CN118084333A - High-strength glass ceramic and preparation method thereof - Google Patents
High-strength glass ceramic and preparation method thereof Download PDFInfo
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- CN118084333A CN118084333A CN202410527199.7A CN202410527199A CN118084333A CN 118084333 A CN118084333 A CN 118084333A CN 202410527199 A CN202410527199 A CN 202410527199A CN 118084333 A CN118084333 A CN 118084333A
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- 239000002241 glass-ceramic Substances 0.000 title claims description 98
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000011521 glass Substances 0.000 claims abstract description 39
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 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 abstract description 17
- 229910052670 petalite Inorganic materials 0.000 claims abstract description 17
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 16
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 16
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 16
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052912 lithium silicate Inorganic materials 0.000 claims abstract description 16
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims abstract description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005728 strengthening Methods 0.000 claims description 50
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 36
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 36
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 36
- 238000012360 testing method Methods 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 235000010333 potassium nitrate Nutrition 0.000 claims description 18
- 239000004323 potassium nitrate Substances 0.000 claims description 18
- 235000010344 sodium nitrate Nutrition 0.000 claims description 18
- 239000004317 sodium nitrate Substances 0.000 claims description 18
- 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 14
- 229910052642 spodumene Inorganic materials 0.000 claims description 14
- 229910004742 Na2 O Inorganic materials 0.000 claims description 11
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 10
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052637 diopside Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000012071 phase Substances 0.000 description 25
- 238000004321 preservation Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000006064 precursor glass Substances 0.000 description 8
- 244000137852 Petrea volubilis Species 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 229910004762 CaSiO Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 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 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- Glass Compositions (AREA)
Abstract
The invention discloses high-strength microcrystalline glass and a preparation method thereof, wherein the main crystal phase of the high-strength microcrystalline glass is petalite and lithium silicate, and the composition of the high-strength microcrystalline glass is ：67-70mol%SiO2、3.5-4.5mol%Al2O3、0.5-1.5mol%P2O5、21-23mol%Li2O、0.05-0.1mol%Na2O、0.05-0.1mol%K2O、0-0.1mol%Sb2O3、2.5-3mol%ZrO2, one or more of MgO, caO, srO and BaO; the thickness of a CS layer of the high-strength microcrystalline glass is more than or equal to 120 mu m, the central tensile stress density is more than 350Mpa/mm, and the Vickers hardness is more than or equal to 860kgf/mm 2.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to high-strength glass ceramics and a preparation method thereof.
Background
Glass ceramics (glass-ceramic), also known as microcrystalline glass, and microcrystalline ceramics, are invented by well-known glass chemists and inventers, s.d. Stookey, in the middle of the 50 th year of the 20 th century, and are polycrystalline solid phase materials containing glass bodies, which are prepared by controlled nucleation and crystallization of certain base glasses with specific compositions at certain temperatures. The properties of glass ceramics are mainly determined by the main crystal phase, which can be achieved by controlling nucleation, crystallization and selecting different mother glass components. The glass ceramic has the characteristics of both glass and ceramic, and is superior to metal and polymer in thermal, chemical, biological, optical and electrical properties.
With the upgrading of smart phones, many mobile phone manufacturers apply glass ceramics to the field of cover glass of mobile display equipment with high strength requirements.
The invention discloses a high-strength glass-ceramic, a glass-ceramic precursor and a preparation method thereof, wherein the glass-ceramic comprises SiO 2,Al2O3 and Li 2 O, and the crystal phase comprises a lithium silicate crystal phase, a lithium feldspar solid solution and/or a petalite crystal phase, and the glass-ceramic is transparent and colorless; for glass ceramics with the thickness of 1mm, the glass ceramics has the transmittance of at least 86 percent in the wavelength range of 450nm to 1000 nm. According to the invention, tiO 2 is introduced, the composition of a material formula is optimized, and a lithium feldspar solid solution crystal phase is introduced in a crystallization process, so that the phenomena of warping and glass sheet fragmentation caused by large expansion coefficient difference between the petalite crystal phase and the lithium silicate crystal phase are greatly improved. The microcrystalline glass has low dielectric loss and high thermal conductivity, and simultaneously meets the requirement of 5G communication on the microcrystalline glass.
Disclosure of Invention
The application provides high-strength glass ceramics, which has better anti-falling performance, preferably, glass ceramics with better anti-falling performance and better performance still can be maintained in a long-time high-temperature and high-humidity environment. The specific technical scheme of the application is as follows:
the main crystal phase of the high-strength glass ceramic is petalite and lithium silicate, the thickness of a CS layer of the glass ceramic is more than or equal to 120 mu m, the central tensile stress density is more than 350Mpa/mm, and the Vickers hardness is more than or equal to 860kgf/mm 2. The CS layer refers to the exchange of ions with larger radius in molten salt and ions with smaller radius in glass, so that a compressive stress layer is generated on the surface of the glass.
Furthermore, the high-strength microcrystalline glass also contains one or more crystal phases of spodumene, mg 0.6Al1.2Si1.8O6 crystal phases, beta CaSiO 3 and diopside, wherein petalite and lithium silicate account for more than 50% of the total weight of the microcrystalline glass;
further, CS 50/|ct-cv| of the high strength glass ceramic is >1.05, wherein CS50 refers to a stress value corresponding to 50 μm in depth, and |ct-cv| refers to an absolute value of a maximum tensile stress in a tensile stress layer.
Further, CS50 of the high-strength glass ceramic is more than or equal to 100Mpa; the |CT-CV| is greater than or equal to 90Mpa.
Further, under the thickness of 0.6mm, 80-mesh sand paper is adopted for carrying out sand paper drop resistance test on the high-strength microcrystalline glass, and the average sand paper drop resistance height is not less than 1.8m.
Furthermore, in the high-strength glass ceramic, the total weight of spodumene, mg 0.6Al1.2Si1.8O6 crystal phase, beta CaSiO 3 and diopside is not more than 50% of the total weight of the glass ceramic.
The high-strength glass ceramic comprises ：67-70mol%SiO2、3.5-4.5mol%Al2O3、0.5-1.5mol%P2O5、21-23mol%Li2O、0.05-0.1mol%Na2O、0.05-0.1mol%K2O、0-0.1mol%Sb2O3、2.5-3mol%ZrO2、0-1mol%MgO、0-1mol%CaO、0-1mol%SrO and 0-1mol% of BaO in terms of mole percent.
Further, the total amount of Li 2O、Na2 O and K 2 O is 21.1 to 23.2mol%, and preferably Li 2 O accounts for 98mol% or more of the total amount of Li 2O、Na2 O and K 2 O.
Further, the total amount of MgO, caO, srO and BaO is 0.5 to 1mol%.
Further, the molar ratio of the total of Li 2O、Na2 O and K 2 O to the four of MgO, caO, srO and BaO is 21-47.
In the high-strength microcrystalline glass, the average size of crystal grains is less than or equal to 100nm.
The preparation method of the high-strength glass ceramic comprises the following steps: heat treatment, crystallization and chemical strengthening, wherein the composition of the strengthening salt in the chemical strengthening process is 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate, the strengthening temperature is above 500 ℃, and the strengthening time is above 4 hours. Preferably, the strengthening temperature is 500-550 ℃, and the strengthening time is 4-8h.
Further, the depth of ion diffusion in the strengthening process is more than or equal to 100 mu m; preferably, the depth of ion diffusion in the strengthening process is greater than or equal to 105 mu m.
And under the condition of high temperature and high humidity, the sodium ion concentration of the surface of the high-strength glass ceramic is not lower than 12mol% after more than 240 hours.
In some embodiments, the high-strength glass-ceramic comprises petalite and lithium silicate as main crystal phases, and spodumene, wherein the petalite and the lithium silicate account for more than 50% of the total weight of the glass-ceramic; CS 50/|CT-CV| of the microcrystalline glass is more than 1.05; in some embodiments, the main crystal phase of the high-strength glass-ceramic is petalite and lithium silicate, and the high-strength glass-ceramic also contains spodumene and Mg 0.6Al1.2Si1.8O6 crystal phases, wherein the petalite and the lithium silicate account for more than 50% of the total weight of the glass-ceramic; CS 50/|CT-CV| of the microcrystalline glass is more than 1.05; in some embodiments, the main crystal phase of the high-strength glass-ceramic is petalite and lithium silicate, and the high-strength glass-ceramic also contains spodumene and beta CaSiO 3, wherein the petalite and the lithium silicate account for more than 50% of the total weight of the glass-ceramic; CS 50/|CT-CV| of the microcrystalline glass is more than 1.05; in some embodiments, the main crystal phase of the high-strength glass-ceramic is petalite and lithium silicate, and the high-strength glass-ceramic also contains spodumene, mg 0.6Al1.2Si1.8O6 crystal phase and beta CaSiO 3, wherein the petalite and the lithium silicate account for more than 50% of the total weight of the glass-ceramic; CS 50/|CT-CV| of the microcrystalline glass is more than 1.05; in some embodiments, the main crystal phase of the high-strength glass-ceramic is petalite and lithium silicate, and the high-strength glass-ceramic also contains spodumene, mg 0.6Al1.2Si1.8O6 crystal phase, beta CaSiO 3, XX and XX, wherein the petalite and the lithium silicate account for more than 50% of the total weight of the glass-ceramic; the CS 50/|CT-CV| of the microcrystalline glass is more than 1.05.
In some embodiments, the high strength glass-ceramic has a center tensile stress density >380Mpa/mm; in some embodiments, the high strength glass-ceramic has a center tensile stress density of >390Mpa/mm; in some embodiments, the high strength glass-ceramic has a center tensile stress density of >400Mpa/mm; in some embodiments, the high strength glass-ceramic has a center tensile stress density of >410Mpa/mm; in some embodiments, the high strength glass-ceramic has a center tensile stress density of >420Mpa/mm.
In some embodiments, the CS50 of the high strength glass ceramic is greater than or equal to 100Mpa, and |CT-CV| is greater than or equal to 90Mpa; in some embodiments, CS50 of the high-strength glass ceramic is more than or equal to 120Mpa, and |CT-CV| is more than or equal to 95Mpa; in some embodiments, CS50 of the high-strength glass ceramic is more than or equal to 130Mpa; and |CT-CV| is more than or equal to 100Mpa.
In some embodiments, 80 mesh sandpaper is used for the sandpaper drop test on the microcrystalline glass at the thickness of 0.6mm, and the average sandpaper drop resistance height is not less than 1.8m; in some embodiments, 80 mesh sandpaper is used for the sandpaper drop test on the microcrystalline glass at the thickness of 0.6mm, and the average sandpaper drop height is not less than 1.9m; in some embodiments, 80-mesh sand paper is adopted to carry out sand paper drop resistance test on microcrystalline glass at the thickness of 0.6mm, and the average sand paper drop resistance height is not less than 2m; in some embodiments, the glass-ceramic is subjected to a sandpaper drop test of 80 mesh with a thickness of 0.6mm, and the average sandpaper drop height is not less than 2.1m.
In some embodiments, the total weight of spodumene, mg 0.6Al1.2Si1.8O6 crystalline phase, βcasio 3, diopside in the glass-ceramic is no more than 50% of the total glass-ceramic weight; in some embodiments, the total weight of spodumene, mg 0.6Al1.2Si1.8O6 crystalline phase, βcasio 3, diopside in the glass-ceramic is no more than 40% by weight of the overall glass-ceramic; in some embodiments, the total weight of spodumene, mg 0.6Al1.2Si1.8O6 crystalline phase, βcasio 3, diopside in the glass-ceramic is no more than 30% of the total glass-ceramic weight; in some embodiments, the total weight of spodumene, mg 0.6Al1.2Si1.8O6 crystalline phase, βcasio 3, diopside in the glass-ceramic is no more than 20% by weight of the bulk glass-ceramic; in some embodiments, the total weight of spodumene, mg 0.6Al1.2Si1.8O6 crystalline phases, βcasio 3, diopside in the glass-ceramic is no more than 10% by weight of the overall glass-ceramic.
In some embodiments, the glass-ceramic has a composition of ：67-70mol%SiO2、3.5-4.5mol%Al2O3、0.5-1.5mol%P2O5、21-23mol%Li2O、0.05-0.1mol%Na2O、0.05-0.1K2O、0-0.1mol%Sb2O3、2.5-3mol%ZrO2、0-1mol%MgO、0-1mol%CaO、0-1mol%SrO and 0-1mol% bao, in mole percent; in some embodiments, the glass-ceramic has a composition of ：68-70mol%SiO2、3.5-4mol%Al2O3、0.5-1mol%P2O5、21-22mol%Li2O、0.05-0.1mol%Na2O、0.05-0.1K2O、0-0.1mol%Sb2O3、2.5-3mol%ZrO2、0-1mol%MgO、0-1mol%CaO、0-1mol%SrO and 0-1mol% bao, in mole percent; in some embodiments, the glass-ceramic has a composition of ：67-70mol%SiO2、3.5-4.5mol%Al2O3、0.5-1.5mol%P2O5、21-23mol%Li2O、0.05-0.1mol%Na2O、0.05-0.1K2O、0-0.1mol%Sb2O3、2.5-3mol%ZrO2、0.1-0.8mol%MgO、0-1mol%CaO、0.2-0.8mol%SrO and 0.3 to 0.7 mole% BaO, in mole percent.
In some embodiments, the glass-ceramic has a composition of ：67-70mol%SiO2、3.5-4.5mol%Al2O3、0.5-1.5mol%P2O5、21-23mol%Li2O、0.05-0.1mol%Na2O、0.05-0.1K2O、0-0.1mol%Sb2O3、2.5-3mol%ZrO2、0-1mol%MgO、0-1mol%CaO、0-1mol%SrO and 0-1mol% BaO, wherein the total of the three Li 2O、Na2 O and K 2 O is 21-23.2mol%, the total of the four Li MgO, caO, srO and BaO is 0.5-1mol%, the total of the four MgO, caO, srO and BaO is 0.5-1mol%, and the ratio of the total of the three Li 2O、Na2 O and K 2 O to the four MgO, caO, srO and BaO is 21-46; in some embodiments, the glass-ceramic has a composition of ：68-70mol%SiO2、3.5-4mol%Al2O3、0.5-1mol%P2O5、21-22mol%Li2O、0.05-0.1mol%Na2O、0.05-0.1K2O、0-0.1mol%Sb2O3、2.5-3mol%ZrO2、0-1mol%MgO、0-1mol%CaO、0-1mol%SrO and 0-1mol% BaO, wherein the total of the three Li 2O、Na2 O and K 2 O is 21.1-23.2mol%, the total of the four MgO, caO, srO and BaO is 0.5-1mol%, the total of the four MgO, caO, srO and BaO is 0.5-1mol%, and the ratio of the total of the three Li 2O、Na2 O and K 2 O to the four MgO, caO, srO and BaO is 27-46; in some embodiments, the glass-ceramic has a composition of ：67-70mol%SiO2、3.5-4.5mol%Al2O3、0.5-1.5mol%P2O5、21-23mol%Li2O、0.05-0.1mol%Na2O、0.05-0.1mol%K2O、0-0.1mol%Sb2O3、2.5-3mol%ZrO2、0.1-0.8mol%MgO、0-1mol%CaO、0.2-0.8mol%SrO and 0.3-0.7 mole% BaO, wherein the total of the three Li 2O、Na2 O and K 2 O is 21-23.2 mole%, the total of the four MgO, caO, srO and BaO is 0.5-1 mole%, the total of the four MgO, caO, srO and BaO is 0.5-1 mole%, and the ratio of the total of the three Li 2O、Na2 O and K 2 O to the four MgO, caO, srO and BaO is 21-46.
The preparation method of the high-strength glass ceramic comprises the following steps: melting, heat treatment, crystallization and chemical strengthening, wherein the composition of the strengthening salt in the chemical strengthening process is 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate, the strengthening temperature is above 500 ℃, and the strengthening time is above 4 hours. Preferably, the strengthening temperature is 500-550 ℃, and the strengthening time is 4-8h.
Further, the raw materials in melting are: in mole percent, in some embodiments, the glass-ceramic has a composition of ：67-70mol%SiO2、3.5-4.5mol%Al2O3、0.5-1.5mol%P2O5、21-23mol%Li2O、0.05-0.1mol%Na2O、0.05-0.1mol%K2O、0-0.1mol%Sb2O3、2.5-3mol%ZrO2、0-1mol%MgO、0-1mol%CaO、0-1mol%SrO and 0-1 mole% bao; in some embodiments, the glass-ceramic has a composition of ：68-70mol%SiO2、3.5-4mol%Al2O3、0.5-1mol%P2O5、21-22mol%Li2O、0.05-0.1mol%Na2O、0.05-0.1mol%K2O、2.5-3mol%ZrO2、0-1mol%MgO、0-1mol%CaO、0-1mol%SrO and 0-1mol% bao, in mole percent; in some embodiments, the glass-ceramic has a composition of ：67-70mol%SiO2、3.5-4.5mol%Al2O3、0.5-1.5mol%P2O5、21-23mol%Li2O、0.05-0.1mol%Na2O、0.05-0.1mol%K2O、2.5-3mol%ZrO2、0.1-0.8mol%MgO、0-1mol%CaO、0.2-0.8mol%SrO and 0.3 to 0.7 mole% BaO, in mole percent.
Further, the heat treatment process comprises the following steps: treating at 550-600deg.C for 3.5-4.5 hr, and then treating at 720-750deg.C for 0.8-1.2 hr.
Further, the sodium ion concentration of the surface of the prepared glass ceramics is not lower than 12mol% after more than 240 hours under the conditions of high temperature and high humidity; in some embodiments, the glass-ceramic has a sodium ion concentration of not less than 11mol% on the surface of the glass-ceramic after more than 360 hours under high temperature and high humidity conditions.
According to the application, aluminum oxide is introduced to form [ AlO 4 ] in glass, so that the volume and the gap of a glass network are increased, meanwhile, the ionic radiuses of Li +, mg 2+,Na+, ca 2+,K+ and Ba 2+ are close, the specific proportion of alkaline earth metal to alkali metal is set, the charge of alkaline earth metal with the same ionic radius is 2 times that of the alkali metal, the efficiency and the exchange depth of Li +、Na+、K+ ion exchange are further increased, and although the same ion exchange needs higher temperature and longer time, the higher central tensile stress can be realized through the blocking effect of alkaline earth metal with the specific proportion in the application, the mechanical property is improved, particularly 80-mesh sand paper falls, and the anti-falling height of glass ceramics with the thickness of 0.6mm is higher than 1.8m. More particularly, the glass ceramic after the hindered exchange has the advantages that Na + on the surface layer is not easy to hydrolyze and separate out, so that the glass ceramic has better performance when being tested in a high-temperature high-humidity environment, and the failure time of the glass ceramic is longer than 240 hours under the high-temperature high-humidity condition.
Drawings
FIG. 1 is an XRD pattern of the product obtained in example 1 of the present invention;
FIG. 2 is a chart showing the thickness of the surface pressure layer of the product prepared in example 1 of the present invention;
FIG. 3 is a graph showing the results of a 348-hour failure test in a high-temperature and high-humidity environment for the product prepared in example 1 of the present invention;
FIG. 4 is a graph showing the results of measuring the concentration of sodium ions on the surface of the product prepared in example 1 of the present invention after 360 hours in a high temperature and high humidity environment;
FIG. 5 is a graph showing the results of the tensile stress density test of the center of the product prepared in comparative example 1;
FIG. 6 is a graph showing the results of 180-240 hours of failure test in a high temperature and high humidity environment of the product prepared in comparative example 1.
Detailed Description
In the following detailed description, for purposes of explanation and not limitation, example embodiments disclosing specific details are set forth in order to provide a thorough understanding of the various principles of the present disclosure. It will be apparent to those skilled in the art having the benefit of this disclosure that the present disclosure may be practiced in other embodiments that depart from the specific details disclosed herein. In addition, descriptions of well-known devices, methods and materials may be omitted so as to not obscure the description of the various principles of the present invention.
Ranges may be expressed herein as from "about" another particular value, and/or to "about" another particular value, as a termination. As used herein, the term "about" means that the amounts, dimensions, formulations, parameters, and other variables and characteristics are not, nor need be, exact, but may be approximated and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding and measurement error and the like, among other factors known to those of skill in the art. When the term "about" is used to describe a range of values or endpoints, it is to be understood that the present disclosure includes the specific value or endpoint to which reference is made. Whether or not the numerical values of the specification or the endpoints of the ranges are expressed as "about," the numerical values or the endpoints of the ranges are intended to include the two embodiments: one modified with "about" and one without "about". It will also be understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
The terms "substantially," "essentially," and variations thereof as used herein are intended to mean that the feature being described is the same or approximately the same as the value or description. For example, a "substantially planar" surface is intended to mean a planar or near-planar surface. Furthermore, "substantially" is intended to mean that the two values are equal or approximately equal. In some embodiments, "substantially" may mean that the values are within about 10% of each other, such as within about 5% of each other, or within about 2% of each other.
No method described herein is intended to be construed as requiring that its steps be performed in a specific order unless expressly stated otherwise. Thus, when a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically expressed in the claims or descriptions that the steps are limited to a specific order, it is not intended that such an order be implied. The same applies to any possible non-explicitly stated interpretation basis including: logic regarding the setup step or operational flow; the general meaning obtained from grammatical structures or punctuation; the number or variety of embodiments described in the specification.
Example 1
The microcrystalline glass is prepared according to the following steps:
Firstly, preparing the following raw materials ：67.1mol%SiO2、4.2mol%Al2O3、1.12mol%P2O5、22.96mol%Li2O、0.1mol%Na2O、0.1mol%K2O、0.08mol%Sb2O3、2.99mol%ZrO2、0.95mol%MgO、0.2mol%CaO and 0.2mol% SrO according to mole percentage, transferring the raw materials into a platinum crucible, placing the platinum crucible into a high-temperature furnace, gradually heating to 1500 ℃, preserving heat for 6 hours, bubbling and homogenizing (the purpose of bubbling is to bring out small bubbles in glass and eliminate bubbles in glass liquid), pouring the molten liquid into a preheated die after melting for molding, and then annealing at 450 ℃ for 8 hours to obtain a precursor glass block; then, slicing the obtained precursor glass block by a diamond wire slicing machine to obtain a precursor glass sheet; the precursor glass flakes obtained were then heat treated, specifically by first incubating at 570 ℃ for 4 hours and then at 740 ℃ for 1 hour.
And then carrying out chemical strengthening: the composition of the strengthening salt in the chemical strengthening process is 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate, the strengthening temperature is 500 ℃, and the strengthening time is 8 hours.
Testing the finally prepared microcrystalline glass, wherein an XRD test chart of the prepared product is shown in figure 1, and as can be seen from figure 1, the main crystal phase of the prepared microcrystalline glass comprises petalite, lithium disilicate and spodumene; the surface compressive stress of the prepared product is tested by adopting a Japanese folding original SLP-2000 scattered light photoelastic stress meter, the test result is shown in figure 2, and the surface compressive stress of the prepared microcrystalline glass is 350Mpa as can be known from figure 2; meanwhile, failure test is carried out on the prepared product under the high-temperature and high-humidity condition, and as can be seen from an SEM (scanning electron microscope) graph of the product obtained in the embodiment after 348 hours under the 85 ℃ temperature condition and the 85% humidity condition, the product obtained in the embodiment has better high-temperature and high-humidity resistance; the test result of the sodium ion concentration on the surface of the product after 360 hours at 85 ℃ and 85% humidity is shown in fig. 4, and as can be seen from fig. 4, after 360 hours, the sodium ion concentration on the surface of the glass-ceramic is 11.2%.
Examples 2 to 12 differ from example 1 in the raw materials and experimental part parameters.
Comparative example 1
Firstly, preparing the following raw materials ：69.10mol%SiO2、4mol%Al2O3、1mol%P2O5、22.15mol%Li2O、0.07mol%Na2O、0.07mol%K2O、0.1mol%MgO、0.6mol%SrO、2.8mol%ZrO2 and 0.08mol% Sb 2O3 in terms of mole percentage, transferring the raw materials into a platinum crucible, placing the platinum crucible into a high-temperature furnace, gradually heating to 1500 ℃, preserving heat for 6 hours, bubbling and homogenizing (the purpose of bubbling is to bring out small bubbles in glass and eliminate bubbles in glass liquid), pouring the molten liquid into a preheated die after melting, forming, and then annealing at 450 ℃ for 8 hours to obtain a precursor glass block; then, slicing the obtained precursor glass block by a diamond wire slicing machine to obtain a precursor glass sheet; the precursor glass flakes obtained were then heat treated, specifically by first incubating at 570 ℃ for 4 hours and then at 740 ℃ for 1 hour.
And then carrying out chemical strengthening: the composition of the strengthening salt in the chemical strengthening process is 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate, the strengthening temperature is 500 ℃, and the strengthening time is 8 hours.
The center tensile stress density of the prepared product is tested, the test result is shown in figure 5, and as can be seen from figure 5, the center tensile stress density of the microcrystalline glass prepared in the comparative example is measured; meanwhile, failure test is performed on the prepared product under the condition of high temperature and high humidity, and fig. 6 is an SEM image of the product obtained in the comparative example after 240 hours under the condition of 85 ℃ and 85% humidity, and as can be seen from fig. 6, the product obtained in the embodiment has poor high temperature and high humidity resistance.
The raw material compositions and process parameters and the results of the resulting product tests of examples 1-7 are shown in Table 1.
TABLE 1 raw material compositions and process parameters and test results tables for the produced products of examples 1-7
| Raw material mol% | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| SiO2 | 67.10 | 67.10 | 67.70 | 68.40 | 68.90 | 69.07 | 69.25 |
| Al2O3 | 4.20 | 4.25 | 3.60 | 3.98 | 4.00 | 4.05 | 4.15 |
| P2O5 | 1.12 | 0.90 | 0.60 | 0.70 | 0.80 | 1.01 | 1.12 |
| Li2O | 22.96 | 22.75 | 22.15 | 22.90 | 22.65 | 22.16 | 21.90 |
| Na2O | 0.10 | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 | 0.09 |
| K2O | 0.10 | 0.07 | 0.06 | 0.07 | 0.08 | 0.07 | 0.09 |
| ZrO2 | 2.99 | 2.85 | 2.80 | 2.80 | 2.80 | 2.78 | 2.50 |
| MgO | 0.95 | 0.50 | 0.05 | 0.40 | 0.10 | 0.80 | |
| CaO | 0.20 | 0.50 | 0.30 | 0.60 | 0.71 | 0.10 | |
| SrO | 0.20 | 0.73 | 0.60 | ||||
| BaO | 0.20 | 0.70 | |||||
| Sb2O3 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | ||
| Melting process | Heat preservation for 2-24 hours at 1500-1600 DEG C | Heat preservation for 2-24 hours at 1500-1600 DEG C | Heat preservation for 2-24 hours at 1500-1600 DEG C | Heat preservation for 2-24 hours at 1500-1600 DEG C | Heat preservation for 2-24 hours at 1500-1600 DEG C | Heat preservation for 2-24 hours at 1500-1600 DEG C | Heat preservation for 2-24 hours at 1500-1600 DEG C |
| Heat treatment of | Heat-insulating at 570 deg.C for 4 hr, then at 740 deg.C for 1 hr | Heat-insulating at 570 deg.C for 4 hr, then at 740 deg.C for 1 hr | Heat-insulating at 570 deg.C for 4 hr, then at 740 deg.C for 1 hr | Heat-insulating at 570 deg.C for 4 hr, then at 740 deg.C for 1 hr | Heat-insulating at 570 deg.C for 4 hr, then at 740 deg.C for 1 hr | Heat-insulating at 570 deg.C for 4 hr, then at 740 deg.C for 1 hr | Heat-insulating at 570 deg.C for 4 hr, then at 740 deg.C for 1 hr |
| Strengthening treatment | Strengthening salt: 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate; strengthening temperature and time: 500 ℃ for 8h | Strengthening salt: 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate; strengthening temperature and time: 500-530 deg.C for 6-8h | Strengthening salt: 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate; strengthening temperature and time: 500-530 deg.C for 6-8h | Strengthening salt: 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate; strengthening temperature and time: 500-530 deg.C for 6-8h | Strengthening salt: 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate; strengthening temperature and time: 500-530 deg.C for 6-8h | Strengthening salt: 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate; strengthening temperature and time: 500-530 deg.C for 6-8h | Strengthening salt: 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate; strengthening temperature and time: 500-530 deg.C for 6-8h |
| Crystallinity% | 84 | 85 | 80 | 88 | 86 | 89 | 80 |
| CS layer thickness (mum) | 125 | 124 | 122 | 125 | 123 | 130 | 121 |
| Glass center tensile stress Density (Mpa/mm) | 356 | 355 | 353 | 357 | 353 | 362 | 351 |
| High temperature and high humidity failure time (h) | 348 | 341 | 340 | 345 | 339 | 350 | 340 |
| Vickers hardness ((kgf/mm 2) | 862 | 866 | 864 | 869 | 863 | 878 | 861 |
The raw material compositions and the process parameters and the results of the obtained product tests of examples 8 to 12 and comparative example 1 are shown in Table 2.
Table 2 raw material compositions and process parameters and results of the tests for the obtained products of examples 8 to 12 and comparative example 1
| Raw material mol% | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Comparative example 1 |
| SiO2 | 69.55 | 70.07 | 69.10 | 69.10 | 69.10 | 69.10 |
| Al2O3 | 4.05 | 4.05 | 4.00 | 4.00 | 4.00 | 4.00 |
| P2O5 | 1.02 | 1.01 | 1.00 | 1.00 | 1.00 | 1.00 |
| Li2O | 22.16 | 22.16 | 22.15 | 22.15 | 22.15 | 22.15 |
| Na2O | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 |
| K2O | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 |
| ZrO2 | 2.78 | 2.78 | 2.80 | 2.80 | 2.80 | 2.80 |
| MgO | 0.70 | 0.10 | 0.10 | |||
| CaO | 0.71 | 0.60 | ||||
| SrO | 0.72 | 0.60 | ||||
| BaO | 0.70 | |||||
| Sb2O3 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | |
| Melting process | Heat preservation for 2-24 hours at 1500-1600 DEG C | Heat preservation for 2-24 hours at 1500-1600 DEG C | Heat preservation for 2-24 hours at 1500-1600 DEG C | Heat preservation for 2-24 hours at 1500-1600 DEG C | Heat preservation for 2-24 hours at 1500-1600 DEG C | Heat preservation for 2-24 hours at 1500-1600 DEG C |
| Heat treatment of | Heat-insulating at 570 deg.C for 4 hr, then at 740 deg.C for 1 hr | Heat-insulating at 570 deg.C for 4 hr, then at 740 deg.C for 1 hr | Heat-insulating at 570 deg.C for 4 hr, then at 740 deg.C for 1 hr | Heat-insulating at 570 deg.C for 4 hr, then at 740 deg.C for 1 hr | Heat-insulating at 570 deg.C for 4 hr, then at 740 deg.C for 1 hr | Heat-insulating at 570 deg.C for 4 hr, then at 740 deg.C for 1 hr |
| Strengthening treatment | Strengthening salt: 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate; strengthening temperature and time: 500-530 deg.C for 6-8h | Strengthening salt: 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate; strengthening temperature and time: 500-530 deg.C for 6-8h | Strengthening salt: 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate; strengthening temperature and time: 500-530 deg.C for 6-8h | Strengthening salt: 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate; strengthening temperature and time: 500-530 deg.C for 6-8h | Strengthening salt: 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate; strengthening temperature and time: 500-530 deg.C for 6-8h | Strengthening salt: 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate; strengthening temperature and time: 500-530 deg.C for 6-8h |
| Crystallinity% | 81 | 85 | 83 | 84 | 82 | 70 |
| CS layer thickness (mum) | 121 | 122 | 126 | 124 | 120 | 98 |
| Glass center tensile stress Density (Mpa/mm) | 352 | 355 | 358 | 354 | 351 | 300 |
| High temperature and high humidity failure time (h) | 338 | 340 | 342 | 340 | 338 | 228 |
| Vickers hardness ((kgf/mm 2) | 860 | 863 | 867 | 864 | 861 | 680 |
Claims (12)
1. The high-strength glass ceramic is characterized in that the main crystal phase of the high-strength glass ceramic is petalite and lithium silicate, and the high-strength glass ceramic comprises ：67-70mol%SiO2、3.5-4.5mol%Al2O3、0.5-1.5mol%P2O5、21-23mol%Li2O、0.05-0.1mol%Na2O、0.05-0.1mol%K2O、0-0.1mol%Sb2O3、2.5-3mol%ZrO2, mgO, caO, srO and one or more of BaO; the thickness of a CS layer of the high-strength microcrystalline glass is more than or equal to 120 mu m, the central tensile stress density is more than 350Mpa/mm, and the Vickers hardness is more than or equal to 860kgf/mm 2.
2. The glass-ceramic according to claim 1, wherein CS 50/|CT-CV| >1.05 of the high-strength glass-ceramic, wherein CS50 means a stress value corresponding to a depth of 50 [ mu ] m,
The |CT-CV| refers to the absolute value of the maximum tensile stress in the tensile stress layer.
3. The glass-ceramic according to claim 2, wherein the CS50 of the high-strength glass-ceramic is 130Mpa or more; the |CT-CV| is greater than or equal to 120Mpa.
4. The high-strength glass-ceramic according to claim 1 or 2, wherein the high-strength glass-ceramic is subjected to a sandpaper drop test with 80-mesh sandpaper at a thickness of 0.6mm, and the average sandpaper drop height is not less than 1.8m.
5. The glass-ceramic according to claim 1, wherein the glass-ceramic further comprises one or more of spodumene, mg 0.6Al1.2Si1.8O6 crystal phase, βcasio 3 and diopside, and the total weight of the glass-ceramic is not more than 50% of the total weight of the glass-ceramic.
6. The high-strength glass-ceramic according to claim 1, wherein the total amount of three of Li 2O、Na2 O and K 2 O is 21.1 to 23.2mol%.
7. The high strength glass ceramic according to claim 1, wherein the total amount of MgO, caO, srO and BaO is 0.5 to 1mol%.
8. The high-strength glass-ceramic according to claim 1, wherein the ratio of the total molar amount of three of Li 2O、Na2 O and K 2 O to the total molar amount of four of MgO, caO, srO and BaO is 21 to 47.
9. The glass-ceramic according to claim 1, wherein the average size of crystal grains in the high-strength glass-ceramic is 100nm or less.
10. A method for preparing high strength glass ceramics according to any one of claims 1 to 9, comprising the steps of: melting, heat treatment, crystallization and chemical strengthening, wherein the composition of the strengthening salt in the chemical strengthening process is 70-80% of potassium nitrate, 20-30% of sodium nitrate and 0.05-10% of lithium nitrate, the strengthening temperature is above 500 ℃, and the strengthening time is above 4 hours.
11. The method for producing a high-strength glass ceramic according to claim 10, wherein the depth of ion diffusion in the strengthening process is 105 μm or more.
12. The method for producing a high-strength glass-ceramic according to claim 10 or 11, wherein the sodium ion concentration of the glass-ceramic surface is not lower than 12mol% after a lapse of 240 hours or more under high-temperature and high-humidity conditions.
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