CN119461857A - Colored microcrystalline glass and its preparation method and application - Google Patents
Colored microcrystalline glass and its preparation method and application Download PDFInfo
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- CN119461857A CN119461857A CN202411701338.XA CN202411701338A CN119461857A CN 119461857 A CN119461857 A CN 119461857A CN 202411701338 A CN202411701338 A CN 202411701338A CN 119461857 A CN119461857 A CN 119461857A
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- 239000011521 glass Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 64
- 239000003086 colorant Substances 0.000 claims abstract description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 8
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008395 clarifying agent Substances 0.000 claims abstract description 5
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 37
- 238000002425 crystallisation Methods 0.000 claims description 36
- 230000008025 crystallization Effects 0.000 claims description 36
- 239000006121 base glass Substances 0.000 claims description 34
- 238000010899 nucleation Methods 0.000 claims description 29
- 230000006911 nucleation Effects 0.000 claims description 29
- 229910052664 nepheline Inorganic materials 0.000 claims description 17
- 239000010434 nepheline Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 9
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 6
- 238000002834 transmittance Methods 0.000 claims description 6
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 5
- 238000006124 Pilkington process Methods 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000006104 solid solution Substances 0.000 claims description 4
- 229910000500 β-quartz Inorganic materials 0.000 claims description 4
- 238000003490 calendering Methods 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 3
- 239000006025 fining agent Substances 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 abstract description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 description 20
- 239000012071 phase Substances 0.000 description 20
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000000292 calcium oxide Substances 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 229910018068 Li 2 O Inorganic materials 0.000 description 4
- 238000010411 cooking Methods 0.000 description 4
- 238000005034 decoration Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910011763 Li2 O Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000007545 Vickers hardness test Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000758 substrate Substances 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 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 description 1
- 239000005328 architectural glass Substances 0.000 description 1
- -1 bubbles Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 210000001808 exosome Anatomy 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007656 fracture toughness test Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000006064 precursor glass Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses colored microcrystalline glass and a preparation method and application thereof, and relates to the field of microcrystalline glass. The colored glass ceramic comprises, by mole, ：SiO240～60％、Al2O315～25％、Na2O 15～25％、Li2O 1～5％、K2O 0～3％、MgO 0～4％、CaO 0～4％、ZrO21～8％、B2O30.5～8％、P2O50.5～5％、TiO20～3％、 parts of a clarifying agent 0.1-2% and an oxide colorant 0.1-8%, and 16% or more and 30% or less of Na 2O+Li2O+K2 O. The colored microcrystalline glass with the main sodium element, low lithium content and low cost is formed by doping the oxide colorant, and can be applied to the fields of rear covers of consumer electronic products, decorative panels of various display devices, decorative panels of stoves of a kitchen range and the like.
Description
Technical Field
The invention relates to the field of glass ceramics, in particular to colored glass ceramics and a preparation method and application thereof.
Background
In the rear cover of consumer electronic products, decorative panels of various display devices or decorative panels of cooking stoves, in order to meet the individual pursuit of consumers on different colors of products, nonferrous metal materials are required to be used for manufacturing the products, or when transparent materials such as glass or acrylic are used for manufacturing the products, processes such as coating, electroplating, spraying paint and the like are adopted for carrying out printing ink silk-screen processing. Both of these methods can achieve various color effects, but also increase the process cost. In addition, the signal transmission can be affected when the rear cover of the consumer electronic product is made of nonferrous metal materials.
Microcrystalline glass is a functional material obtained by controlling the crystallization process of base glass, and contains a large amount of microcrystalline phase and glass phase. The material has excellent mechanical property, thermal property and chemical stability, so that the material has wide application prospect in various industries (including consumer electronic products). The problems can be solved by introducing colored elements (iron, copper, manganese, nickel, selenium, cobalt, chromium, cadmium or rare earth elements) into glass ceramics, but in the technology disclosed at present, the content of Li element in the glass formula is higher, and the formed crystal forms are mainly petalite, lithium silicate, eucryptite and the like. With the development of the lithium battery industry, the corresponding mineral cost for obtaining Li is increased sharply, so that the cost of the existing colored glass is still high and is not advantageous.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide colored microcrystalline glass, a preparation method and application thereof, and aims to provide colored microcrystalline glass with low cost so as to meet the requirements of materials in different fields on colors.
The technical scheme of the invention is as follows:
In a first aspect of the invention, a colored glass-ceramic is provided, wherein, the colored microcrystalline glass comprises the following components in percentage by mole:
SiO2 40％～60％、Al2O3 15％～25％、Na2O 15％～25％、Li2O 1％～5％、K2O0％～3％、MgO 0％～4％、CaO 0％～4％、ZrO2 1％～8％、B2O3 0.5％～8％、P2O50.5％～5％、TiO20％～3％、 0.1-2% of clarifying agent and 0.1-8% of oxide colorant;
Wherein Na 2O+Li2O+K2 O is more than or equal to 16% and less than or equal to 30%.
Optionally, the fining agent includes at least one of SnO 2, naCl, and Sb 2O3, and/or,
The oxide colorant includes at least one of CeO2、Fe2O3、NiO、V2O5、Cr2O3、CuO、Er2O3、La2O3、Y2O3、Nd2O3 and Ho 2O3.
Optionally, the crystalline phase of the colored glass-ceramic includes at least one of nepheline, nepheline solid solution, tricked nepheline, zirconia, and beta quartz solid solution.
Optionally, when the thickness of the colored microcrystalline glass is 0.7mm, the average transmittance of the colored microcrystalline glass to light in the wavelength range of 380-800 nm is 20% -80%.
Optionally, the crystallinity of the colored microcrystalline glass is more than or equal to 25% and less than or equal to 80%.
In a second aspect of the present invention, a method for preparing colored glass ceramics is provided, which comprises the following steps:
The components of the colored microcrystalline glass are mixed according to the invention to obtain a mixture;
after the mixture is melted, forming and annealing are carried out to obtain base glass;
And (3) sequentially carrying out nucleation treatment and crystallization treatment on the base glass to obtain the colored microcrystalline glass.
Optionally, after the base glass is subjected to nucleation treatment and crystallization treatment in sequence, the step of obtaining the colored microcrystalline glass specifically comprises the following steps:
And (3) sequentially carrying out nucleation treatment and crystallization treatment on the base glass, and then placing the base glass in molten salt for ion exchange chemical strengthening to obtain the colored microcrystalline glass.
Optionally, heating the mixture at 1450-1700 ℃ for 2-6 hours to melt;
The forming method comprises a float method, a drawing method, a calendaring method or a casting method;
the annealing temperature is 300-600 ℃, and the annealing time is 2-6 h.
Optionally, the temperature of the nucleation treatment is 400-600 ℃, and the time of the nucleation treatment is 2-8 hours;
the temperature of the crystallization treatment is 540-950 ℃, and the time of the crystallization treatment is 0.25-3 h.
In a third aspect, the present invention provides an application of the colored glass-ceramic disclosed by the present invention or the colored glass-ceramic prepared by the preparation method disclosed by the present invention in a rear cover of a consumer electronic product, various decoration panels of display equipment or a decoration panel of a stove.
The colored microcrystalline glass has the beneficial effects that the colored microcrystalline glass is formed by mixing the oxide colorant in the glass component, and meanwhile, the colored microcrystalline glass is mainly made of sodium element, has low lithium content and low cost, and can be applied to the fields of rear covers of consumer electronic products, decorative panels of various display equipment, decorative panels of cooking stoves and the like.
Drawings
Fig. 1 is an XRD pattern of the colored glass in example 1.
Detailed Description
The invention provides colored microcrystalline glass, a preparation method and application thereof, and aims to make the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention is further illustrated by the following specific examples.
Some terms in the present invention are explained as follows:
And the base glass is glass which is formed by uniformly mixing compounds corresponding to various oxides (including silicon dioxide, aluminum oxide, sodium oxide, calcium oxide and the like), adopting one forming mode of a float method, an overflow pull-down method, a rolling method and a pouring method after high-temperature melting, and is not subjected to nucleation, crystallization treatment and ion exchange chemical strengthening treatment after annealing treatment.
Microcrystalline glass is a solid composite material which is prepared by carrying out controlled crystallization treatment with a set target on base glass and simultaneously comprises a glass phase and a crystal phase (microcrystalline phase and crystalline phase).
Nucleation, namely, the base glass is subjected to heat treatment to enable nucleation substances in the glass to grow into tiny crystal nuclei.
Crystallization, in which the base glass is grown into a certain crystal on the basis of the crystal nucleus by heat treatment.
The crystal phase is a microstructure of crystallization and is a collective term for a large number of solid phase components in a crystalline state.
Crystallinity is used to represent the proportion of crystals in glass ceramics, generally the mass proportion of crystalline phases to the entire glass ceramics.
The glass phase is amorphous mineral phase, has low refractoriness, is in the glass phase at normal temperature, is gradually softened in the heating process, and finally is in the liquid phase. The glass phase is filled in the main crystal phase to form a material matrix, also called a bonding phase, alone or together with a part of the crystal mineral.
Transmittance is the ratio of the radiant energy projected through an object to the total radiant energy projected onto the object during the time that the incident light flux leaves from the illuminated or medium incident surface to the other surface.
Lab value Lab is a physiological feature-based color model where L represents brightness, a includes colors from dark green to gray to bright powder, and b includes colors from bright blue to gray to yellow.
The embodiment of the invention provides colored microcrystalline glass, which comprises the following components in percentage by mole:
SiO2 40％～60％、Al2O3 15％～25％、Na2O 15％～25％、Li2O 1％～5％、K2O0％～3％、MgO 0％～4％、CaO 0％～4％、ZrO2 1％～8％、B2O3 0.5％～8％、P2O50.5％～5％、TiO20％～3％、 0.1-2% of clarifying agent and 0.1-8% of oxide colorant;
Wherein Na 2O+Li2O+K2 O is more than or equal to 16% and less than or equal to 30%, and the sum of the mole percentages of the components is 100%.
According to the embodiment of the invention, the colored microcrystalline glass is formed by doping the oxide colorant into the glass component, and meanwhile, the colored microcrystalline glass is mainly sodium (sodium can form natrium nepheline or triclinite), so that the lithium content is low, the cost is low, and the colored microcrystalline glass can be applied to the fields of rear covers of consumer electronic products, decorative panels of various display equipment, decorative panels of cooking stoves and the like.
In the embodiment of the invention, the colored glass ceramic can have a transmission color coordinate in a Lab color space in the following range of L=15-95, a=60-60, and b=60-60. Further, the colored glass ceramic can have a transmission color coordinate in Lab color space in a range of L=30-90, a=40-50, and b=0-50.
The colored glass-ceramic is absorptive over the visible range. The colored microcrystalline glass with the thickness of 0.7mm has an average light transmittance of 20% -80% for light in a wavelength range of 380-800 nm.
In this embodiment, siO 2,SiO2 is introduced into the components of the colored glass ceramic to obtain the components with the highest content. SiO 2 is used as a main network forming agent, can stabilize a network structure, forms a main structure of a precursor and colored microcrystalline glass, and is also a main component of a partial crystalline phase. The overall performance of the colored glass-ceramic is weakened when the SiO 2 content is too low, the molar content of SiO 2 is not lower than 40%, the melting and forming are difficult when the SiO 2 content is too high, and the components contain higher silicon components, so that the difficulty of melting the precursor of the colored glass-ceramic is further increased. Therefore, considering comprehensively that the molar content of SiO 2 is controlled to be 40% -60%, for example, the molar content of SiO 2 is 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60% or any one of the numerical ranges consisting of any two of the above numerical values as an end point. Specifically, the molar content of SiO 2 is 44% -59%.
Al 2O3 is an intermediate oxide formed by colored glass ceramics, is also a main component of crystal forms such as natrium nepheline, triclinite and the like, can obviously improve the thermal stability of base glass and colored glass ceramics, and simultaneously, because [ AlO 4 ] is larger than [ SiO 4 ], can provide larger space for ion exchange, and therefore, al 2O3 can promote the ion exchange. However, an excessively high content of Al 2O3 increases the viscosity of the base glass, which is disadvantageous for melting, and comprehensively considers that the molar content of Al 2O3 is 15% -25%, for example, the molar content of Al 2O3 is 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, or any one of the numerical ranges consisting of any two of the above numerical values as an end point. Specifically, the molar content of Al 2O3 is 16% -23%.
Na 2 O is one of the main components of nepheline and tricked nepheline, and is also an important element in the subsequent chemical strengthening process. Meanwhile, na 2 O is a fluxing agent for high-temperature melting of the base glass, so that the melting temperature of the base glass can be obviously reduced, but when the content of Na 2 O is higher than 25%, the chemical stability of the colored microcrystalline glass can be obviously reduced, so that the ideal molar content of Na 2 O is less than or equal to 25%, and at the moment, the melting temperature can be kept within a proper range, and good ion exchange characteristics can be ensured. Considering comprehensively, the molar content of Na 2 O is 15% -25%, for example, the molar content of Na 2 O is 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25% or any one value in a numerical range consisting of any two of the above values as an end point, specifically, the molar content of Na 2 O is 15% -23%.
Li 2 O is an oxide with higher alkali metal activity, is an oxide of an external body of a glass network, is used as one of additives for reducing the high-temperature viscosity of base glass, and can obviously improve the high-temperature fluidity of the glass. Meanwhile, li + can participate in ion exchange chemical strengthening reaction in the colored glass ceramics, so that the mechanical properties of the colored glass ceramics are further enhanced. In the invention, li element does not participate in crystallization, but can be used for secondary chemical strengthening of glass, so that the mechanical property of the glass is further improved. Considering comprehensively, the molar content of Li 2 O is 1% -5%, for example, the molar content of Li 2 O is 1%, 2%, 3%, 4%, 5% or any one value in a numerical range consisting of any two values of the above values as the end points.
K 2 O is an optional component for improving the low-temperature meltability and formability of the glass, but if the molar content of K 2 O is too high, the chemical stability of the glass is easily lowered. Comprehensively considering that the molar content of K 2 O is 0% -3%, for example, the molar content of K 2 O is 0%, 1%, 2%, 3% or any one value in a numerical range formed by taking any two values of the above values as endpoints.
Considering comprehensively that the total molar content of three of Na 2O、Li2 O and K 2 O is 16% -30%, for example, the total molar content of three of Na 2O、Li2 O and K 2 O is 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% or any one of the numerical ranges consisting of any two of the above values as the end points.
MgO can improve the melting of the base glass, reduce the liquidus temperature and is beneficial to improving the thermal stability of the colored microcrystalline glass. Meanwhile, the MgO can improve the chemical stability and mechanical strength of the colored microcrystalline glass and reduce the crystallization tendency of the colored microcrystalline glass. However, when the content is too high, the crystallization property of the colored glass-ceramics is lowered, which is unfavorable for obtaining the desired crystal phase type and crystal grain size of the colored glass-ceramics. Accordingly, the molar content of MgO in the glass ceramic component may be, for example, 0%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or any one of the numerical ranges having any two of the above values as the end points. Specifically, the molar content of MgO is 0% -2%.
CaO is used as a network external oxide formed by the colored microcrystalline glass, is beneficial to reducing the viscosity of the colored microcrystalline glass, inhibits crystallization of the colored microcrystalline glass during molding of the colored microcrystalline glass, and can improve the low-temperature melting property of the colored microcrystalline glass, but excessive CaO can reduce the devitrification resistance of the colored microcrystalline glass. The effect of reducing the viscosity of the colored glass-ceramic and not affecting the crystallization performance of the colored glass-ceramic can be achieved by adding a proper amount of CaO, and the molar content of CaO is 0% -4%, for example, 0%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% and any two of the above numerical values form any one of the ranges. Specifically, the molar content of CaO is 0.2% -2%.
ZrO 2 is an intermediate oxide formed by colored glass ceramics, can improve the chemical stability of the colored glass ceramics, increase the hardness, scratch resistance and drop resistance of the colored glass ceramics, and has a large accumulation effect on the structure of the colored glass ceramics due to the high cationic charge and strong field of ZrO 2, thus being used as a nucleating agent in the colored glass ceramics. However, excessive ZrO 2 can significantly increase the viscosity of the colored glass-ceramic and affect the forming ability of the colored glass-ceramic. Comprehensively, the molar content of ZrO 2 is 1% -8%, for example, the molar content of ZrO 2 is 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% or any one of the numerical ranges consisting of any two of the above numerical values as endpoints.
B 2O3 is used as a network exosome oxide of colored microcrystalline glass, is filled in the gaps of a silicon oxygen tetrahedral framework, the cation coordination of the B 2O3 is rarely changed, and part of the property of the oxide can be considered as a constant value. B 2O3 helps to provide a base glass with a low melting temperature. In addition, the damage resistance of the colored microcrystalline glass can be improved by adding the B 2O3. Considering comprehensively that the molar content of B 2O3 is 0.5% -8%, for example, the molar content of B 2O3 is 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% or any one of the numerical ranges consisting of any two of the above numerical values as endpoints. Specifically, the molar content of B 2O3 is 0.5% -7%.
P 2O5 is used as a nucleating agent to promote the phase separation and overall crystallization ability of the base glass, and if the content of P 2O5 is too low, the base glass is not crystallized and crystals are formed only at a higher temperature and a low viscosity from the surface inwards, and if the content of P 2O5 is too high, it is difficult to control devitrification when cooling is performed during the formation of the base glass. Considering comprehensively, the molar content of P 2O5 is 0.5% -5%, for example, the molar content of P 2O5 is 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% or any one of the numerical ranges consisting of any two of the above numerical values as endpoints.
TiO 2 is one of nucleating agents for crystal nucleation and growth in microcrystalline glass, can effectively promote crystal nucleus growth of base glass in the process of nucleation and crystallization treatment, and meanwhile, stability of the glass is improved, tiO 2 is introduced to effectively promote precipitation of crystal nuclei in the process of nucleation, and meanwhile, tiO 2 is introduced to enable phase separation to occur on the base glass easily, so that crystallization is caused, and glass formation is affected. Comprehensively, the molar content of TiO 2 is 0% -3%, for example, the molar content of TiO 2 is 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% or any one value in a numerical range formed by taking any two values of the above values as endpoints.
In some embodiments, the fining agent includes at least one of SnO 2, naCl, and Sb 2O3. SnO 2、NaCl、Sb2O3 is used as a good clarifying agent in the production of colored microcrystalline glass, can effectively homogenize the components of precursor glass and reduce the formation of undesirable substances such as bubbles, stones and the like. In general, the total molar content of one or more of the three of SnO 2、NaCl、Sb2O3 is 0.1% -2%, for example, the molar content of one or more of the three is 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2% or any one of the numerical ranges consisting of any two of the above numerical values as endpoints. Specifically, the content is 0.5% -2%.
In some embodiments, the oxide colorant comprises at least one of CeO2、Fe2O3、NiO、V2O5、Cr2O3、CuO、Er2O3、La2O3、Y2O3、Nd2O3 and Ho 2O3. Considering comprehensively, the molar content of the oxide colorant is 0.1% -8%, for example, the molar content of the oxide colorant is 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, or any one of the numerical ranges consisting of any two of the above numerical values as endpoints.
In some embodiments, the crystalline phase of the colored glass-ceramic includes at least one of nepheline, nepheline solid solution, tricked nepheline, zirconia, and beta quartz solid solution.
In some embodiments, the colored glass-ceramic has a crystallinity of 25% or more and 80% or less.
The embodiment of the invention also provides a preparation method of the colored microcrystalline glass, which comprises the following steps:
s1, mixing the components of the colored microcrystalline glass to obtain a mixture;
s2, after the mixture is melted, forming and annealing are carried out to obtain base glass;
and S3, sequentially carrying out nucleation treatment and crystallization treatment on the base glass to obtain the colored microcrystalline glass.
The preparation method provided by the invention is simple, oxide coloring agents are doped into the components to form the colored microcrystalline glass, meanwhile, the colored microcrystalline glass is mainly made of sodium (sodium forms nepheline and triclinite), the lithium content is low, the cost is low, and the colored microcrystalline glass can be applied to the fields of rear covers of consumer electronic products, decorative panels of various display equipment, decorative panels of cooking bench stoves and the like.
In step S2, in some embodiments, the mixture is heated at a temperature of 1450-1700 ℃ (e.g., 1450 ℃, 1500 ℃, 1550 ℃, 1600 ℃, 1650 ℃, 1700 ℃, or any one of the numerical ranges consisting of any two of the above values) for 2-6 hours (e.g., 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, or any one of the numerical ranges consisting of any two of the above values).
In some embodiments, the molding method includes a float method, a drawing method, a calendaring method, or a casting method, but is not limited thereto.
In some embodiments, the annealing is performed at a temperature of 300-600 ℃ (e.g., 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃, or any one of a range of values ending in any two of the foregoing values), the annealing time is 2-6 h (for example, 2h, 3h, 4h, 5h, 6h or any one value in a numerical range formed by taking any two values as endpoints).
In step S3, in some embodiments, the temperature of the nucleation is 400 to 600 ℃ (for example, may be 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃ or any one of the numerical ranges formed by taking any two of the above numerical values as the end points), and the time of the nucleation is 2 to 8 hours (for example, may be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours or any one of the numerical ranges formed by taking any two of the above numerical values as the end points).
In some embodiments, the crystallization process is performed at a temperature of 540 to 950 ℃ (e.g., 540 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or any one of the numerical ranges consisting of any two of the above values as endpoints), and the crystallization process is performed for a time of 0.25 to 3 hours (e.g., 0.25 hours, 0.5 hours, 1.0 hours, 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours or any one of the numerical ranges consisting of any two of the above values as endpoints).
In the process of preparing colored glass-ceramics, the temperature and time of the heat treatment step need to be strictly controlled, so that the type of precipitated crystals, the crystal size and the crystal ratio are controlled, and the final integrity, quality, color and/or opacity of the obtained colored glass-ceramics can be influenced. In some embodiments, the crystalline phase of the colored glass-ceramic produced by the production method includes at least one of nepheline, nepheline solid solution, tricked nepheline, zirconia, and beta quartz solid solution, with a crystallinity in the range of 25% to 80%.
In step S3, in some embodiments, the step of obtaining the colored glass-ceramic after subjecting the base glass to a nucleation treatment and a crystallization treatment in sequence specifically includes:
and (3) sequentially carrying out nucleation treatment and crystallization treatment on the base glass, and then placing the base glass in molten salt for ion exchange chemical strengthening to obtain the colored microcrystalline glass (namely the strengthened colored microcrystalline glass can also be chemically strengthened colored microcrystalline glass).
The invention further provides application of the colored glass-ceramic disclosed by the embodiment of the invention or the colored glass-ceramic prepared by the preparation method disclosed by the embodiment of the invention in a rear cover of a consumer electronic product, various decoration panels of display equipment or decoration panels of a kitchen range stove.
The colored glass-ceramic provided by embodiments of the present invention may be used in a variety of applications, such as cover glass or glass backplanes in consumer or business electronics (e.g., LCD and LED displays, computer monitors, automated teller machines, televisions, and cameras), touch screens or touch sensors, portable electronics (e.g., mobile telephones, personal media players, and tablet computers), integrated circuits (e.g., semiconductor wafers), photovoltaic (e.g., architectural glass), vehicular (e.g., automotive) glass, and commercial or household appliances.
As an example, the colored glass-ceramic is applied to a consumer electronic device, the consumer electronic device comprising:
A housing;
an electronic assembly located at least partially or entirely within the housing and including at least a controller, a memory, and a display located at or adjacent a front surface of the housing;
and a cover substrate positioned on or over the front surface of the housing such that it is positioned over the display;
wherein at least a portion of at least one of the cover substrate and/or the housing may comprise the colored glass-ceramic.
The invention is further illustrated by the following specific examples.
Table 1, formulation of glass in each example and comparative example
Example 1
The embodiment provides a preparation method of colored microcrystalline glass, which comprises the following steps:
(1) Weighing the raw material powders according to the components and the proportion in the embodiment 1 in the table 1, and then placing the raw material powders in a mixer for mixing for 30min to obtain a mixture;
(2) Transferring the mixture into a platinum crucible, melting for 3 hours at the temperature of 1600 ℃, pouring into a forming die, annealing for 2 hours at the temperature of 420 ℃ after a casting forming process, and cooling to obtain the base glass.
(3) Putting the base glass into an annealing furnace, preserving heat for 180min at 513 ℃ for nucleation treatment, then heating to 590 ℃ and preserving heat for 20min for crystallization treatment, then cooling to room temperature along with the furnace, and then carrying out ion exchange in molten salt (99 wt% NaNO 3+1wt％KNO3) at 460 ℃ for 8h for chemical strengthening to obtain the colored microcrystalline glass.
Example 2
The present example provides a method for preparing colored glass ceramics, which differs from example 1 only in that the raw material powders are weighed according to the components and proportions in example 2 in table 1;
In the step (3), the nucleation treatment is carried out at 531 ℃ for 300min, and then the crystallization treatment is carried out after the temperature is raised to 613 ℃ and the temperature is kept for 40 min.
Example 3
This example provides a method for preparing colored glass ceramics, which differs from example 1 only in that the raw material powders are weighed according to the components and proportions in example 3 in table 1;
in the step (3), the nucleation treatment is carried out at 563 ℃ for 360min, then the temperature is raised to 681 ℃ and the crystallization treatment is carried out at 30min.
Example 4
This example provides a method for preparing colored glass ceramics, which differs from example 1 only in that the raw material powders are weighed according to the components and proportions in example 4 in table 1;
In the step (3), the nucleation treatment is carried out at 515 ℃ for 240min, and then the crystallization treatment is carried out after the temperature is raised to 601 ℃ and the temperature is kept for 60 min.
Example 5
This example provides a method for preparing colored glass ceramics, which differs from example 1 only in that the raw material powders are weighed according to the components and proportions in example 5 in table 1;
in the step (3), the nucleation treatment is carried out at 533 ℃ for 240min, and then the crystallization treatment is carried out by heating to 640 ℃ and preserving the temperature for 30 min.
Example 6
The present example provides a method for preparing colored glass ceramics, which differs from example 1 only in that each raw material powder is weighed according to the components and proportions in example 6 in table 1;
In the step (3), the nucleation treatment is carried out at the temperature of 588 ℃ for 360min, and then the crystallization treatment is carried out after the temperature is raised to 670 ℃ and the temperature is kept for 15 min.
Comparative example 1
This comparative example provides a process for producing a glass-ceramic, which differs from example 1 only in that each raw material powder is weighed according to the components and proportions in comparative example 1 in Table 1;
in the step (3), the nucleation treatment is carried out at 533 ℃ for 240min, and then the crystallization treatment is carried out by heating to 640 ℃ and preserving the temperature for 30 min.
Comparative example 2
This comparative example provides a method for producing chemically strengthened glass ceramics, which differs from example 1 only in that each raw material powder is weighed according to the components and proportions in comparative example 2 in table 1;
In the step (3), the nucleation treatment is carried out at the temperature of 523 ℃ for 240min, and then the crystallization treatment is carried out by heating to 619 ℃ and preserving the temperature for 60 min.
And (3) testing:
1. Crystalline form and crystallinity test:
microcrystalline glass is ground to powder, subjected to a physical Smartlab X Ray Diffraction (XRD) test, and analyzed for crystal phase composition and crystallinity by using Jade.
2. L value, a value and b value in Lab test:
the L value, a value and b value of the glass in each example were tested using a colorimeter (model CM-3600A).
3. Average transmittance test:
And testing the average value of the transmittance of the glass sample sheet with the thickness of 0.7mm to the 380-800 nm light wave band by using an Shimadzu ultraviolet-visible spectrophotometer UV-2600.
4. Vickers hardness test:
The vickers hardness of the microcrystalline glass is tested by adopting a digital display small-load vickers hardness tester VTD405 (Beijing Warewet technology Co., ltd.) according to the national standard GB/T37900-2019 "ultra-thin glass hardness and fracture toughness test method small-load vickers hardness indentation method". When the invention is used for the Vickers hardness test, the test is carried out on a glass sample sheet with the length, width and thickness of 50mm multiplied by 0.7 mm.
5. Impact strength test:
average anti-sand paper falling height refers to the ratio of the sum of the measured anti-sand paper falling heights of each sample sheet to the number of the glass sample sheets in the same glass sample sheets, and is used for representing the anti-falling performance of the glass. At least 10 identical glass samples were taken each time and tested to obtain an average sandpaper drop height.
The test method of the anti-sand paper falling height of each glass sample sheet comprises the following steps:
and step 1, sticking 120-mesh sand paper on the lower surface of a 160g model machine, and placing the model machine on a green map LT-SKDL-CD drop machine.
And 2, placing a glass sample wafer to be tested with the length and width of 50mm multiplied by 0.7mm under the model machine, and enabling the glass sample wafer to face the sand paper. The molding machine is impacted and falls at a certain falling height to impact the glass sample sheet positioned right below the molding machine. If the glass sample sheet is not broken, the falling height of the model machine is increased according to a certain rule. For example, the falling height starts from 40cm, and the glass sample sheet is subjected to one falling impact, if not broken, and the glass sample sheet is again fallen by increasing the height by 10cm each time until the glass sample sheet is broken.
And 3, recording the last falling height of the glass sample wafer when the glass sample wafer is broken as the anti-sand paper falling height, for example, the falling height of the glass sample wafer when the glass sample wafer is broken is 100cm, and the anti-sand paper falling height of the glass sample wafer is 90cm.
The results of the above measurements are shown in fig. 1 and table 2.
Table 2, test results of examples and comparative examples
From the results, the colored microcrystalline glass with different colors can be prepared, and each colored microcrystalline glass has higher vickers hardness and impact strength. As is clear from comparative example 2, when Li 2 O is not added, although colored glass ceramics (such as light green glass ceramics) can be prepared, the mechanical properties of the prepared colored glass ceramics are obviously reduced.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. The colored microcrystalline glass is characterized by comprising the following components in percentage by mole:
SiO2 40％～60％、Al2O3 15％～25％、Na2O 15％～25％、Li2O 1％～5％、K2O 0％～3％、MgO 0％～4％、CaO 0％～4％、ZrO2 1％～8％、B2O3 0.5％～8％、P2O5 0.5％～5％、TiO2 0％～3％、 0.1-2% of clarifying agent and 0.1-8% of oxide colorant;
Wherein Na 2O+Li2O+K2 O is more than or equal to 16% and less than or equal to 30%.
2. The colored glass-ceramic of claim 1, wherein the fining agent comprises at least one of SnO 2, naCl and Sb 2O3, and/or,
The oxide colorant includes at least one of CeO2、Fe2O3、NiO、V2O5、Cr2O3、CuO、Er2O3、La2O3、Y2O3、Nd2O3 and Ho 2O3.
3. The colored glass-ceramic of claim 1, wherein the crystalline phase of the colored glass-ceramic comprises at least one of nepheline, nepheline solid solution, tricked nepheline, zirconia, and beta quartz solid solution.
4. The colored glass-ceramic according to claim 1, wherein the crystallinity of the colored glass-ceramic is 25% or more and 80% or less.
5. The colored glass-ceramic according to claim 1, wherein when the thickness of the colored glass-ceramic is 0.7mm, the average transmittance of the colored glass-ceramic to light in a wavelength range of 380 to 800nm is 20 to 80%.
6. The preparation method of the colored microcrystalline glass is characterized by comprising the following steps:
The colored glass-ceramic according to claim 1 is prepared to obtain a mixture;
after the mixture is melted, forming and annealing are carried out to obtain base glass;
And (3) sequentially carrying out nucleation treatment and crystallization treatment on the base glass to obtain the colored microcrystalline glass.
7. The method according to claim 6, wherein the step of obtaining the colored glass-ceramic after subjecting the base glass to the nucleation treatment and the crystallization treatment in this order comprises:
And (3) sequentially carrying out nucleation treatment and crystallization treatment on the base glass, and then placing the base glass in molten salt for ion exchange chemical strengthening to obtain the colored microcrystalline glass.
8. The preparation method according to claim 6, wherein the mixture is heated at 1450-1700 ℃ for 2-6 hours to melt;
The forming method comprises a float method, a drawing method, a calendaring method or a casting method;
the annealing temperature is 300-600 ℃, and the annealing time is 2-6 h.
9. The method according to claim 6, wherein the temperature of the nucleation is 400-600 ℃, and the time of the nucleation is 2-8 hours;
the temperature of the crystallization treatment is 540-950 ℃, and the time of the crystallization treatment is 0.25-3 h.
10. Use of the colored glass-ceramic according to any one of claims 1 to 5 or prepared by the preparation method according to any one of claims 6 to 9 in rear covers of consumer electronics products, decorative panels of various display devices or decorative panels of cooktops.
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