.50mol％，Na 2 O：0.00mol％-1.00mol％，K 2 o: more than 0.00mol% and not more than 0.50mol%, li 2 O:20.00mol percent to 25.00mol percent, caO: greater than 0.50mol% and not greater than 1.60mol%, B 2 O 3 :0.00mol% to 1.00mol%. The network structure of the transparent glass ceramics is further improved by adjusting the content relation of necessary oxides Thereby being beneficial to ensuring the large-size mass production effect of the transparent glass ceramics and ensuring the excellent optical performance and strength performance of the mass-produced products.
4. The transparent glass-ceramic according to any one of claims 1 to 3, wherein the transparent glass-ceramic does not contain a quartz crystal phase. The quartz crystal phase is prevented from being precipitated in the transparent glass ceramics with the petalite crystal phase and the lithium disilicate crystal phase as main crystal phases, so that the optical performance and the overall uniformity of the transparent glass ceramics are further ensured.
5. The transparent glass-ceramic according to any one of claims 1 to 4, wherein the transparent glass-ceramic has a crystallinity of at least 70.00wt%, preferably at least 80.00wt%; in the transparent microcrystalline glass, the average crystal size is not more than 100nm. The high content of the microcrystalline phase is beneficial to improving the mechanical strength performance of the microcrystalline glass. But meets the smaller average crystal size, and is beneficial to ensuring the excellent optical performance of the transparent glass ceramics.
6. The transparent glass-ceramic according to any one of claims 1 to 5, wherein the petalite crystal phase accounts for 35.00 to 50.00wt% of the transparent glass-ceramic, and the lithium disilicate crystal phase accounts for 35.00 to 50.00wt% of the transparent glass-ceramic. The petalite crystal phase and the lithium disilicate crystal phase are adjusted to meet proper proportion relation, so that a specific microstructure is formed, and further the transparent microcrystalline glass is guaranteed to have high mechanical strength and fracture toughness.
7. The transparent glass-ceramic according to any one of claims 1 to 6, wherein the transparent glass-ceramic further comprises one or more of a lithium silicate crystal phase, a lithium phosphate crystal phase, and a spodumene crystal phase as a secondary crystal phase.
8. The transparent glass-ceramic according to claim 7, wherein the glass-ceramic has a secondary crystal phase of 30.00wt% or less based on the mass of the glass-ceramic, preferably 10.00wt% or less based on the mass of the glass-ceramic. The low content of the secondary crystal phase is controlled, so that the high content of the main crystal phase is ensured, and the excellent mechanical strength performance of the transparent glass ceramics is ensured.
9. The transparent glass-ceramic according to any one of claims 1 to 8, wherein when the transparent glass-ceramic has a gauge of (200 mm to 500 mm) x (100 mm to 500 mm) x (10 mm to 40 mm), the difference in b value at nine points on the main surface of the transparent glass-ceramic is 2.00 or less, preferably 1.50 or less, more preferably 1.00 or less. The smaller the extremely poor value of b at nine positions on the main surface of the transparent glass-ceramic meeting the specification is, the better the overall uniformity and the better the optical effect are when the transparent glass-ceramic is produced into the specification, and further the glass-ceramic sheet cut by the transparent glass-ceramic meeting the specification is beneficial to meeting the excellent optical performance requirement and the display effect requirement.
Wherein, the positions of nine positions are respectively: (1) The test positions of the test circles I tangent to the long side and the adjacent short side on the main surface are in total four places; (2) Taking the point closest to the middle of the long side or the short side of the main surface on the line segment formed by the centers of the four test circles I as a round point, and forming four test positions where the four test circles II are located, wherein the four test positions are in total; (3) And taking the center point of the main surface as the center of a circle to form a test circle III.
10. The transparent glass-ceramic according to any one of claims 1 to 8, wherein when the thickness and length of the transparent glass-ceramic is (45 mm to 450 mm) x (45 mm to 350 mm) x (0.4 mm to 2.0 mm), the difference in the value of b at nine points on the main surface of the transparent glass-ceramic is not more than 0.30, preferably not more than 0.10, more preferably not more than 0.06. Nine positions are the same as the technical scheme 9. The smaller the extreme difference of the value b at nine positions of the main surface of the glass ceramic sheet in the specification is, the better the overall uniformity of the transparent glass ceramic is, and the better the overall display effect is.
11. The transparent glass-ceramic according to any one of claims 1 to 10, wherein the transparent glass-ceramic has a b value of 1.00 or less, preferably 0.70 or less, a haze of 0.25 or less, preferably 0.18 or less, and a transmittance of 90.00 or more at a wavelength of 550nm when the thickness of the transparent glass-ceramic is 0.6 mm.
Preferably, when the thickness of the transparent microcrystalline glass is 0.6mm, the b value is less than or equal to 0.60, the haze is less than or equal to 0.16%, and the transmittance of the transparent microcrystalline glass under 550nm wavelength light is more than or equal to 90.50%. The higher the transmittance, the smaller the b value and the haze, indicating that the transparent glass-ceramic is more excellent in optical properties.
12. A substrate glass which is heat treated to produce the transparent glass-ceramic according to any one of claims 1 to 11, wherein the composition of the substrate glass, in terms of mole percent of oxides, comprises:
SiO 2 ：60.90mol％-72.65mol％，Al 2 O 3 ：1.50mol％-5.00mol％，P 2 O 5 ：0.85mol％-1.50mol％，ZrO 2 ：2.00mol％-4.00mol％，Na 2 O：0.00mol％-1.00mol％，K 2 O：0.00mol％-0.50mol％，Li 2 O：20.00mol％-30.00mol％，CaO：0.00mol％-1.60mol％，B 2 O 3 ：0.00mol％-1.00mol％；
the composition of the substrate glass, expressed as mole percent of each oxide in the composition of the substrate glass, satisfies:
18.200≤Li 2 O/P 2 O 5 ≤25.500；
14.000≤2×Li 2 O/(0.5×ZrO 2 +CaO). Ltoreq. 23.000. By enabling the base material glass to meet the composition requirements, not only can the good melting condition of the base material glass brick be ensured, but also the transparent microcrystalline glass brick with good overall uniformity, good display effect, excellent optical performance and excellent mechanical performance, the main crystal phase of which is petalite crystal phase and lithium disilicate crystal phase, can be prepared, and further the mass production yield of the transparent microcrystalline glass of the system can be improved.
13. The substrate glass according to claim 12, wherein the composition of the substrate glass, expressed as a mole percentage of each oxide in the composition of the substrate glass, satisfies:
4.100≤(Li 2 O+Na 2 O+K 2 O+B 2 O 3 )/(P 2 O 5 +ZrO 2 +CaO) is less than or equal to 6.000; and/or the number of the groups of groups,
0.100≤P 2 O 5 ×(CaO+ZrO 2 +Li 2 O+Al 2 O 3 )/(Na 2 O+K 2 O+B 2 O 3 ) Less than or equal to 0.900, preferably less than or equal to 0.190P 2 O 5 ×(CaO+ZrO 2 +Li 2 O+Al 2 O 3 )/(Na 2 O+K 2 O+B 2 O 3 ) Less than or equal to 0.900. By making the composition satisfy at least one of the above-mentioned relational expressions, it is advantageous to further improve the network structure of the glass, and thus it is advantageous to produce transparent glass ceramics having excellent properties (particularly optical properties, strength properties, etc.) satisfying the specific structure.
14. The substrate glass according to claim 12 or 13, wherein the substrate glass is heated from room temperature to 900 ℃ at a heating rate of 10 ℃/min under a nitrogen protective atmosphere to obtain a heating DSC curve in which at least two exothermic peaks exist, wherein the first exothermic peak temperature T 1 600-730 ℃, the second exothermic peak temperature T 2 740-800 ℃ and T 1 And T 2 The relation is satisfied: t at 100℃ or more 2 -T 1 Not less than 40 ℃, preferably not less than 80 ℃ and not less than T 2 -T 1 Not less than 50 ℃. The large-size substrate glass brick manufactured by adopting the substrate glass scheme meeting the characteristic of a specific DSC curve is subjected to heat treatment under the production line process condition of mass production of glass ceramics, so that the transparent glass ceramics with optical performance and display effect meeting the use requirement of a display screen can be manufactured, and the problems that the glass brick is easily cracked, the b value difference of different areas of the glass brick is large, unexpected color, flower flakes, poor display and the like in mass production of the glass ceramics in the prior art can be well solved.
15. The substrate glass according to any one of claims 12 to 14, wherein the substrate glass is heated from room temperature to 1400 ℃ for 10min at a temperature rising rate of 10 ℃/min under a nitrogen protection atmosphere and then cooled from 1400 ℃ to 450 ℃ at a temperature falling rate of 10 ℃/min to obtain a cooled DSC curve, wherein the sum S of the integrated areas of the exothermic peak and the endothermic peak contained therein is less than or equal to 10, preferably no endothermic peak and/or exothermic peak, more preferably s=0 in the range of 500 ℃ to 900 ℃. The large-size substrate glass brick manufactured by adopting the substrate glass scheme meeting the characteristic of a specific DSC curve is subjected to heat treatment under the production line process condition of mass production of glass ceramics, so that the transparent glass ceramics with optical performance and display effect meeting the use requirement of a display screen can be manufactured, and the problems that the glass brick is easily cracked, the b value difference of different areas of the glass brick is large, unexpected color, flower flakes, poor display and the like in mass production of the glass ceramics in the prior art can be well solved.
16. The substrate glass according to any one of claims 12 to 15, wherein the substrate glass is warmed from room temperature to T at a warming rate of 10 ℃/min 1-30 The temperature is kept for 240min at the temperature point, and the content of quartz crystal phase in the product obtained after the treatment is less than 15wt%; wherein T is 1-30 ＝T 1 -30℃。
17. The substrate glass of any one of claims 12-16, wherein the substrate glass is warmed from room temperature to T at a warming rate of 10 ℃/min 1-60 The temperature is kept for 240min at the temperature point, and the quartz crystal phase content in the product obtained after the treatment is less than 5wt%, preferably no quartz crystal phase; wherein T is 1-60 ＝T 1 -60℃。
At T 1-30 And/or T 1-60 When the substrate glass meeting the requirement of specific quartz crystal phase content is subjected to heat treatment at the temperature, the quartz crystal phase affecting the optical performance of the glass ceramics can be effectively prevented from being separated out from the target glass ceramics during the preparation of the target glass ceramics by heat treatment, and the large-size transparent glass ceramics meeting the use requirement can be produced in a large scale.
18. A chemically strengthened glass-ceramic, wherein the composition at the center of the chemically strengthened glass-ceramic is the same as the composition of the transparent glass-ceramic of any one of claims 1 to 11, the chemically strengthened glass-ceramic comprising a compressive stress layer region extending from the surface of the transparent glass-ceramic to a compressive depth, and having a tensile stress inside the chemically strengthened glass-ceramic. The compressive stress layer is formed on the surface of the transparent glass ceramics, so that the mechanical property of the transparent glass ceramics is further improved.
19. The chemically strengthened glass ceramic of claim 18 wherein the chemical strengthening isThe glass ceramic is obtained by performing chemical strengthening treatment on the transparent glass ceramic according to any one of the technical schemes 1 to 11, wherein the salt bath for the chemical strengthening treatment is mixed molten salt, and the composition of the mixed molten salt comprises: naNO 0 < 3 ＜100wt％、0＜KNO 3 ＜100wt％，0＜LiNO 3 ≤0.2wt％。
Preferably, the temperature of the salt bath for the chemical strengthening treatment is 430-530 ℃, and the time of the chemical strengthening treatment is 0.5-15.0 h. The chemical strengthening is performed by adopting the strengthening process, which is beneficial to improving the chemical strengthening efficiency and simultaneously ensures that the chemically strengthened microcrystalline glass obtains the expected stress level.
20. The chemically strengthened glass ceramic of claim 18 or 19, wherein the surface Na of the chemically strengthened glass ceramic 2 The O concentration is 5.0wt% to 20.0wt%. By satisfying the above range of surface Na 2 The O concentration not only can ensure that the chemically strengthened glass ceramics has better surface stress level, but also can ensure that the chemically strengthened glass ceramics has better weather resistance and chemical durability.
21. The chemically strengthened glass ceramic of any one of claims 18-20 wherein the chemically strengthened glass ceramic has a cs_50 of 110-200MPa, cs_50 being the compressive stress value at a depth of 50 μm from the major surface of the chemically strengthened glass ceramic. The cs_50 range of the chemically strengthened glass ceramic is within the above range, which indicates that the chemical strengthened glass ceramic has high compressive stress at the depth of 50 μm from the surface, indicating that the chemical strengthened glass ceramic has higher surface stress level, and the more the drop impact residual energy can be counteracted by the higher surface compressive stress level, thereby ensuring that the chemical strengthened glass ceramic has excellent damage resistance.
22. The chemically strengthened glass ceramic of any one of claims 18-21 wherein the chemically strengthened glass ceramic has an absolute value of the average tensile stress of |ct_av|, of 84-140 MPa. In the above range, the |CT_AV| of the chemically strengthened glass ceramic shows that the chemically strengthened glass ceramic has higher tensile stress level, and reflects that the glass ceramic has higher surface stress level, and the more the drop impact residual energy can be counteracted by the higher surface compressive stress level, so that the glass ceramic is ensured to have excellent damage resistance.
23. The chemically strengthened glass ceramic of any one of claims 18-22 wherein the depth of compressive stress layer dol_0 of the chemically strengthened glass ceramic is 0.18t-0.25t, t being the thickness of the chemically strengthened glass ceramic. The DOL_0 of the chemically strengthened glass ceramic is in the range, which shows that the chemically strengthened glass ceramic has high depth of layer of compressive stress, and is more beneficial to counteracting the energy driving crack growth, thereby ensuring the excellent damage resistance.
24. The chemically strengthened glass ceramic according to any one of claims 18 to 23, wherein the chemically strengthened glass ceramic having a thickness of 0.6mm is subjected to a plurality of fixed-point height drop tests with 120-mesh sand paper, the fixed-point height of the test being 1.0m, and the number of times the chemically strengthened glass ceramic drops to break is not less than 30, preferably not less than 50. When the glass is broken by fixed-point high falling, the more times of falling to break, the better the anti-falling damage performance of the chemically strengthened glass ceramics is.
25. A method for preparing transparent glass ceramics according to any one of claims 1 to 11, comprising: heat treating the substrate glass of any of claims 12-17 to produce the transparent glass-ceramic.
The heat treatment comprises a nucleating treatment and a crystallization treatment, wherein the temperature of the nucleating treatment is (Tg-20 ℃) to (Tg+40 ℃), the time of the nucleating treatment is 0min-6000min, and the temperature of the crystallization treatment is (T) 1 -20 ℃ C.) to (T) 1 The crystallization treatment time is 30min-6000min at +20deg.C; tg is the glass transition temperature of the substrate glass.
Preferably, the heating rate of the heat treatment process is 5-15 ℃/min.
26. A glass device, wherein the glass device comprises the transparent glass-ceramic of any one of claims 1-11 or comprises the chemically strengthened glass-ceramic of any one of claims 18-24.
27. An electronic device, wherein the electronic device comprises the transparent glass-ceramic of any one of claims 1-11 or comprises the chemically strengthened glass-ceramic of any one of claims 18-24.
One or more of the above technical solutions have the following advantages or beneficial effects:
According to the glass formula optimization method, the glass scheme meeting specific composition requirements is adopted, particularly the relation between the oxide content and the specific oxide content under specific conditions is met, the problem that when transparent glass ceramics with large size and main crystal phases of petalite crystal phase and lithium disilicate crystal phase are produced in batches, the glass ceramics is easy to crack can be solved, meanwhile, the prepared transparent glass ceramics can be ensured to have excellent optical performance and strength performance, and the display effect can be ensured to meet the requirements.
The oxide content and the specific oxide content relation under specific conditions met by the technical scheme can ensure the generation of petalite and lithium disilicate serving as main crystal phases, avoid the problem that when a large-size base material glass brick is used for preparing a microcrystalline glass brick, the microcrystalline glass brick is wholly blued, fogged and even cracked, and are favorable for obtaining excellent optical performance and strength of transparent microcrystalline glass, so that the whole display effect of the transparent microcrystalline glass can meet the application requirement of a display screen cover plate. Meanwhile, after the transparent glass ceramics are subjected to chemical strengthening treatment, the chemically strengthened glass ceramics with high strength can be obtained, and proved by verification, the chemically strengthened glass ceramics have excellent anti-falling capability.
Proved by verification, under the large-size specification, the range of the value b of nine positions on the main surface of the transparent glass ceramic prepared by the technical scheme of the application is less than or equal to 2.00; under the small-size specification, the extremely poor value of b at nine positions on the main surface of the transparent glass-ceramic prepared by the technical scheme is less than or equal to 0.30, preferably less than or equal to 0.10, which indicates that the difference of b values of the transparent glass-ceramic prepared by the technical scheme in different areas of the main surface is small no matter the transparent glass-ceramic is large in size or small in size, the optical performance of the transparent glass-ceramic is good, and the whole display effect can meet the application requirement of a display screen cover plate. And under large-size specification, the microcrystalline glass can meet the requirement that the b value is uniform, and the high product yield is ensured.
Another one or more of the above technical solutions has the following advantages or beneficial effects:
the large-size substrate glass brick manufactured by adopting the specific substrate glass scheme meeting the characteristics of the specific DSC curve is subjected to heat treatment under the production line process condition of mass production of glass ceramics, so that the transparent glass ceramics with optical performance and display effect meeting the use requirements of a display screen can be manufactured, and the problems that the glass brick is cracked, the b values of different areas of the glass brick are large in difference, unexpected colors, flower pieces, poor display and the like in mass production of the glass ceramics in the prior art can be well solved. Therefore, before preparing the large-size glass ceramic tile, a glass sample can be prepared by melting according to a glass formula, whether the glass scheme is suitable for producing large-size glass ceramic, especially qualified glass ceramic products with large thickness is verified in advance according to the obtained DSC curve characteristics, if the glass scheme is not suitable for producing large-size glass ceramic, the glass can be adjusted in time until the glass scheme is suitable for large-size preparation after meeting the special DSC curve characteristics, so that time and cost can be greatly saved, and waste of resources can be effectively avoided.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting the scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a DSC graph of the temperature decrease of the substrate glass of example 1;
FIG. 2 is a DSC graph of the temperature decrease of the substrate glass of comparative example 4;
FIG. 3 is a DSC graph of the temperature rise of the base glass of example 1;
FIG. 4 is a DSC graph of the temperature rise of the base glass of example 22;
FIG. 5 is a DSC graph of the temperature rise of the base glass of comparative example 1;
FIG. 6 is a DSC graph of the temperature rise of the substrate glass of comparative example 2;
FIG. 7 shows a substrate glass of example 3 subjected to heat treatment process A (crystallization temperature T 1-60 The crystallization treatment time is 240 min), and the XRD diffraction pattern of the obtained product is obtained;
FIG. 8 shows a substrate glass of comparative example 2 subjected to heat treatment process A (crystallization temperature T 1-60 The crystallization treatment time is 240 min), and the XRD diffraction pattern of the obtained product is obtained;
FIG. 9 is an XRD diffraction pattern of the glass ceramic obtained by treating the base glass of example 3 with the heat treatment process B;
FIG. 10 is an XRD diffraction pattern of the glass ceramic obtained by treating the base glass of comparative example 2 with the heat treatment process B;
FIG. 11 is Li 3 PO 4 The crystal is attached with a structural schematic diagram of lithium silicate crystal;
FIG. 12 is a standard XRD diffraction pattern for quartz present in glass-ceramic;
FIG. 13 is a schematic diagram of nine test positions when nine b-value tests are performed on the main surface of glass ceramic, and circles in the diagram are all test circle positions;
FIG. 14 is a schematic view showing a state of a glass ceramic flower;
FIG. 15 is a comparison of XRD diffraction patterns of a 0.6mm thick glass-ceramic sheet of example 1 at the position of maximum b and at the position of minimum b in a nine-pass b test;
FIG. 16 is a comparison of XRD diffraction patterns of a 0.6mm thick glass-ceramic sheet (with flower) of comparative example 6 at the position of maximum b and at the position of minimum b in the nine-position b test;
FIG. 17 is a graph showing the transmittance of the glass ceramic obtained by treating the base glass of example 6 by the heat treatment process B, wherein the thickness of the glass ceramic is 0.6 mm;
FIG. 18 is a graph showing the transmittance of the glass ceramic obtained by heat treatment process B of the substrate glass of comparative example 4 at a thickness of 0.6 mm;
FIG. 19 is a photograph of a substrate glass tile of comparative example 9;
fig. 20 is a photograph of the glass-ceramic tile obtained by subjecting the base glass tile of comparative example 7 to heat treatment process B.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. Wherein the terms "optional" and "optionally" mean either comprising or not comprising (or may not be present).
Noun interpretation and test method:
substrate glass: refers to glass that has not been nucleated, crystallized, or strengthened.
Microcrystalline glass: also known as glass ceramics, are a class of solid composites comprising both a glassy phase and a crystalline phase (or also called microcrystalline, crystalline phase) prepared by targeted controlled crystallization of a substrate glass.
Transparent glass ceramics: meaning that the glass-ceramic is transparent in the visible range.
Chemically strengthened glass ceramics: the solid composite material is obtained after the microcrystalline glass is subjected to chemical strengthening treatment. When high-temperature chemical strengthening treatment is carried out, alkali metal ions (such as potassium ions and sodium ions) with large ion radius in molten salt bath can replace alkali metal ions (such as sodium ions and lithium ions) with small ion radius in microcrystalline glass, so that ion exchange volume difference is generated, and compressive stress is generated on the surface of the microcrystalline glass.
Main crystal phase: refers to a crystalline phase having a higher weight content than other crystalline phases present in the transparent glass-ceramic.
Major surface: refers to the surface of the glass block or glass sheet with the largest surface area, such as the upper and lower surfaces of the cover glass.
Transmittance: the ratio of the radiant energy projected through the object to the total radiant energy projected onto the object during the exit of the incident light flux from the illuminated or medium incident face to the other face.
b value: belongs to a Lab color model, a color mode is set by the International Commission on illumination, and the b value is positive and negative to represent yellow and blue.
Haze: haze (haze) is the percentage of the total transmitted light intensity that is greater than 2.5 from the incident light.
And (3) nucleating: the nucleation substances in the glass grow small crystal nuclei through heat treatment.
Crystallization: the glass is grown with a certain crystal on the basis of the crystal nucleus by heat treatment.
Flower piece: when strong light is incident on the glass sheet from the side, the main surface of the glass sheet exhibits localized coloration and/or the entire glass sheet is unevenly colored, as shown in FIG. 14. The product with the flower sheets cannot meet the display use requirement of the cover plate glass of the display screen, and is defined as a defective product in the production process.
Precursor: one form of presence before the target is obtained.
Glass transition temperature: tg, the brittleness temperature of glass, which is the highest temperature at which glass becomes brittle, is known as the unit of C, corresponding to a viscosity of 10 12 Pa·s, also known as the upper annealing temperature, at which internal stresses of the glass article due to uneven cooling can be eliminated. Tg is obtained through a temperature rising DSC curve of the base material glass, a step which is represented on the DSC curve and changes from a base line to an endothermic direction is formed, and tangent lines are respectively formed on the extending lines of the two base lines before and after the step and the inflection point of the curve, so that the average value of the temperatures corresponding to the two intersection points is the glass transition temperature.
Cs_50: refers to the compressive stress value at a depth of 50 μm from the main surface of the chemically strengthened glass ceramic.
Dol_0: the depth of layer of compressive stress, also called the depth of layer of compressive stress, refers to the distance from any surface of the glass to a position near the surface where the compressive stress is zero in the thickness direction of the glass.
Ct_av: the absolute value of the average tensile stress in the tensile stress layer refers specifically to the absolute value of the average of all tensile stresses in the tensile stress layer.
Test conditions of cs_50, |ct_av|, dol_0: the test was performed using SLP-2000 of japan collagen, light source wavelength of 518nm, soc=25.5 (nm/cm)/MPa, refractive index=1.54, exposure time: 300usec.
When testing the surfaces CS_50, |CT_AV|, DOL_0, firstly, dripping a conducting liquid on a stress meter, then wiping a chemically strengthened microcrystalline glass sample to be tested, placing the chemically strengthened microcrystalline glass sample on a test path, and testing the stress value of the chemically strengthened microcrystalline glass sample. Wherein the stress meter is SLP-2000 and the conducting liquid used by the stress meter is a conducting liquid with a refractive index of 1.51.
Optical performance test of microcrystalline glass with thickness of more than 2 mm: and testing b values of different parts of the main surface of the glass ceramic by adopting a YJD-3600C haze meter to obtain nine parts of b value range data and b value average value data. In this application, a YJD-3600C haze meter was used having a test aperture of 16.5mm, which was in accordance with the ASTM D1003/D1044, ISO13468/ISO14782 dual standard. In order to ensure accuracy, the test method is suitable for testing microcrystalline glass with the thickness of more than 2 mm. In the application, a transmission mode of a YJD-3600C haze meter is selected for testing the optical performance of microcrystalline glass.
Testing the optical performance of microcrystalline glass with the thickness of less than 2 mm: the haze, L value, a value and b value of the microcrystalline glass are tested by adopting a spectrocolorimeter CM-3600A of Kenicamantadine, and the testing aperture of the adopted spectrocolorimeter CM-3600A is 25.6mm. The transmittance and the curve thereof are tested by using an Shimadzu UV-2000 ultraviolet visible spectrophotometer. To ensure accuracy, the test method is suitable for testing glass sheets with thickness below 2 mm. In the application, the transmission mode of the spectrocolorimeter CM-3600A is selected to test the optical performance of the glass ceramics.
Synchronous thermal analysis test: testing is carried out by adopting a Metrele-tolidol TGA/DSC < 3+ > synchronous thermal analyzer according to a required process, and the obtained curves are called DSC curves, including a heating DSC curve and a cooling DSC curve.
Test conditions for the temperature rising DSC curve: grinding the base material glass, sieving with 200 meshes to obtain a sample to be tested, weighing 20The sample of about mg was heated from room temperature to 900 ℃ at a heating rate of 10 ℃/min under a nitrogen atmosphere to obtain a heating DSC curve of the sample. The differential thermal analyzer for testing the temperature rise DSC curve adopted by the application is a Metrele-tolidol TGA/DSC < 3+ > synchronous thermal analyzer, and the standard substance used for testing is alpha-Al 2 O 3 The powder, the container for placing the sample is a platinum crucible, the ambient temperature for placing the instrument is 24 ℃, and the air humidity is 40%.
Test conditions of the cooling DSC curve: grinding substrate glass, sieving with 200 meshes to obtain a sample to be tested, weighing about 20mg of the sample, heating the sample to 1400 ℃ from room temperature at a heating rate of 10 ℃/min under the protection atmosphere of nitrogen, preserving heat for 10min, and cooling the sample to 450 ℃ at a cooling rate of 10 ℃/min to obtain a cooling DSC curve of the sample. The temperature-decreasing DSC curve is processed by the origin 2022b software, and the sum of the integral areas of the endothermic peak and the exothermic peak on the curve can be obtained by adopting Gaussian (Gaussian) fitting. The differential thermal analyzer for testing the cooling DSC curve adopted by the application is a Metrele-tolidol TGA/DSC < 3+ > synchronous thermal analyzer, and the standard substance used for testing is alpha-Al 2 O 3 The powder, the container for placing the sample is a platinum crucible, the ambient temperature for placing the instrument is 24 ℃, and the air humidity is 40%.
Thickness of glass: and the test is carried out by a laser thickness gauge.
Glass sheet dimensional specification measurement: and (3) testing by adopting a secondary measuring machine (the model of the instrument is MiyuMY-YXCL-4030), placing the glass sheet to be tested on a measuring table of the secondary measuring machine, setting a program, and automatically grabbing and measuring the length and the width of the glass sheet by the instrument.
XRD test: and crushing the microcrystalline glass, grinding the microcrystalline glass into samples with the particle size smaller than 75 mu m, and testing the ground samples by using an X-ray diffractometer to obtain XRD diffraction peak curves and XRD diffraction data. The X-ray diffractometer is Shimadzu XRD-6100, the incidence angle range used in the test is 2θ=10-80 °, the scanning speed is 3 °/min, the working voltage is 40kV, and the working current is 30mA.
Determination of the crystalline phase: the XRD test result (RAW format) is imported into X-ray diffraction data Rietveld refinement software JADE Standard8.6 for fitting and analysis, and the crystalline phase in the microcrystalline glass sample can be determined.
The crystal content in the application refers to the percentage of the crystal or crystalline phase in the mass of the glass ceramics, and is the weight percentage.
Determination of the crystal content: and (3) introducing a test result (RAW format) of XRD into X-ray diffraction data Rietveld finishing software JADE Standard8.6 to perform fitting and calculation, thus obtaining the crystal content in the microcrystalline glass sample. Specifically, the ratio of the fitted peak area of the crystalline phase to the fitted total peak area is the crystal content.
Average crystal size test: using the resulting data from the XRD test, the average crystal size of the sample can be calculated according to Scherrer formula d=kλ/(βcosθ). Where λ is the X-ray wavelength, λ= 0.154056nm, β is the diffraction peak half-width, k=0.89, and θ is the bragg diffraction angle. Specifically, a file (diffraction pattern) of RAW output from the XRD instrument is curve-fitted in JADE standard8.6 software, JADE outputs a fitting report, and Peak FWHM values (diffraction Peak full width at half maximum) are converted into radians according to the angle 2θ value and Peak FWHM value corresponding to each diffraction Peak in the fitting report: beta= (FWHM/180×3.14), the grain size of each diffraction peak is calculated by Scherrer formula d=kλ/(βcosθ) and then averaged to obtain an average crystal size.
Surface Na 2 O concentration test: surface Na 2 O concentration is equal to surface Na 2 O mass/total mass of surface oxide, wherein the total mass of surface oxide comprises SiO 2 、Al 2 O 3 、P 2 O 5 、ZrO 2 、Na 2 O、K 2 O, caO and other XRF can accurately test the obtained oxide, and does not contain Li 2 O、B 2 O 3 The equivalent XRF does not allow accurate measurement of the oxide content obtained. Surface Na of the chemically strengthened glass ceramic 2 The O concentration was measured by X-ray fluorescence spectroscopy (XRF) using a device of ThermoScientific ARL TM PERFORM' X. The target material is Rh (rhodium), the light tube voltage is 40KW, the current is 60mA, the collimator is 0.15, the crystal is LiF200, the detector is FPC, the test range is 29mm circle, and the analysis software isUniQuant no-standard analysis. The XRF test was performed using an unlabeled test, and the concentration of elements having atomic numbers 6 and 6 or less or oxides thereof in the glass was not measured. I.e. in the present application, surface Na is tested by XRF 2 At the O concentration, the total mass of the surface oxides excludes the mass of elements or oxides thereof having atomic numbers 6 and below in the glass.
Fixed point height drop test:
(1) Sticking 120-mesh sand paper on the lower surface of a 187g model machine, and placing the model machine on a Wonder Inno drop test machine;
(2) Placing a glass ceramic sample wafer to be tested with the length, width and thickness specification of 50mm multiplied by 0.6mm on a smooth marble plate right below the model machine, and enabling the glass ceramic sample wafer to face sand paper;
(3) The molding machine was allowed to impact down from a fixed point height of 1.0m, impacting the glass ceramic coupon located directly below the molding machine. If the glass ceramics sample is not broken, repeating the drop impact process after replacing the sand paper on the lower surface of the model machine until the glass ceramics is broken, and recording the drop times during breaking.
And taking at least 10 identical microcrystalline glass sample wafers from each batch for carrying out fixed-point height drop test, and calculating the average value of test results of the 10 microcrystalline glass sample wafers for representing the drop resistance of the microcrystalline glass.
As described above, in some embodiments of the present application, there is provided a transparent glass-ceramic and a base glass for preparing the same, which is subjected to a heat treatment to obtain the transparent glass-ceramic, and thus it is understood that the composition of the base glass is the same as that of the transparent glass-ceramic in terms of oxide.
In some embodiments of the present application, the transparent glass-ceramic comprises petalite (liaalsi) as the main crystal phase 4 O 10 ) Crystalline and main crystalline phases lithium disilicate (Li) 2 Si 2 O 5 ) A crystalline phase. By "primary crystalline phase" is meant herein that the majority of the crystalline phase content in the transparent glass-ceramic of the present application is that the petalite crystalline phase and the lithium disilicate crystalline phase have a higher weight percentage than the other crystalline phases present in the transparent glass-ceramic.
In some embodiments of the present application, the composition of the transparent glass-ceramic or substrate glass, in mole percent of oxides, comprises: siO (SiO) 2 ：60.90mol％-72.65mol％，Al 2 O 3 ：1.50mol％-5.00mol％，P 2 O 5 ：0.85mol％-1.50mol％，ZrO 2 ：2.00mol％-4.00mol％，Na 2 O：0.00mol％-1.00mol％，K 2 O：0.00mol％-0.50mol％，Li 2 O：20.00mol％-30.00mol％，CaO：
0.00mol％-1.60mol％，B 2 O 3 ：0.00mol％-1.00mol％；
The composition of the transparent microcrystalline glass or the substrate glass is expressed by the mol percent of each oxide in the composition of the transparent microcrystalline glass or the substrate glass, and the composition of the transparent microcrystalline glass or the substrate glass meets the following conditions:
18.200≤Li 2 O/P 2 O 5 ≤25.500；
14.000≤2×Li 2 O/(0.5×ZrO 2 +CaO). Ltoreq. 23.000. Through meeting the relation between the oxide content and the specific oxide content under specific conditions, not only can the generation of petalite and lithium disilicate in a main crystal phase be ensured, but also the problem that when a glass brick is prepared from a large-size substrate glass brick, the glass brick is blue and fogged and even cracked wholly is avoided under the condition that the good melting condition of the substrate glass brick is ensured, and the transparent glass ceramic is favorable for obtaining excellent optical performance and strength, so that the whole display effect of the transparent glass ceramic can meet the application requirement of a display screen cover plate. Meanwhile, after the transparent glass ceramics are subjected to chemical strengthening treatment, the chemically strengthened glass ceramics with high strength can be obtained.
In the glass system of the present application, siO 2 Is an oxide forming a glass network skeleton, is used for stabilizing the network structure of base material glass and microcrystalline glass, and is an important component forming crystalline phases such as lithium silicate, petalite, beta-spodumene, quartz and the like. SiO (SiO) 2 When the content is too small, the glass tends to have a high thermal expansion coefficient, and the thermal shock resistance is lowered; siO (SiO) 2 When the content is too large, the glass becomes poor in meltingThe viscosity of the molten glass increases, which makes it difficult to clarify the glass, and the difficulty in molding glass increases, and the productivity decreases, which also leads to a longer crystallization heat treatment time for the base glass. In the application, the transparent microcrystalline glass or the substrate glass comprises 60.90mol% to 72.65mol% of SiO 2 。
In some embodiments, the transparent glass ceramic or substrate glass may each comprise 60.90mol% to 72.65mol%, 60.90mol% to 72.00mol%, 60.90mol% to 71.00mol%, 60.90mol% to 70.00mol%, 60.90mol% to 69.00mol%, 60.90mol% to 68.00mol%, 62.00mol% to 72.00mol%, 63.00mol% to 72.00mol%, 64.00mol% to 72.00mol%, 65.00mol% to 72.00mol%, 66.00mol% to 72.00mol%, 67.00mol% to 72.00mol%, or 67.50mol% to 71.00mol% SiO 2 . In some embodiments, the transparent glass ceramic or substrate glass may each comprise 60.90mol%, 62.00mol%, 63.00mol%, 64.00mol%, 65.00mol%, 66.00mol%, 67.00mol%, 67.50mol%, 68.00mol%, 69.00mol%, 70.00mol%, 71.00mol%, 72.00mol%, or 72.65mol% SiO 2 Or SiO within a numerical range of any 2 of the specific values mentioned above as endpoints 2 . It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramic or substrate glass having the properties required for the present application is obtained.
In the glass system of the present application, al 2 O 3 Can be used for constructing a glass skeleton and is an indispensable component for forming petalite. Al (Al) 2 O 3 The crystal nuclei are coordinated around the crystal nuclei to form a "center-shell" structure, which makes it difficult to supply the crystal nuclei components from the outside of the shell, and the crystal nuclei are not easily grown large and a plurality of fine crystal grains are easily formed. Al (Al) 2 O 3 When the content is too small, the glass tends to have a high thermal expansion coefficient, the chemical durability is reduced, crystal nuclei are liable to become large, and glass ceramics are liable to be cloudy; al (Al) 2 O 3 When the content is too large, the glass becomes poor in meltability, and production becomes difficult, and crystals of mullite are easily precipitated to devitrify the glass. In the present applicationIn the glass system, the transparent microcrystalline glass or the substrate glass comprises 1.50mol percent to 5.00mol percent of Al 2 O 3 Al satisfying the content range 2 O 3 The glass network structure is stabilized, the mechanical property and chemical durability of the transparent glass ceramics are improved, the phase separation of the glass is inhibited, the thermal expansion coefficient is reduced, and the strain point is improved.
In some embodiments, the transparent glass ceramic or substrate glass may each comprise 1.50mol% to 5.00mol%, 3.50mol% to 4.00mol%, 3.50mol% to 4.50mol%, 4.00mol% to 5.00mol% or 4.50mol% to 5.00mol% Al 2 O 3 . In some embodiments, the transparent glass ceramic or substrate glass may each comprise 1.50mol%, 2.00mol%, 2.50mol%, 3.00mol%, 3.50mol%, 4.00mol%, 4.50mol%, or 5.00mol% Al 2 O 3 Or Al in a numerical range of any 2 specific values as the end points 2 O 3 . It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramic or substrate glass having the properties required for the present application is obtained.
In the glass system of the present application, li 2 O is a main component of petalite crystal phase and lithium silicate crystal phase, and is also an essential component for chemical strengthening. When Li 2 When the O content is too small, the glass melting property is easy to be reduced or the viscosity is easy to be increased, so that the glass liquid is difficult to be clarified, the substrate glass is difficult to form, crystalline phases such as mullite and the like are easy to be separated out from the glass, and the glass is devitrified; while Li is 2 When the O content is too large, the crystallization ability of the glass becomes too strong, the glass tends to devitrify, and the glass ceramics becomes easily broken. In the glass system of the application, the transparent microcrystalline glass or the substrate glass comprises 20.00mol% to 30.00mol% of Li 2 O, li satisfying the content range 2 And the O is beneficial to ensuring that the performances such as transparency, melting and crystallization capacity of the glass ceramics meet the requirements.
In some embodiments, the transparent glass ceramic or substrateThe material glass can contain 20.00mol% to 30.00mol%, 20.00mol% to 25.00mol%, 20.00mol% to 24.00mol%, 20.00mol% to 23.00mol%, 20.00mol% to 22.00mol%, 20.00mol% to 21.00mol% or 21.00mol% to 23.00mol% of Li 2 O. In some embodiments, the transparent glass ceramic or substrate glass may each comprise 20.00mol%, 21.00mol%, 22.00mol%, 23.00mol%, 24.00mol%, 25.00mol%, 26.00mol%, 27.00mol%, 28.00mol%, or 30.00mol% Li 2 O, or Li in a numerical range of any 2 specific values as the end points 2 O. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramic or substrate glass having the properties required for the present application is obtained.
In the glass system of the present application, P 2 O 5 Is a glass forming oxide which is formed by phosphorus-oxygen tetrahedra [ PO ] 4 ]Is present in the network architecture. P (P) 2 O 5 In the heat treatment process, the glass is firstly phase-separated and aggregated to form a precursor phase Li with an amorphous state 3 PO 4 Then by Li 3 PO 4 As heterogeneous nucleation sites, crystalline phases such as lithium silicate attach to Li in an amorphous form 3 PO 4 And (5) growing. With P 2 O 5 The content is increased, the non-homogeneous nucleation point is increased, li is used as 3 PO 4 The crystal grains of nucleation points are effectively refined, which is beneficial to improving the overall transmittance of the microcrystalline glass, the uniformity of the glass and reducing the b value. But when P 2 O 5 When the content is too high, the crystallization upper limit temperature is raised, and more Li is easily generated 3 PO 4 Crystals such that lithium silicate and petalite Li are formed 2 The insufficient O content can further cause that the substrate glass is easy to precipitate quartz crystals, so that the transmittance of the microcrystalline glass is reduced, the optical uniformity of the whole microcrystalline glass is reduced, and furthermore, the substrate glass is directly crystallized during fusion molding. While when P 2 O 5 When the content is too small, zrO may be easily precipitated 2 Coarse crystals devitrify the glass. In the glass system of the application, the transparent microcrystalline glass or the substrate glass comprises 085mol% to 1.50mol% of P 2 O 5 P in the content range 2 O 5 The glass ceramic has high transmittance and good optical uniformity, is beneficial to obviously reducing the value b, and achieves the best gain effect.
In some embodiments, the transparent glass ceramic or substrate glass may each comprise 0.85mol% to 1.50mol%, 0.85mol% to 1.40mol%, 0.85mol% to 1.30mol%, 0.85mol% to 1.20mol%, 0.85mol% to 1.10mol%, 0.85mol% to 1.00mol% or 1.00mol% to 1.30mol% P 2 O 5 . In some embodiments, the transparent glass ceramic or substrate glass may each comprise 0.85mol%, 0.95mol%, 1.00mol%, 1.10mol%, 1.20mol%, 1.30mol%, 1.40mol%, or 1.50mol% P 2 O 5 Or P in a numerical range in which any 2 specific numerical values mentioned above are set forth as endpoints 2 O 5 . It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramic or substrate glass having the properties required for the present application is obtained.
In the glass system of the present application, due to P 2 O 5 Preferential formation of Li in amorphous form during heat treatment 3 PO 4 And P is 2 O 5 The increase of (2) tends to compete for more Li 2 O, thereby reducing the production amount of lithium silicate and petalite, and therefore, a certain degree of Li supplementation is required 2 O. In contrast, in the system of the present application, the composition of the transparent glass ceramic or the substrate glass, expressed as the mole percentage of each oxide in the composition of the transparent glass ceramic or the substrate glass, satisfies the following conditions: 18.200 Li is less than or equal to 2 O/P 2 O 5 And less than or equal to 25.500, wherein the chemical formula in the formula represents the mole percent of the oxide, which is beneficial to ensuring the generation of a main crystal phase and improving the strength performance of the glass. In some embodiments, li 2 O/P 2 O 5 The values of (3) may be, for example, 18.200, 18.300, 18.400, 18.500, 18.600, 18.700, 18.800, 18.900, 19.000, 19.100, 19.200, 19.300, 19.400, 19.500, 19.600, 19.700, 19.800, 19.900, 20.000. 20.100, 20.200, 20.300, 20.400, 20.500, 20.600, 20.700, 20.800, 20.900, 21.000, 21.100, 21.200, 21.300, 21.400, 21.500, 21.600, 21.700, 21.800, 21.900, 22.000, 22.100, 22.200, 22.300, 22.400, 22.500, 22.600, 22.700, 22.800, 22.900, 23.000, 23.100, 23.200, 23.300, 23.400, 23.500, 23.600, 23.700, 23.800, 23.900, 24.000, 24.100, 24.200, 24.300, 24.400, 24.500, 24.600, 24.700, 24.800, 24.900, 25.000, 25.100, 25.200, 25.300, 25.400, or 25.500, or may be a value within a range of values consisting of any 2 of the specific values as endpoints.
In the glass system of the present application, an appropriate amount of ZrO 2 After heat treatment, the glass ceramic exists in a residual glass phase, which is beneficial to improving the mechanical property of the glass ceramic. But excessive ZrO 2 The difficulty of melting the base material glass is increased, white zirconium precipitation is easily generated in the base material glass, and the transparent microcrystalline glass is not produced easily. In the glass system of the application, the transparent microcrystalline glass or the substrate glass comprises 2.00mol percent to 4.00mol percent of ZrO 2 ZrO satisfying the content range 2 Is beneficial to producing transparent glass ceramics and improving the mechanical property of the transparent glass ceramics.
In some embodiments, the transparent glass ceramic or substrate glass may each comprise 2.00mol% to 4.00mol%, 2.50mol% to 3.50mol%, 2.50mol% to 3.30mol%, 2.50mol% to 3.10mol%, 2.50mol% to 3.00mol%, 2.50mol% to 2.80mol%, 2.80mol% to 3.50mol%, 2.80mol% to 3.40mol%, 2.80mol% to 3.30mol% or 2.80mol% to 3.10mol% ZrO 2 . In some embodiments, the transparent glass ceramic or substrate glass may each comprise 2.00mol%, 2.50mol%, 2.70mol%, 2.90mol%, 3.00mol%, 3.10mol%, 3.30mol%, 3.50mol%, or 4.00mol% ZrO 2 Or ZrO within a numerical range of any 2 specific numerical values as described above as the end points 2 . It is to be understood that in the specific embodiment, any of the above ranges may be combined with any other range as long as the desired properties of the present application are obtained in the transparent glass ceramic or substrate glassMay be used.
In the glass system of the present application, an appropriate amount of B 2 O 3 Helping to lower the melting temperature of the substrate glass. B (B) 2 O 3 With boron-oxygen triangle [ BO ] 3 ]And boron oxygen tetrahedra [ BO ] 4 ]As a structural unit, with B 2 O 3 The increase in the content causes the inversion of the structure and properties due to the relative content changes of the boron oxide triangle and the boron oxide tetrahedron. When B is 2 O 3 When the addition amount is too large, on the one hand, the boron oxide tetrahedron [ BO ] with three-dimensional rack-like structure 4 ]Boron-oxygen triangle [ BO ] converted into two-degree space lamellar structure 3 ]While the tridentate boron-oxygen triangle [ BO ] 3 ]Unlike boron oxygen tetrahedra [ BO ] 4 ]High strength, the effect of opening the network structure can occur, and meanwhile, the residual glass phase B 2 O 3 The increase of the content can reduce the viscosity of the residual glass phase and promote the growth of crystals such as lithium silicate and the like; on the other hand, siO is more likely to be precipitated in the base glass 2 The crystalline phase (e.g., cristobalite) affects the transmittance of the glass and also deteriorates the overall uniformity of the glass block. In the glass system of the application, the transparent microcrystalline glass or the substrate glass comprises 0.00mol percent to 1.00mol percent of B 2 O 3 B satisfying the content range 2 O 3 The glass substrate is beneficial to reducing the melting temperature of the substrate glass and improving the performances of the microcrystalline glass such as transmittance, overall uniformity and the like.
In some embodiments, the transparent glass ceramic or substrate glass may each comprise 0.00mol% to 1.00mol%, 0.00mol% to 0.90mol%, 0.00mol% to 0.80mol%, 0.00mol% to 0.70mol%, 0.00mol% to 0.60mol%, 0.00mol% to 0.50mol%, 0.00mol% to 0.40mol%, 0.20mol% to 1.00mol%, 0.30mol% to 0.80mol% or 0.30mol% to 0.50mol% of B 2 O 3 . In some embodiments, the transparent glass ceramic or substrate glass may each comprise 0.00mol%, 0.10mol%, 0.20mol%, 0.30mol%, 0.40mol%, 0.50mol%, 0.70mol%, 0.90mol%, or 1.00mol% B 2 O 3 Or B in a numerical range of any 2 of the specific values as defined above 2 O 3 . It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramic or substrate glass having the properties required for the present application is obtained.
In the glass system of the present application, na 2 O、K 2 O is an external oxide of the glass network, and can provide free oxygen to increase the oxygen-silicon ratio in the glass structure, thus, excessive Na 2 O、K 2 O affects the network structure of the glass, and affects the optical properties, thermal stability, chemical stability, mechanical strength, and weather resistance of the glass. However, in the glass system of the present application, an appropriate amount of Na 2 O and K 2 O is an effective amount of Na, e.g 2 The O can play roles in adjusting grain size, promoting crystallization of lithium silicate structure, reducing crystallization tendency of base material glass and the like, so that the transmittance of the microcrystalline glass can be properly increased, and the thermal stability, chemical stability, mechanical strength, weather resistance and the like of the microcrystalline glass are properly improved. Therefore, in the glass system of the present application, it is preferable that the transparent glass ceramics or the base glass each contain Na in an amount of 0.00mol% to 1.00mol% 2 O, 0.00mol% to 0.50mol% K 2 O。
In some embodiments, the transparent glass ceramic or substrate glass may each comprise 0.00mol% to 1.00mol%, 0.00mol% to 0.90mol%, 0.00mol% to 0.80mol%, 0.00mol% to 0.70mol%, 0.00mol% to 0.60mol%, 0.00mol% to 0.50mol%, 0.00mol% to 0.40mol%, 0.20mol% to 1.00mol%, 0.30mol% to 0.80mol% or 0.30mol% to 0.50mol% Na 2 O. In some embodiments, the transparent glass ceramic or substrate glass may each comprise 0.00mol%, 0.10mol%, 0.20mol%, 0.30mol%, 0.40mol%, 0.50mol%, 0.70mol%, 0.90mol%, or 1.00mol% Na 2 O, or Na within a range of values defined by any 2 of the specific values as endpoints 2 O. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramic or substrate glass having the properties required for the present application is obtained.
In some embodiments, the transparent glass ceramic or substrate glass may each comprise 0.00mol% to 0.50mol%, 0.00mol% to 0.40mol%, 0.00mol% to 0.30mol%, 0.00mol% to 0.20mol%, 0.00mol% to 0.10mol%, 0.10mol% to 0.50mol% or 0.20mol% to 0.40mol% K 2 O. In some embodiments, the transparent glass ceramic or substrate glass may each comprise 0.00mol%, 0.10mol%, 0.20mol%, 0.30mol%, 0.40mol%, or 0.50mol% K 2 O, or K in a range of values defined by any 2 of the specific values as endpoints 2 O. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramic or substrate glass having the properties required for the present application is obtained.
In the glass system, a proper amount of CaO is beneficial to increasing the chemical stability and mechanical strength of the glass, reducing the viscosity of the glass, enhancing the meltability and formability of the glass and adjusting the thermal expansion coefficient and refractive index of the microcrystalline glass. However, when the CaO content is too large, the glass is liable to be devitrified after crystallization treatment, and excessive CaO remains in the glass phase and the main crystal phase cause a refractive index difference, which leads to a decrease in the transmittance and an increase in haze of the glass ceramic. In the glass system, the transparent microcrystalline glass or the substrate glass comprises 0.00mol% to 1.60mol% of CaO.
In some embodiments, the transparent glass ceramic or the substrate glass may each comprise 0.00mol% to 1.60mol%, 0.50mol% to 1.50mol%, 0.50mol% to 1.30mol%, 0.50mol% to 1.20mol%, 0.50mol% to 1.00mol%, 0.50mol% to 0.85mol%, 0.85mol% to 1.40mol%, 0.85mol% to 1.30mol%, 0.85mol% to 1.20mol%, 0.85mol% to 1.10mol%, 0.85mol% to 1.00mol%, or 1.00mol% to 1.30mol% CaO. In some embodiments, the transparent glass ceramic or the base glass may each contain 0.00mol%, 0.50mol%, 0.70mol%, 0.85mol%, 0.95mol%, 1.00mol%, 1.10mol%, 1.20mol%, 1.30mol%, 1.40mol%, 1.50mol%, or 1.60mol% CaO, or CaO within a range of values defined by any 2 of the specific values as the endpoints. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramic or substrate glass having the properties required for the present application is obtained.
In the glass system, the composition of the transparent microcrystalline glass or the substrate glass, expressed as the mole percentage of each oxide in the composition of the transparent microcrystalline glass or the substrate glass, is as follows: 14.000.ltoreq.2XLi 2 O/(0.5×ZrO 2 And +CaO). Ltoreq. 23.000, wherein the chemical formula represents the mole percent of the oxide, which is beneficial to the mass production of transparent glass ceramics with large size and optical performance meeting the requirement. In some embodiments, 2×li 2 O/(0.5×ZrO 2 +cao) may be, for example, 14.000, 15.000, 16.000, 17.000, 18.000, 19.000, 20.000, 21.000, 22.000, or 23.000, or may be a value within a range of values defined by any 2 of the specific values as endpoints.
In some embodiments, the composition of the transparent glass-ceramic or substrate glass, expressed as mole percent of each oxide in the composition, is such that: 4.100 less than or equal to (Li) 2 O+Na 2 O+K 2 O+B 2 O 3 )/(P 2 O 5 +ZrO 2 +CaO). Ltoreq.6.000, wherein the chemical formula represents the mole percent of the oxide, thereby being beneficial to forming transparent microcrystalline glass with excellent performance (especially optical and strength performance) meeting specific structure. In some embodiments of the present invention, in some embodiments,
(Li 2 O+Na 2 O+K 2 O+B 2 O 3 )/(P 2 O 5 +ZrO 2 +cao) may be, for example, 4.100, 4.200, 4.300, 4.400, 4.500, 4.600, 4.700, 4.800, 4.900, 5.000, 5.100, 5.200, 5.300, 5.400, 5.500, 5.600, 5.700, 5.800, 5.900, or 6.000 and any value between these adjacent point values, or may be a value within a range of values consisting of any 2 of the specific values as described above as endpoints.
In some embodiments, in transparent microThe composition of the transparent microcrystalline glass or the substrate glass is calculated according to the content expressed by mole percent of each oxide in the composition of the crystalline glass or the substrate glass, and the composition of the transparent microcrystalline glass or the substrate glass meets the following conditions: p is more than or equal to 0.100 2 O 5 ×(CaO+ZrO 2 +Li 2 O+Al 2 O 3 )/(Na 2 O+K 2 O+B 2 O 3 ) P is not more than 0.900, preferably not more than 0.190 2 O 5 ×(CaO+ZrO 2 +Li 2 O+Al 2 O 3 )/(Na 2 O+K 2 O+B 2 O 3 ) And less than or equal to 0.900, wherein the chemical formula represents the mole percent of oxide, thereby being beneficial to forming transparent microcrystalline glass with excellent performance (especially optical and strength performance) meeting specific structure. In some embodiments, P 2 O 5 ×(CaO+ZrO 2 +Li 2 O+Al 2 O 3 )/(Na 2 O+K 2 O+B 2 O 3 ) The value of (c) may be, for example, 0.100, 0.200, 0.300, 0.400, 0.500, 0.600, 0.700, 0.800 or 0.900, or may be a value within a range of values defined by any 2 of the specific values as the endpoints.
In some preferred embodiments, the composition of the transparent glass-ceramic or substrate glass, in mole percent of oxides, comprises: siO (SiO) 2 ：67.50mol％-71.00mol％，Al 2 O 3 ：
3.50mol％-5.00mol％，P 2 O 5 ：0.85mol％-1.50mol％，ZrO 2 ：
2.50mol％-3.50mol％，Na 2 O：0.00mol％-1.00mol％，K 2 O: more than 0.00mol% and not more than 0.50mol%, li 2 O:20.00mol percent to 25.00mol percent, caO: greater than 0.50mol% and not greater than 1.60mol%, B 2 O 3 :0.00mol% to 1.00mol%. The network structure of the glass ceramics is further improved by adjusting the content relation of the necessary oxides, so that the large-size mass production effect of the transparent glass ceramics is ensured, and the excellent optical performance and strength performance of the mass production product are ensured.
In some embodiments, the transparent glass-ceramic is free of quartz crystal phases. In the microcrystalline glass with the main crystal phases of petalite crystal phase and lithium disilicate crystal phase, if quartz crystal phase is precipitated, the transmittance of the microcrystalline glass is reduced, the optical performance of the microcrystalline glass is affected, the overall uniformity of the microcrystalline glass brick is easily degraded, and the problems of larger difference of b values in different areas of the glass, flower chips and the like occur. In some embodiments, the transparent glass-ceramic has a crystallinity of greater than or equal to 70.00wt%, preferably greater than or equal to 80.00wt%. The "crystallinity of transparent glass ceramics" refers to the percentage of all crystal phases/crystals in the glass ceramics in mass of the glass ceramics. The high content of the microcrystalline phase is beneficial to improving the mechanical strength performance of the microcrystalline glass. In some embodiments, the transparent glass-ceramic may have a crystallinity of 70.00wt%, 75.00wt%, 80.00wt%, 85.00wt%, 90.00wt%, 93.00wt%, 95.00wt%, 98.00wt%, or 100.00wt%, or a crystallinity within a range of values defined by any 2 of the specific values as endpoints. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramics of the properties required in the present application are obtained.
In some embodiments, the transparent glass ceramic has an average crystal size of no more than 100nm. Meets smaller average crystal size and is beneficial to ensuring the excellent optical performance of the microcrystalline glass. In some embodiments, the average crystal size may be 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, or 100nm, or an average crystal size within a range of values defined by any 2 of the specific values recited above as endpoints. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramics of the properties required in the present application are obtained.
In some embodiments, the transparent glass ceramic comprises petalite crystal phase accounting for 35.00wt% to 50.00wt% of the transparent glass ceramic, and lithium disilicate crystal phase accounting for 35.00wt% to 50.00wt% of the transparent glass ceramic. In some embodiments, the percentage of petalite crystalline phase in the transparent glass ceramic mass may be 35.00wt% to 50.00wt%, 35.00wt% to 45.00wt%, 35.00wt% to 40.00wt%, or 40.00wt% to 50.00wt%. In some embodiments, the transparent glass-ceramic may contain 35.00wt%, 40.00wt%, 45.00wt%, or 50.00wt% petalite crystal phase, or petalite crystal phase within a range of values defined by any of the 2 specific values as endpoints. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramics of the properties required in the present application are obtained. In some embodiments, the percentage of the lithium disilicate crystalline phase by mass of the transparent glass ceramic may be 35.00wt% to 50.00wt%, 35.00wt% to 45.00wt%, 35.00wt% to 40.00wt%, or 40.00wt% to 50.00wt%. In some embodiments, the transparent glass-ceramic may contain 35.00wt%, 40.00wt%, 45.00wt%, or 50.00wt% of a lithium disilicate crystal phase, or a lithium disilicate crystal phase within a range of values defined by any of the 2 specific values recited above as endpoints. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramics of the properties required in the present application are obtained. The petalite crystal phase and the lithium disilicate crystal phase are adjusted to meet a proper proportion relation, so that a specific microstructure is formed, and further the microcrystalline glass is guaranteed to have high mechanical strength and fracture toughness.
In some embodiments, the transparent glass ceramic comprises lithium silicate (Li 2 SiO 3 ) Crystalline phase, lithium phosphate (Li) 3 PO 4 ) One or more of the crystalline phase and spodumene crystalline phase is used as a secondary crystalline phase. In some embodiments, the transparent glass ceramic comprises less than 30.00wt% of the transparent glass ceramic in a secondary crystalline phase, preferably less than 10.00wt% of the transparent glass ceramic in a secondary crystalline phase. In the transparent glass ceramic, the secondary crystal phase content is low, so that the high content of the main crystal phase is guaranteed, and the excellent mechanical strength performance of the glass ceramic is guaranteed. In some embodiments, the percentage of the secondary crystalline phase to the transparent glass-ceramic mass may be 0wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, or 30.00wt%, or a number consisting of any 2 of the specific values as the endpointsA secondary crystalline phase within the range of values. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramics of the properties required in the present application are obtained.
In some embodiments, the transparent glass ceramic comprises less than 5.00wt% of lithium silicate crystal phase, and the total amount of lithium phosphate crystal phase and spodumene crystal phase is less than 5.00wt% of transparent glass ceramic.
In some embodiments, when the transparent glass-ceramic has a gauge of (200 mm-500 mm) x (100 mm-500 mm) x (10 mm-40 mm), the range of values of b at nine locations on the major surface of the transparent glass-ceramic is 2.00 or less, preferably 1.50 or less, more preferably 1.00 or less. The "extreme difference of the nine b values" herein refers to the difference between the maximum value and the minimum value of the b values at the nine positions tested on the glass main surface. In some embodiments, the range of values for nine b on the major surface of the transparent glass-ceramic under this specification may be 0, 0.10, 0.50, 0.80, 1.00, 1.20, 1.50, 1.70, 1.80, 1.90, or 2.00, or within a range of values defined by any 2 of the specific values recited above as endpoints. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramics of the properties required in the present application are obtained. The smaller the extremely poor value of b at nine positions on the main surface of the glass-ceramic meeting the specification is, the better the overall uniformity and the better the optical effect are when the glass-ceramic is produced into the specification, and further the glass-ceramic sheet cut by the glass-ceramic meeting the specification is beneficial to meeting the excellent optical performance requirement and the display effect requirement.
In some embodiments, when the transparent glass-ceramic has a gauge of (45 mm-450 mm) x (45 mm-350 mm) x (0.4 mm-2.0 mm), the difference in b value at nine locations on the major surface of the transparent glass-ceramic is 0.30 or less, preferably 0.10 or less, preferably 0.06 or less. In some embodiments, the range of values for nine b on the major surface of the transparent glass-ceramic under this specification may be 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20, or 0.30, or within a range of values consisting of any 2 of the specific values recited above as endpoints. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramics of the properties required in the present application are obtained. The smaller the extreme difference of the value b at nine positions of the main surface of the microcrystalline glass sheet in the specification is, the better the overall uniformity of the microcrystalline glass sheet is, and the better the overall display effect is.
Wherein, nine positions are respectively: (1) The test positions of the test circles I tangent to the long side and the adjacent short side on the main surface are in total four places; (2) Taking the point closest to the middle of the long side or the short side of the main surface on the line segment formed by the centers of the four test circles I as a round point, and forming four test positions where the four test circles II are located, wherein the four test positions are in total; (3) The center point of the main surface is used as the center of the circle, and a test circle III is formed at the position shown in fig. 13. In combination with the above-mentioned b-value test method, it is known that each place to be tested is a circle having a test aperture, and the center of the circle coincides with the above-mentioned test circle i, test circle ii or test circle iii.
In some embodiments, the transparent glass-ceramic has a b value of 1.00 or less, preferably 0.70 or less, a haze of 0.25 or less, preferably 0.18 or less, and a transmittance of 90.00 or more at 550nm wavelength of light at a thickness of 0.6 mm. In some preferred embodiments, the b value is 0.60 or less and the haze is 0.16 or less at a thickness of 0.6mm for the transparent glass-ceramic, and the transmittance of the transparent glass-ceramic is 90.50 or more at a wavelength of 550 nm. The higher the transmittance, the smaller the b value and the haze, indicating that the more excellent the optical properties of the glass-ceramic.
In some embodiments, the 0.6mm thick transparent glass ceramic may have a transmittance of 90.00%, 90.50%, 91.00%, 92.00%, 93.00%, 94.00%, 95.00%, 96.00%, 97.00%, 98.00%, 99.00%, or 100.00% at a wavelength of 550nm, or a transmittance within a range of values defined by any 2 of the specific values as endpoints. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramics of the properties required in the present application are obtained. In some embodiments, the b value of a 0.6mm thick transparent glass ceramic may be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0, or a value within a range of values defined by any 2 of the specific values recited above as endpoints. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramics of the properties required in the present application are obtained. In some embodiments, the haze of a 0.6mm thick transparent glass ceramic may be 0, 0.01%, 0.05%, 0.08%, 0.10%, 0.12%, 0.14%, 0.16%, 0.18%, 0.20%, or 0.25%, or a haze within a range of values defined by any 2 of the specific values recited above as endpoints. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the transparent glass ceramics of the properties required in the present application are obtained.
As described above, the value of b at nine positions of the main surface of the transparent glass-ceramic is extremely small, namely, the value of b at different areas of the transparent glass-ceramic is close; the transparent glass ceramic has high transmittance, low b value and low haze, and the transparent glass ceramic has better optical performance and good uniformity, and can meet the application requirements of a display screen cover plate.
In some embodiments, the substrate glass is heated from room temperature to 900 ℃ at a ramp rate of 10 ℃/min under a protective atmosphere of nitrogen via simultaneous thermal analysis testing to yield a ramp DSC curve in which at least two exothermic peaks are present, wherein the first exothermic peak temperature T 1 600-730 ℃, the second exothermic peak temperature T 2 740-800 ℃ and T 1 And T 2 The relation is satisfied: t at 100℃ or more 2 -T 1 Not less than 40 ℃, preferably not less than 80 ℃ and not less than T 2 -T 1 ≥50℃。
In some embodiments, the substrate glass is heated from room temperature to 1400 ℃ for 10min at a heating rate of 10 ℃/min under a nitrogen protection atmosphere, and then cooled from 1400 ℃ to 450 ℃ at a cooling rate of 10 ℃/min, so as to obtain a cooled DSC curve, wherein the sum of the integrated areas of the exothermic peak and the endothermic peak contained in the cooled DSC curve is less than or equal to 10, preferably no endothermic peak and/or exothermic peak, more preferably s=0 in the range of 500 ℃ -900 ℃.
The large-size substrate glass brick manufactured by adopting the specific substrate glass proposal meeting the specific DSC curve characteristics (comprising the specific temperature rise DSC curve characteristics and the specific temperature reduction DSC curve characteristics) is subjected to heat treatment under the production line technological conditions of mass production of glass ceramics, so that the transparent glass ceramics with optical performance and display effect meeting the use requirements of display screens can be manufactured, and the problems of glass brick cracking, larger difference of b values in different areas of the glass brick, undesirable color, flower flakes, poor display and the like which are easily caused in the mass production of the glass ceramics in the prior art can be well solved. Therefore, before preparing the large-size microcrystalline glass brick, a glass sample can be prepared according to a glass formula, whether the glass scheme is suitable for producing a large-size qualified microcrystalline glass product, especially a large-thickness microcrystalline glass product, is verified through the obtained DSC curve characteristics, if the glass scheme is not suitable for producing the large-size qualified microcrystalline glass product, the glass sample can be timely adjusted until the glass scheme is suitable for preparing the large-size microcrystalline glass product after meeting the special DSC curve characteristics, so that time and cost can be greatly saved, and waste of resources can be effectively avoided.
In some embodiments, the substrate glass is warmed from room temperature to T at a ramp rate of 10 ℃/min 1-30 The temperature is kept for 240min for treatment, and the content of quartz crystal phase in the product obtained after the treatment is less than 15wt%; wherein T is 1-30 ＝T 1 -30℃。
In some embodiments, the substrate glass is warmed from room temperature to T at a ramp rate of 10 ℃/min 1-60 The temperature and the heat preservation at the temperature are carried out for 240min, and the content of quartz crystal phase in the product obtained after the treatment is less than 5wt percent, preferably no quartz crystal phase; wherein T is 1-60 ＝T 1 -60℃。
At T 1-30 And/or T 1-60 The substrate glass meeting the requirement of specific quartz crystal phase content after heat treatment at the temperature can effectively avoid separating out quartz crystal phase affecting the optical performance of the glass ceramics in the target glass ceramics brick when the target glass ceramics is prepared by heat treatment, thereby ensuringAnd the large-size transparent glass ceramic bricks meeting the use requirements can be produced in a large-scale mode.
The methods of making or forming the substrate glass of the present application include, but are not limited to, float, overflow, calendaring, casting, continuous melting, and the like. In order to improve the yield, the present application preferably uses a continuous melting method to prepare the base glass. The continuous melting method refers to a melting method of continuously feeding and continuously discharging. Specifically, the raw materials can be continuously put into a melting furnace through an automatic feeding device, heated to 1500-1600 ℃, melted for 24-72 hours, then drawn and formed, continuously drawn and cut into substrate glass products with any length.
The preparation method of the transparent glass ceramic comprises the following steps: and carrying out heat treatment on the base glass to obtain the transparent microcrystalline glass. The conditions for the heat treatment described in this application are widely selectable and can be selected by those skilled in the art according to the actual requirements.
In some embodiments, the heat treatment includes a nucleation treatment and a crystallization treatment, wherein the temperature of the nucleation treatment is from (Tg-20deg.C) to (Tg+40deg.C), and may be, for example, (Tg-20deg.C), (Tg-15deg.C), (Tg-10deg.C), (Tg-5deg.C), (Tg-2deg.C), tg, (Tg+2deg.C), (Tg+5deg.C), (Tg+10deg.C), (Tg+15deg.C) or any value between these adjacent dot values. Wherein Tg is the glass transition temperature of the substrate glass.
In some embodiments, the time of the nucleation is 0min-6000min, for example, it may be 0min, 30min, 50min, 70min, 100min, 130min, 150min, 180min, 200min, 250min, 280min, 300min, 330min, 360min, 600min, 800min, 900min, 1500min, 2000min or 6000min, or any value between these adjacent spot values.
In some embodiments, the crystallization process is at a temperature (T 1 -20 ℃ C.) to (T) 1 +20℃ C.) may be, for example, (T) 1 -20℃)、(T 1 -15℃)、(T 1 -10℃)、(T 1 -5℃)、(T 1 -2℃)、T 1 、(T 1 +2℃)、(T 1 +5℃)、(T 1 +10℃)、(T 1 +15℃ C.) or (T) 1 +20℃), or these neighborsAny value between the point values.
In some embodiments, the crystallization treatment time is 30min-6000min, for example, 30min, 50min, 70min, 100min, 130min, 150min, 180min, 200min, 250min, 280min, 300min, 330min, 360min, 400min, 450min, 500min, 550min, 600min, 1000min, 2000min, 3000min, 4000min, 5000min, or 6000min, or any value between these adjacent spot values.
In some embodiments, the heating rate of the heat treatment process is 5-15 ℃ per minute, for example, may be 5 ℃, 8 ℃, 10 ℃, 12 ℃, 14 ℃ or 15 ℃ per minute, or any value between these adjacent spot values.
It should be understood that, in the present application, the nucleation is performed by heating to a predetermined temperature (also referred to as a nucleation temperature) and maintaining the temperature for a certain period of time after reaching the temperature of the nucleation, where the period of time is referred to as a time of the nucleation (also referred to as a nucleation time). The crystallization treatment is to raise the temperature to a predetermined crystallization treatment temperature (also referred to as crystallization temperature), and to keep the temperature for a certain period of time after reaching the crystallization treatment temperature, wherein the heat-retaining time is the crystallization treatment time (also referred to as crystallization time). The adoption of the heat treatment condition is favorable for preparing a transparent microcrystalline glass product which has a specific microstructure and uniform structure, takes petalite crystalline phase and lithium disilicate crystalline phase as main crystalline phases and has excellent optical performance and mechanical property.
In some embodiments, the process for preparing transparent glass ceramics further comprises a step of performing cold working treatment on the transparent glass ceramics (bricks) prepared by heat treatment of the base material glass to obtain the transparent glass ceramics with the required specification and dimension (such as thickness of 0.2mm-2.0 mm). The cold working treatment herein includes shaping treatment, slicing treatment, CNC treatment, grinding treatment, polishing treatment, and the like, which are commonly used in the art. One skilled in the art can select one or more of the above modes to cold work the transparent glass ceramics according to the actual requirements.
The application provides chemically strengthened glass ceramics, which is prepared from the transparent glass ceramics through chemical strengthening treatment. The composition at the center of the chemically strengthened glass-ceramic is substantially the same as the composition of the transparent glass-ceramic, the chemically strengthened glass-ceramic comprises a compressive stress layer region extending from the surface of the transparent glass-ceramic to a depth of compression, and has a tensile stress inside the chemically strengthened glass-ceramic.
After the chemical strengthening treatment, it is understood that the composition at the surface of the glass-ceramic may be different from the composition of the as-formed glass-ceramic (i.e., the glass-ceramic has not been subjected to an ion exchange process prior to being subjected to the chemical strengthening treatment). This is because ion exchange occurs during the chemical strengthening treatment, and alkali metal ions (e.g., li + Or Na (or) + ) Respectively by larger alkali metal ions (e.g. Na + Or K + ) Instead of Na as in glass ceramics + With K in molten salt bath + Exchange by K + Alternatively, and/or, li in glass ceramics + With Na in molten salt bath + Exchange with Na + Instead of it. However, in embodiments, the composition of the glass-ceramic at or near the center of the depth of the glass article will still have the composition of the freshly formed glass-ceramic. That is, in the chemically strengthened glass ceramic of the present application, the composition of the compressive stress layer formed by ion exchange on the surface may be different from that of the unreinforced glass ceramic, while the composition of the tensile stress layer having tensile stress (also referred to as tensile stress) inside or the composition at the center of the glass ceramic may still have that of the unreinforced glass ceramic.
The conditions for the chemical strengthening treatment in the application can be selected in a wide range, and can be selected by a person skilled in the art according to actual requirements. In some embodiments, the salt bath for chemical strengthening treatment is a mixed molten salt having a composition comprising: naNO 0 < 3 ＜100wt％、0＜KNO 3 < 100wt% and 0 < LiNO 3 ≤0.2wt％。
In various embodiments, naNO in the mixed molten salt is based on 3 And KNO 3 Based on the total amount, the mixed fused salt contains 0 < NaNO 3 Less than 100wt%. For example, the mixed molten salt may comprise 20wt% to 50wt%, 10wt% to 40wt%, 20wt% to 90wt%, or 40wt% to 90wt% NaNO 3 . In various embodiments, naNO in the mixed molten salt is based on 3 And KNO 3 Total amount of mixed fused salt containing KNO of 0 < 3 Less than 100wt%. For example, the mixed molten salt may comprise KNO in an amount of 20wt% to 50wt%, 10wt% to 40wt%, 20wt% to 90wt%, or 40wt% to 90wt% 3 . In various embodiments, naNO in the mixed molten salt is based on 3 And KNO 3 In total, the mixed fused salt also contains 0 < LiNO 3 Less than or equal to 0.2wt%. For example, the mixed molten salt may comprise 0.01wt% to 0.20wt%, 0.01wt% to 0.18wt%, 0.01wt% to 0.15wt%, 0.01wt% to 0.10wt% or 0.01wt% to 0.05wt% LiNO 3 。
In some embodiments, the temperature of the salt bath for the chemical strengthening treatment is 430 ℃ to 530 ℃ and the time of the chemical strengthening treatment is 0.5h to 15.0h.
The chemical strengthening is performed by adopting the strengthening process, which is beneficial to improving the chemical strengthening efficiency and simultaneously ensures that the chemically strengthened microcrystalline glass obtains the expected stress level.
In some embodiments, the temperature of the salt bath for chemical strengthening treatment may be 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, or 530 ℃, or may be a value within a range of values consisting of any 2 specific values as the endpoints.
In some embodiments, the time of the chemical strengthening treatment may be 0.5h, 1.0h, 2.0h, 3.0h, 4.0h, 5.0h, 6.0h, 7.0h, 8.0h, 9.0h, 10.0h, 11.0h, 12.0h, 13.0h, 14.0h, or 15.0h, or may be a value within a range of values consisting of any 2 of the specific values as the endpoints.
In some embodiments, the surface Na of the chemically strengthened glass-ceramic 2 The O concentration is 5.0wt% to 20.0wt%. For example, surface Na of the chemically strengthened glass ceramic 2 O concentration can beThe amount may be 5.0wt%, 6.0wt%, 7.0wt%, 8.0wt%, 9.0wt%, 10.0wt%, 11.0wt%, 12.0wt%, 13.0wt%, 14.0wt%, 15.0wt%, 16.0wt%, 17.0wt%, 18.0wt%, 19.0wt% or 20.0wt%, or may be a value within a range of values defined by any 2 of the specific values as the endpoints. By satisfying the above range of surface Na 2 The O concentration not only can ensure that the chemically strengthened glass ceramics has better surface stress level, but also can ensure that the chemically strengthened glass ceramics has better weather resistance and chemical durability.
In some embodiments, the chemically strengthened glass-ceramic has a cs_50 of 110-200MPa, cs_50 referring to the compressive stress value at a depth of 50 μm from the major surface of the chemically strengthened glass-ceramic. For example, the chemically strengthened glass ceramic has CS_50 of 110-200MPa, 110-180MPa, 110-160MPa, 110-150MPa, 110-130MPa, 130-180MPa, or 130-150 MPa. The cs_50 range of the chemically strengthened glass ceramic is within the above range, which indicates that the chemical strengthened glass ceramic has high compressive stress at the depth of 50 μm from the surface, indicating that the chemical strengthened glass ceramic has higher surface stress level, and the more the drop impact residual energy can be counteracted by the higher surface compressive stress level, thereby ensuring that the chemical strengthened glass ceramic has excellent damage resistance. In some embodiments, the chemically strengthened glass ceramic has an absolute value of |ct_av|, ct_av|, of 84-140MPa, referring to the average tensile stress. For example, the chemically strengthened glass ceramic has an absolute CT_AV of 84-140MPa, 85-120MPa, 85-100MPa, 90-140MPa, 100-140MPa, or 120-140 MPa. In the above range, the |CT_AV| of the chemically strengthened glass ceramic shows that the chemically strengthened glass ceramic has higher tensile stress level, and reflects that the glass ceramic has higher surface stress level, and the more the drop impact residual energy can be counteracted by the higher surface compressive stress level, so that the glass ceramic is ensured to have excellent damage resistance.
In some embodiments, the depth of compression stress layer dol_0 of the chemically strengthened glass ceramic is 0.18t to 0.25t, where t is the thickness of the chemically strengthened glass ceramic. For example, the depth of layer of compressive stress DOL_0 of the chemically strengthened glass ceramic may be 0.18t-0.25t, 0.18t-0.22t, 0.18t-0.20t, 0.20t-0.25t, or 0.22t-0.25t. Illustratively, when the thickness of the chemically strengthened glass ceramic is 0.6mm, the dol_0 of the chemically strengthened glass ceramic may be 0.108mm, 0.120mm, 0.130mm, 0.140mm, 0.145mm, or 0.150mm. The DOL_0 of the chemically strengthened glass ceramic is in the range, which shows that the chemically strengthened glass ceramic has high depth of layer of compressive stress, and is more beneficial to counteracting the energy driving crack growth, thereby ensuring the excellent damage resistance.
Meets specific stress characteristics, and can ensure that the chemically strengthened glass ceramic has excellent mechanical strength performance and mechanical strength performance, in particular excellent anti-drop performance.
In some embodiments, the chemically strengthened glass-ceramic having a thickness of 0.6mm is subjected to a plurality of fixed-point height drop tests with a fixed-point height of 1.0m using 120-mesh sand paper, and the chemically strengthened glass-ceramic is dropped to a break number of 30 or more, preferably 50 or more. This indicates that the chemically strengthened glass-ceramic of the present application is excellent in drop resistance.
The transparent glass ceramics or chemically strengthened glass ceramics with excellent optical performance and mechanical performance can be used for glass devices of any needed glass ceramics and can be used for a plurality of applications. Such as countertops, other surfaces, covers for electronic devices or equipment, appliance doors, floor tiles, wall panels, storage containers, etc. Other surfaces may include, but are not limited to, exterior wall surfaces, stair tread surfaces, stud veneers, counter surfaces, etc., the types of electronic devices or equipment may include, but are not limited to, hand held, desktop mounted, wall mounted, etc., covers may include, but are not limited to, cell phone covers, cell phone backplates, tablet computer covers, etc., and storage containers may include, but are not limited to, trays, beverage bottles, etc. The following detailed description of the embodiments of the present application is exemplary and is provided for purposes of illustration only and is not to be construed as limiting the application.
In the example numbers of the following tables, S refers to the embodiment, e.g., S1 refers to embodiment 1; d refers to the comparative example, e.g., D1 refers to comparative example 1.
Example 1
(1) Preparation of a base material glass: the continuous melting method is used for producing the base material glass, the raw materials are prepared according to the proportion of each oxide in S1 of the table 1, after being uniformly mixed, the raw materials are continuously put into a melting furnace through an automatic feeding device, heated to 1600 ℃, melted for 24 hours, then drawn and formed, continuously drawn and cut into the required specification, and the base material glass (brick) product is obtained. For example, a base glass (brick) having a molding size of 360mm (length) ×180mm (width) ×30mm (thickness) can be cut.
Test of the substrate glass obtained in S1:
and I, observing, wherein the whole substrate glass prepared in the step S1 is clear and transparent.
II, determining Tg, a temperature rise DSC curve and a temperature reduction DSC curve of the substrate glass in the S1, and recording the temperature T of a first exothermic peak in the temperature rise DSC curve 1 Second exothermic peak temperature T 2 And the difference value data, the sum S data of the integral areas of the exothermic peak and the endothermic peak contained in the temperature-reducing DSC curve at the temperature of 500-900 ℃ are respectively shown in table 3, figure 1 and figure 3. Table 2 shows the results of calculation of the relation between the contents of the oxides in Table 1.
III, respectively heating the substrate glass prepared in S1 from room temperature to T at a heating rate of 10 ℃/min 1-30 Temperature and T 1-60 Temperature, and respectively at T 1-30 Temperature and T 1-60 The temperature was kept for 240min for treatment, and the quartz crystal phase content in the treated product was measured, and the results are shown in Table 3.
(2) Preparing microcrystalline glass: the glass substrate was subjected to a heat treatment process using a heat treatment roller kiln line to produce a glass ceramic tile, wherein the heat treatment process is shown in Table 4, and comprises a nucleation treatment and a crystallization treatment (denoted as a heat treatment process B) which were sequentially performed. The temperature rising rate in the heat treatment process is 10 ℃/min. And discharging the glass ceramic tile from the furnace to obtain the glass ceramic tile.
Test of the microcrystalline glass brick obtained in S1:
and I, observing, wherein the whole glass ceramic tile prepared in the step S1 is clear and transparent.
II, the crystalline phase composition, the crystalline phase content and the crystallinity in the glass ceramics were measured, and the results are shown in Table 4. And the average crystal size in the microcrystalline glass is 19nm through calculation.
III, test the glass ceramics having dimensions of 360mm (length). Times.180 mm (width). Times.30 mm (thickness) were extremely poor in the values of b at nine places on the main surface, and the results are shown in Table 4.
(3) And (3) carrying out cold processing treatment on the microcrystalline glass brick: and (3) carrying out cold working treatment on the glass ceramic tile, wherein the cold working treatment comprises shaping treatment, slicing treatment, CNC treatment, grinding treatment and polishing treatment which are sequentially carried out, so as to obtain the glass ceramic tile with the size of 170mm (length) ×80mm (width) ×0.6mm (thickness).
Test of the glass ceramic sheet obtained in S1:
and I, testing the optical properties of the glass-ceramic sheet, wherein the optical properties comprise nine b values of the main surface of the glass-ceramic sample sheet are extremely bad, and nine b values of the main surface of the glass-ceramic sample sheet are average, haze and transmittance. The test results are shown in Table 4.
And II, respectively testing XRD diffraction curves of the microcrystalline glass sheet at the maximum position of b value and the minimum position of b value in the nine-position b value test, wherein the comparison situation is shown in figure 15. As can be seen from fig. 15, in the glass-ceramic sheet, the crystal phase structure of the maximum position of the b value and the minimum position of the b value of the main surface is basically unchanged or has little difference, which indicates that the glass-ceramic sheet is uniform in whole and the optical display effect tends to be consistent. .
(4) Preparing chemically strengthened microcrystalline glass: the glass-ceramic sheet obtained in the step (3) and having a size of 170mm (length). Times.80 mm (width). Times.0.6 mm (thickness) was placed at 470 ℃ in 70.00wt% KNO 3 +30.00wt％NaNO 3 +0.03wt％LiNO 3 (here, naNO in the mixed molten salt 3 And KNO 3 The mixed molten salt contains 0.03wt% LiNO based on the total amount 3 ) And (3) treating the glass in a mixed nitrate salt bath for 7.0h to obtain the chemically strengthened glass ceramic with t=0.6 mm.
Testing the chemically strengthened glass ceramics obtained in the step S1:
performing a 1.0m fixed-point high anti-drop performance test on the obtained chemically strengthened microcrystalline glass through 120-mesh sand paper; testing surface Na of chemically strengthened glass ceramics 2 O concentration, cs_50, |ct_av|, dol_0. The test data are shown in table 5, respectively.
Example 2-example 28
Which were conducted with reference to example 1, respectively, except that the raw material compositions of each example and the corresponding test results thereof are shown in tables 1 to 5, respectively. The transparent glass ceramics of examples 2 to 28 all satisfy: the whole appearance is clear and transparent, and no cracking phenomenon exists; the crystal phase of the transparent microcrystalline glass is mainly Li 2 Si 2 O 5 、LiAlSi 4 O 10 No quartz crystal phase exists. The average crystal size of the glass ceramics of examples 2-28 was calculated to be between 10-50 nm.
The base glass of example 3 was subjected to heat treatment process A (crystallization temperature T 1-60 ) The XRD diffraction pattern of the resulting product is shown in FIG. 7, and FIG. 7 shows that the crystal phase of the product obtained after the substrate glass of example 3 is subjected to the heat treatment process A comprises petalite, lithium disilicate, lithium monosilicate and lithium phosphate crystal phases. The XRD diffraction pattern of the product obtained after the substrate glass of example 3 was subjected to the heat treatment process B is shown in FIG. 9, and the crystal phase is shown in Table 4. The transmittance curve of the glass ceramic sheet obtained by heat treatment process B of the base glass of example 6 at a thickness of 0.6mm is shown in FIG. 17. The temperature rise DSC curve of the substrate glass of example 22 is shown in FIG. 4.
Comparative example 1-comparative example 13
Which were conducted with reference to example 1, respectively, except that the raw material compositions of each comparative example and the corresponding test results thereof are shown in tables 6 to 11, respectively. The temperature rise DSC curve of the substrate glass of comparative example 1 is shown in FIG. 5. The temperature-rising DSC curve of the base glass of comparative example 2 is shown in FIG. 6, and the base glass of comparative example 2 is subjected to the heat treatment process A (crystallization temperature T 1-60 ) The XRD diffraction pattern of the obtained product is shown in FIG. 8, the XRD diffraction pattern of the obtained product after the substrate glass of comparative example 2 is subjected to the heat treatment process B is shown in FIG. 10, and the crystal phase is shown in Table 9. The temperature-decreasing DSC curve of the base glass of comparative example 4 is shown in FIG. 2, and the transmittance curve of the glass-ceramic sheet obtained by heat-treating the base glass of comparative example 4 at a thickness of 0.6mm is shown in FIG. 18.
In the test of b value of the glass-ceramic sheet (with flower) of comparative example 6, as shown in fig. 16, the XRD diffraction curves of the maximum b value position and the minimum b value position are clearly different from each other, which indicates that the glass-ceramic sheet has a large difference in overall structure, and that the overall display effect is also different, and that the local color development and/or the overall color development of the main surface are uneven. The molten appearance of the substrate glass of comparative example 9 was milky white, as shown in fig. 19. After the substrate glass tile of comparative example 7 was subjected to the heat treatment process B, the glass ceramic tile was cracked, and as shown in fig. 20, a significant crack was seen in the square frame of fig. 20. The average crystal size of the glass ceramics of comparative examples 1 to 12 was calculated to be larger than 20nm.
TABLE 1
| Composition (mol%) | SiO 2 | Al 2 O 3 | P 2 O 5 | ZrO 2 | Na 2 O | K 2 O | Li 2 O | CaO | B 2 O 3 |
| S1 | 69.29 | 4.11 | 1.01 | 2.64 | 0.29 | 0.08 | 21.49 | 0.79 | 0.30 |
| S2 | 70.36 | 4.17 | 1.03 | 2.68 | 0.30 | 0.08 | 20.28 | 0.80 | 0.30 |
| S3 | 70.00 | 4.15 | 1.02 | 2.66 | 0.29 | 0.09 | 20.68 | 0.80 | 0.31 |
| S4 | 69.64 | 4.13 | 1.02 | 2.65 | 0.29 | 0.08 | 21.09 | 0.80 | 0.30 |
| S5 | 68.59 | 4.07 | 1.00 | 2.61 | 0.29 | 0.08 | 22.27 | 0.79 | 0.30 |
| S6 | 67.91 | 4.03 | 0.99 | 2.58 | 0.29 | 0.08 | 23.04 | 0.78 | 0.30 |
| S7 | 69.36 | 4.11 | 0.91 | 2.64 | 0.29 | 0.08 | 21.51 | 0.79 | 0.31 |
| S8 | 69.22 | 4.10 | 1.11 | 2.63 | 0.29 | 0.08 | 21.47 | 0.79 | 0.31 |
| S9 | 69.49 | 4.12 | 1.02 | 2.64 | 0.00 | 0.08 | 21.55 | 0.80 | 0.30 |
| S10 | 69.07 | 4.09 | 1.01 | 2.63 | 0.61 | 0.08 | 21.42 | 0.79 | 0.30 |
| S11 | 68.79 | 4.08 | 1.01 | 2.63 | 1.00 | 0.08 | 21.33 | 0.79 | 0.29 |
| S12 | 69.50 | 4.12 | 1.02 | 2.64 | 0.29 | 0.08 | 21.55 | 0.80 | 0.00 |
| S13 | 69.23 | 4.10 | 1.01 | 2.63 | 0.29 | 0.08 | 21.47 | 0.79 | 0.40 |
| S14 | 69.08 | 4.09 | 1.01 | 2.63 | 0.29 | 0.08 | 21.42 | 0.79 | 0.61 |
| S15 | 68.87 | 4.08 | 1.01 | 2.62 | 0.29 | 0.08 | 21.36 | 0.79 | 0.90 |
| S16 | 69.36 | 3.71 | 1.02 | 2.64 | 0.29 | 0.08 | 21.81 | 0.79 | 0.30 |
| S17 | 69.15 | 4.30 | 1.01 | 2.63 | 0.29 | 0.08 | 21.44 | 0.79 | 0.31 |
| S18 | 68.94 | 4.59 | 1.01 | 2.62 | 0.29 | 0.08 | 21.38 | 0.79 | 0.30 |
| S19 | 69.15 | 4.10 | 1.01 | 2.83 | 0.29 | 0.08 | 21.44 | 0.80 | 0.30 |
| S20 | 69.01 | 4.09 | 1.01 | 3.03 | 0.29 | 0.08 | 21.40 | 0.79 | 0.30 |
| S21 | 68.80 | 4.08 | 1.01 | 3.32 | 0.29 | 0.08 | 21.34 | 0.79 | 0.29 |
| S22 | 69.01 | 4.09 | 0.91 | 2.62 | 0.29 | 0.08 | 21.91 | 0.79 | 0.30 |
| S23 | 68.25 | 4.05 | 1.20 | 2.60 | 0.29 | 0.08 | 22.46 | 0.78 | 0.29 |
| S24 | 69.29 | 4.01 | 0.91 | 2.84 | 0.29 | 0.08 | 21.49 | 0.79 | 0.30 |
| S25 | 69.08 | 3.99 | 0.91 | 2.83 | 0.59 | 0.08 | 21.42 | 0.79 | 0.31 |
| S26 | 69.18 | 4.00 | 0.86 | 2.83 | 0.49 | 0.08 | 21.45 | 0.79 | 0.32 |
| S27 | 69.17 | 4.10 | 1.01 | 2.63 | 0.29 | 0.08 | 21.47 | 0.95 | 0.30 |
| S28 | 68.79 | 4.08 | 1.01 | 2.62 | 0.29 | 0.08 | 21.33 | 1.51 | 0.29 |
TABLE 2
TABLE 3 Table 3
/>
/>
/>
/>
/>
/>
TABLE 6
| Composition (mol%) | SiO 2 | Al 2 O 3 | P 2 O 5 | ZrO 2 | Na 2 O | K 2 O | Li 2 O | CaO | B 2 O 3 |
| D1 | 71.46 | 4.24 | 1.05 | 2.72 | 0.30 | 0.08 | 19.03 | 0.82 | 0.30 |
| D2 | 66.73 | 3.80 | 0.92 | 2.50 | 0.20 | 0.08 | 25.00 | 0.77 | 0.00 |
| D3 | 69.43 | 4.13 | 0.80 | 2.64 | 0.29 | 0.08 | 21.53 | 0.80 | 0.30 |
| D4 | 68.94 | 4.09 | 1.80 | 2.62 | 0.29 | 0.08 | 21.09 | 0.79 | 0.30 |
| D5 | 68.43 | 4.06 | 1.00 | 2.60 | 0.29 | 0.08 | 21.22 | 0.78 | 1.54 |
| D6 | 68.66 | 4.07 | 1.01 | 3.60 | 0.20 | 0.08 | 21.29 | 0.79 | 0.30 |
| D7 | 69.77 | 4.22 | 1.24 | 2.71 | 0.32 | 0.08 | 20.47 | 0.83 | 0.36 |
| D8 | 68.65 | 4.07 | 1.01 | 2.61 | 0.29 | 0.99 | 21.29 | 0.79 | 0.30 |
| D9 | 68.90 | 4.15 | 1.00 | 2.60 | 0.25 | 0.10 | 21.00 | 1.80 | 0.20 |
| D10 | 68.76 | 4.06 | 2.00 | 2.58 | 0.29 | 0.08 | 21.19 | 0.78 | 0.26 |
| D11 | 70.10 | 4.27 | 0.83 | 1.75 | 1.48 | 0.00 | 21.42 | 0.00 | 0.15 |
| D12 | 71.00 | 4.00 | 1.00 | 2.00 | 0.00 | 0.00 | 22.00 | 0.00 | 0.00 |
| D13 | 69.11 | 5.00 | 1.00 | 2.45 | 0.29 | 0.08 | 21.17 | 0.6 | 0.30 |
TABLE 7
TABLE 8
TABLE 9
/>
Table 10
TABLE 11
/>
As is clear from the results of the examples of tables 1 to 5 and the comparative examples of tables 6 to 11, the embodiment of the present application satisfies the respective oxide content ranges and also satisfies the following conditions, compared to the comparative examples: 18.200 Li is less than or equal to 2 O/P 2 O 5 ≤25.500；14.000≤2×Li 2 O/(0.5×ZrO 2 The composition characteristics of +CaO) is less than or equal to 23.000, the appearance of the prepared large-size substrate glass brick is clear and transparent, at least two exothermic peaks exist in a temperature rising DSC curve of the substrate glass subjected to synchronous thermal analysis test at a proper temperature, and the sum S of the integral areas of the exothermic peaks and the endothermic peaks in a temperature lowering DSC curve is less than or equal to 10. The glass ceramic brick obtained by adopting the heat treatment of the substrate glass brick has transparent and clear appearance, the glass ceramic brick has no cracking phenomenon, and the prepared glass ceramic crystal phase contains no quartz crystal phase and has no microcrystalThe difference in b value at nine points on the major surface of the glass is low. By adopting the embodiment scheme of the application, the microcrystalline glass bricks with large size, excellent and uniform optical performance can be produced in batches, and meanwhile, the chemically strengthened microcrystalline glass with excellent optical performance, higher CS_50, |CT_AV|, DOL_0 and excellent anti-falling performance can be prepared.
In the schemes of comparative examples 1 to 8, the formulation of the base glass does not satisfy the following conditions: the content range of each oxide is 18.200 and is less than or equal to Li 2 O/P 2 O 5 ≤25.500；14.000≤2×Li 2 O/(0.5×ZrO 2 +CaO). Ltoreq. 23.000, after the large-size microcrystalline glass bricks are prepared by heat treatment, the optical performance is poor (mainly shown by large difference of b values in different areas and unexpected color of the glass bricks) or the brick cracking is easy to occur. In the schemes of comparative examples 9 to 10, after the large-sized base glass block was prepared, milky white precipitate was directly formed in the base glass block, and the optical properties were deteriorated and the transmittance was lowered. According to the schemes of comparative examples 11 and 12, the required excellent mechanical properties of the produced glass ceramics cannot be achieved after chemical strengthening treatment, and the anti-drop effect is inferior to that of the product of the application. In the case of comparative example 13, milky white precipitate and undissolved substances were found in the large-sized substrate glass tile prepared.
The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto.
Claims (24)
1. A transparent glass-ceramic, characterized in that the transparent glass-ceramic comprises petalite crystal phase and lithium disilicate crystal phase, wherein the petalite crystal phase and the lithium disilicate crystal phase have a higher weight percentage than other crystal phases existing in the transparent glass-ceramic;
the transparent glass ceramics comprises the following components in percentage by mole of oxide:
SiO 2 ：60.90mol％-72.65mol％，Al 2 O 3 ：1.50mol％-5.00mol％，P 2 O 5 ：0.85mol％-1.50mol％，ZrO 2 ：2.00mol％-4.00mol％，Na 2 O：0.00mol％-1.00mol％，K 2 O：0.00mol％-0.50mol％，Li 2 O：20.00mol％-30.00mol％，CaO：0.00mol％-1.60mol％，B 2 O 3 ：0.00mol％-1.00mol％；
the composition of the transparent glass ceramics is expressed by the mol percent of each oxide in the composition of the transparent glass ceramics, and the composition of the transparent glass ceramics meets the following conditions:
18.200≤Li 2 O/P 2 O 5 ≤25.500；
14.000≤2×Li 2 O/(0.5×ZrO 2 +CaO)≤23.000。
2. the transparent glass-ceramic according to claim 1, wherein the composition of the transparent glass-ceramic, expressed as a mole percentage of each oxide in the composition of the transparent glass-ceramic, satisfies:
4.100≤(Li 2 O+Na 2 O+K 2 O+B 2 O 3 )/(P 2 O 5 +ZrO 2 +CaO) is less than or equal to 6.000; and/or, 0.100.ltoreq.P 2 O 5 ×(CaO+ZrO 2 +Li 2 O+Al 2 O 3 )/(Na 2 O+K 2 O+B 2 O 3 ) Less than or equal to 0.900, preferably, 0.190 less than or equal to P 2 O 5 ×(CaO+ZrO 2 +Li 2 O+Al 2 O 3 )/(Na 2 O+K 2 O+B 2 O 3 )≤0.900。
3. The transparent glass-ceramic according to claim 1 or 2, characterized in that the composition of the transparent glass-ceramic comprises, in mole percent of oxides:
SiO 2 ：67.50mol％-71.00mol％，Al 2 O 3 ：3.50mol％-5.00mol％，P 2 O 5 ：0.85mol％-1.50mol％，ZrO 2 ：2.50mol％-3.50mol％，Na 2 O：0.00mol％-1.00mol％，K 2 o: more than 0.00mol% and not more than 0.50mol%, li 2 O:20.00mol percent to 25.00mol percent, caO: greater than 0.50mol% and not greater than 1.60mol%, B 2 O 3 ：0.00mol％-1.00mol％。
4. A transparent glass-ceramic according to any one of claims 1 to 3, wherein the transparent glass-ceramic is free of quartz crystal phases.
5. The transparent glass-ceramic according to any one of claims 1 to 4, wherein the crystallinity of the transparent glass-ceramic is equal to or more than 70.00wt%, preferably equal to or more than 80.00wt%; in the transparent microcrystalline glass, the average crystal size is not more than 100nm.
6. The transparent glass-ceramic according to any one of claims 1 to 5, wherein the petalite crystalline phase comprises 35.00 to 50.00wt% of the transparent glass-ceramic mass and the lithium disilicate crystalline phase comprises 35.00 to 50.00wt% of the transparent glass-ceramic mass.
7. The transparent glass-ceramic according to any one of claims 1 to 6, further comprising one or more of a lithium silicate crystal phase, a lithium phosphate crystal phase, and a spodumene crystal phase as a secondary crystal phase.
8. The transparent glass-ceramic according to claim 7, wherein the secondary crystal phase is 30.00wt% or less of the mass of the transparent glass-ceramic, preferably 10.00wt% or less of the mass of the transparent glass-ceramic.
9. The transparent glass-ceramic according to any one of claims 1 to 8, wherein when the specification of the length, width and thickness of the transparent glass-ceramic is (200 mm to 500 mm) × (100 mm to 500 mm) × (10 mm to 40 mm), the range of the value of b at nine points on the main surface of the transparent glass-ceramic is not more than 2.00, preferably not more than 1.50, more preferably not more than 1.00;
wherein, the positions of nine positions are respectively: (1) The test positions of the test circles I tangent to the long side and the adjacent short side on the main surface are in total four places; (2) Taking the point closest to the middle of the long side or the short side of the main surface on the line segment formed by the centers of the four test circles I as a round point, and forming four test positions where the four test circles II are located, wherein the four test positions are in total; (3) And taking the center point of the main surface as the center of a circle to form a test circle III.
10. The transparent glass-ceramic according to any one of claims 1 to 8, wherein when the transparent glass-ceramic has a gauge of (45 mm to 450 mm) x (45 mm to 350 mm) x (0.4 mm to 2.0 mm), the difference in b value at nine points on the main surface of the transparent glass-ceramic is 0.30 or less, preferably 0.10 or less, more preferably 0.06 or less;
wherein, the positions of nine positions are respectively: (1) The test positions of the test circles I tangent to the long side and the adjacent short side on the main surface are in total four places; (2) Taking the point closest to the middle of the long side or the short side of the main surface on the line segment formed by the centers of the four test circles I as a round point, and forming four test positions where the four test circles II are located, wherein the four test positions are in total; (3) And taking the center point of the main surface as the center of a circle to form a test circle III.
11. The transparent glass-ceramic according to any one of claims 1 to 10, wherein the value of b is not more than 1.00, preferably not more than 0.70, the haze is not more than 0.25%, preferably not more than 0.18% at a thickness of 0.6mm, the transmittance of the transparent glass-ceramic is not less than 90.00% at a wavelength of 550 nm;
preferably, when the thickness of the transparent microcrystalline glass is 0.6mm, the b value is less than or equal to 0.60, the haze is less than or equal to 0.16%, and the transmittance of the transparent microcrystalline glass under 550nm wavelength light is more than or equal to 90.50%.
12. A substrate glass which has been heat treated to produce the transparent glass-ceramic of any one of claims 1 to 11, wherein the composition of the substrate glass, in mole percent of oxides, comprises:
SiO 2 ：60.90mol％-72.65mol％，Al 2 O 3 ：1.50mol％-5.00mol％，P 2 O 5 ：0.85mol％-1.50mol％，ZrO 2 ：2.00mol％-4.00mol％，Na 2 O：0.00mol％-1.00mol％，K 2 O：0.00mol％-0.50mol％，Li 2 O：20.00mol％-30.00mol％，CaO：0.00mol％-1.60mol％，B 2 O 3 ：0.00mol％-1.00mol％；
the composition of the substrate glass, expressed as mole percent of each oxide in the composition of the substrate glass, satisfies:
18.200≤Li 2 O/P 2 O 5 ≤25.500；
14.000≤2×Li 2 O/(0.5×ZrO 2 +CaO)≤23.000。
13. the substrate glass according to claim 12, wherein the composition of the substrate glass, expressed as mole percent of each oxide in the composition of the substrate glass, satisfies:
4.100≤(Li 2 O+Na 2 O+K 2 O+B 2 O 3 )/(P 2 O 5 +ZrO 2 +CaO) is less than or equal to 6.000; and/or, 0.100.ltoreq.P 2 O 5 ×(CaO+ZrO 2 +Li 2 O+Al 2 O 3 )/(Na 2 O+K 2 O+B 2 O 3 ) Less than or equal to 0.900, preferably, 0.190 less than or equal to P 2 O 5 ×(CaO+ZrO 2 +Li 2 O+Al 2 O 3 )/(Na 2 O+K 2 O+B 2 O 3 )≤0.900。
14. The substrate glass according to claim 12 or 13, characterized in that the substrate glass is heated from room temperature to 900 ℃ at a heating rate of 10 ℃/min under a protective atmosphere of nitrogen, resulting in a heating DSC curve, in which at least two exothermic peaks are present, wherein the first exothermic peak temperature T 1 600-730 ℃, the second exothermic peak temperature T 2 740-800 ℃ and T 1 And T 2 The relation is satisfied: t at 100℃ or more 2 -T 1 Not less than 40 ℃, preferably not less than 80 ℃ and not less than T 2 -T 1 ≥50℃。
15. The substrate glass according to any one of claims 12 to 14, wherein the substrate glass is heated from room temperature to 1400 ℃ for 10min at a heating rate of 10 ℃/min under a nitrogen protection atmosphere, and then cooled from 1400 ℃ to 450 ℃ at a cooling rate of 10 ℃/min, resulting in a cooled DSC curve, wherein the sum S of the integrated areas of the exothermic peak and the endothermic peak contained therein is less than or equal to 10, preferably no endothermic peak and/or exothermic peak, more preferably s=0, in the range of 500 ℃ to 900 ℃.
16. The substrate glass according to any one of claims 12 to 15, wherein the substrate glass is raised from room temperature to T at a heating rate of 10 ℃/min 1-30 The temperature is kept for 240min, and the quartz crystal phase content in the product obtained after the treatment is less than 15wt%, wherein T is 1-30 ＝T 1 -30℃；
And/or the number of the groups of groups,
heating the substrate glass from room temperature to T at a heating rate of 10 ℃/min 1-60 Temperature and holding at this temperature for 240min, wherein the content of quartz crystal phase in the product obtained after the treatment is less than 5wt%, preferably no quartz crystal phase, wherein T 1-60 ＝T 1 -60℃。
17. A chemically strengthened glass-ceramic characterized in that the composition at the center of the chemically strengthened glass-ceramic is the same as the composition of the transparent glass-ceramic of any one of claims 1 to 11, the chemically strengthened glass-ceramic comprising a compressive stress layer region extending from the surface of the transparent glass-ceramic to a compressive depth, and having tensile stress inside the chemically strengthened glass-ceramic.
18. The chemically strengthened glass ceramic of claim 17, wherein the chemically strengthened glass ceramic is produced by parallelizing a transparent glass ceramic of any one of claims 1-11The chemical strengthening treatment is obtained by adopting a salt bath for chemical strengthening treatment as a mixed molten salt, wherein the composition of the mixed molten salt comprises: naNO 0 < 3 ＜100wt％、0＜KNO 3 ＜100wt％，0＜LiNO 3 Less than or equal to 0.2wt percent; the temperature of the salt bath for chemical strengthening treatment is 430-530 ℃, and the time of the chemical strengthening treatment is 0.5-15.0 h.
19. The chemically strengthened glass ceramic of claim 17 or 18, wherein the surface Na of the chemically strengthened glass ceramic 2 The O concentration is 5.0wt% to 20.0wt%.
20. The chemically strengthened glass ceramic of any one of claims 17-19, wherein the chemically strengthened glass ceramic has a cs_50 of 110-200MPa, cs_50 being the compressive stress value at a depth of 50 μιη from the major surface of the chemically strengthened glass ceramic;
and/or the number of the groups of groups,
the chemically strengthened glass ceramic has an absolute value of an average tensile stress of |CT_AV| of 84-140 MPa.
21. The chemically strengthened glass ceramic of any one of claims 17-20, wherein the depth of compressive stress layer dol_0 of the chemically strengthened glass ceramic is 0.18t-0.25t, where t is the thickness of the chemically strengthened glass ceramic.
22. Chemically strengthened glass-ceramic according to any one of claims 17 to 21, characterized in that the chemically strengthened glass-ceramic having a thickness of 0.6mm is subjected to a number of fixed point height drop tests with 120-mesh sand paper, the fixed point height of the test being 1.0m, the number of times the chemically strengthened glass-ceramic drops to break being not less than 30, preferably not less than 50.
23. A glass device comprising the transparent glass-ceramic of any one of claims 1-11 or comprising the chemically strengthened glass-ceramic of any one of claims 17-22.
24. An electronic device comprising the transparent glass-ceramic of any one of claims 1-11 or comprising the chemically strengthened glass-ceramic of any one of claims 17-22.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311800621.3A CN117776535A (en) | 2023-12-25 | 2023-12-25 | Transparent glass ceramics, base material glass, chemically strengthened glass ceramics and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311800621.3A CN117776535A (en) | 2023-12-25 | 2023-12-25 | Transparent glass ceramics, base material glass, chemically strengthened glass ceramics and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117776535A true CN117776535A (en) | 2024-03-29 |
Family
ID=90386449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311800621.3A Pending CN117776535A (en) | 2023-12-25 | 2023-12-25 | Transparent glass ceramics, base material glass, chemically strengthened glass ceramics and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117776535A (en) |
-
2023
- 2023-12-25 CN CN202311800621.3A patent/CN117776535A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111320392B (en) | Microcrystalline glass, reinforced microcrystalline glass and preparation method thereof | |
| CN1244511C (en) | Float flat glass | |
| EP3204339B1 (en) | High strength glass-ceramics having petalite and lithium silicate structures | |
| US20230295035A1 (en) | Microcrystalline glass, and microcrystalline glass product and manufacturing method therefor | |
| JP2016529197A5 (en) | ||
| JP2016108218A (en) | Highly crystalline lithium aluminium silicate glass-ceramic and its use | |
| JP7351334B2 (en) | Crystallized glass and chemically strengthened glass and their manufacturing methods | |
| CN111592225A (en) | Lithium-aluminum silicate nanocrystalline transparent ceramic, preparation method thereof and product | |
| CN111362579A (en) | Glass ceramic, strengthened glass ceramic and preparation method thereof | |
| JP2017519715A (en) | Chemically strengthened glass composition for alkali aluminosilicate glass and method for producing the same | |
| CN114907016B (en) | Glass ceramics, glass ceramics product and method for producing the same | |
| CN111592224A (en) | Magnesium aluminum silicate nanocrystalline transparent ceramic, preparation method and product thereof | |
| CN111606572A (en) | Sodium-aluminium silicate nanocrystalline transparent ceramic, preparation method and product thereof | |
| CN116282926A (en) | High-strength transparent zinc lithium silicate glass ceramic capable of being strengthened and preparation method thereof | |
| TW202132232A (en) | 3d glass-ceramic articles and methods for making the same | |
| CN117776535A (en) | Transparent glass ceramics, base material glass, chemically strengthened glass ceramics and application thereof | |
| JP2024504395A (en) | 3D crystallized glass and its manufacturing method and use | |
| CN117776536A (en) | 3D curved surface glass ceramic, chemically strengthened glass ceramic, and preparation method and application thereof | |
| CN115028365B (en) | Glass ceramic, glass ceramic article and method of making the same | |
| CN115259672B (en) | Transparent glass ceramics and transparent glass ceramics products | |
| JP2018528923A (en) | Chemically strengthened glass composition for alkali aluminosilicate glass and its production method with shortened ion exchange time | |
| CN115745411B (en) | Composition for preparing low-expansion transparent glass ceramics, and preparation method and application thereof | |
| WO2024004965A1 (en) | Crystallized glass, chemically toughened glass, and method for producing crystallized glass | |
| WO2024109495A1 (en) | 3d microcrystalline glass, preparation method therefor, and pre-crystallized microcrystalline glass | |
| WO2024017081A1 (en) | Glass-ceramic having excellent acid and alkali resistance, and preparation method therefor and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |