CN113354288A - Microcrystalline glass plate and preparation method thereof - Google Patents
Microcrystalline glass plate and preparation method thereof Download PDFInfo
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- CN113354288A CN113354288A CN202110690382.5A CN202110690382A CN113354288A CN 113354288 A CN113354288 A CN 113354288A CN 202110690382 A CN202110690382 A CN 202110690382A CN 113354288 A CN113354288 A CN 113354288A
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- 239000011521 glass Substances 0.000 title claims abstract description 162
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 30
- 229910052678 stilbite Inorganic materials 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 238000003825 pressing Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004927 clay Substances 0.000 claims abstract description 8
- 238000005498 polishing Methods 0.000 claims abstract description 8
- 238000007500 overflow downdraw method Methods 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 4
- 238000010304 firing Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000005995 Aluminium silicate Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000440 bentonite Substances 0.000 claims description 10
- 229910000278 bentonite Inorganic materials 0.000 claims description 10
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 10
- 239000011118 polyvinyl acetate Substances 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 6
- 239000002241 glass-ceramic Substances 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 4
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 3
- 229910001462 kalsilite Inorganic materials 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 6
- 241001669680 Dormitator maculatus Species 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 43
- 238000002425 crystallisation Methods 0.000 description 38
- 230000008025 crystallization Effects 0.000 description 38
- 238000010899 nucleation Methods 0.000 description 29
- 230000006911 nucleation Effects 0.000 description 29
- 238000010438 heat treatment Methods 0.000 description 27
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 238000000137 annealing Methods 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 10
- 229910021532 Calcite Inorganic materials 0.000 description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 8
- 238000010791 quenching Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- RSCACTKJFSTWPV-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 RSCACTKJFSTWPV-UHFFFAOYSA-N 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 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 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- UGGQKDBXXFIWJD-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;hydrate Chemical compound O.[Ca].O[Si](O)=O UGGQKDBXXFIWJD-UHFFFAOYSA-N 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 239000010977 jade Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010903 primary nucleation Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
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
- C03C10/0036—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 a divalent 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
- 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
- C03C10/16—Halogen containing crystalline phase
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The application provides a microcrystalline glass plate and a preparation method thereof, and a main crystal phase stilbite NaCa of the microcrystalline glass plate2Si4O10F accounts for the following mass percent: 20% -70%; s1, preparing glass frit by adopting a fusion method, drying, and crushing the glass frit into a certain particle range by using a double-roll crusher to obtain glass frit A; s2, stirring and mixing the glass frit A65-85 wt%, the clay B10-27 wt% and the bonding additive C3-15 wt% in a stirring tank uniformly, homogenizing, and performing dry pressing to obtain the microcrystalline glass green body, wherein the glass frit A contains CaO8-15 wt% and Na2O 3‑7％，SiO260-72% of F3-7%; s3, sintering at the temperature of 600 plus materials and 630 ℃ for 30-50min and at the temperature of 880 plus materials and 1000 ℃ for 30-50 min; s4, polishing to obtainThe microcrystalline glass plate is described.
Description
Technical Field
The application relates to the field of microcrystalline glass, in particular to a microcrystalline glass plate and a preparation method thereof.
Background
The microcrystal glass plate is a mixture of microcrystal and glass prepared from proper glass particles through sintering and crystallization. The microcrystalline glass plate looks different from common glass, has the dual characteristics of glass and ceramic, has texture on the outer surface which is more inclined to the ceramic, but has higher brightness than the ceramic, certain light transmittance, and natural jade feeling by combining the crystal morphology, and has stronger toughness, bending strength and bending strength than the glass, and mechanical strength which can meet the use function of paving and pasting the ground and the wall.
The microcrystalline glass plate in the prior art has rich and various main crystal phases, wherein most of the main crystal phases of the jade series microcrystalline glass are the xonotlite, the crystallization temperature required for the production of the crystal phases is 800-900 ℃, the time required for heat preservation and crystallization is more than 60min, the total crystallization energy consumption is high, and the microcrystalline glass taking the xonotlite as the main crystal phase has insufficient impact toughness and poor processing and cutting performance when the light transmittance reaches a certain degree.
The production method of the microcrystalline glass plate in the prior art mainly comprises the following steps
1. Preparing by a rolling method: taking the publication number CN105271642B as an example, the method mainly comprises the steps of adding ingredients into a melting furnace, clarifying the melted ingredients under the condition of stirring to generate a proportional melt, and then feeding the glass melt into a roller press for rolling and calendering to form a glass plate; and finally, entering a roller kiln, and performing primary nucleation, enhanced nucleation and crystallization to obtain the microcrystalline glass plate. The disadvantages of this method are: (1) the productivity is very low, (2) the production process is very unstable, (3) the requirement on production conditions is high, (4) the energy consumption is very high, and finally the whole production cost is very high; in addition, the product has single color and only white color, has higher expansion coefficient and is not easy to carry out secondary decoration on the microcrystalline glass plate.
2. The advanced preparation method of the calendering method comprises the following steps: taking the publication number CN105294168B as an example, the method is to carry out ink-jet decoration on the basis of obtaining a basic microcrystalline glass plate by a rolling method, and then a layer of low-temperature fritted glaze is attached, thereby solving the problem of single product. However, this method requires secondary firing, which increases the cost and energy consumption.
3. Preparing by a sagger method: taking the publication number CN111960674A as an example, the method is formed by sintering a refractory material sagger, and the method is that pre-burning glass ceramics raw materials is carried out to prepare glass ceramics granular materials with different grain diameters, the materials are taken as the composition raw materials, the granular materials are classified and screened, and different granular materials are layered and stacked, and then a kiln is carried out to nucleate and crystallize to obtain the glass ceramics plate. The method is likely to be applied less because of the greater difficulty in industrialization.
The main problems of the prior art for comprehensively producing the microcrystalline glass plate are that the product process is complex, the production process is unstable, the yield is low, and therefore the whole production cost is very high.
Disclosure of Invention
The main purpose of the present application is to provide a main crystal phase of stilbite NaCa2Si4O10F, and provides a preparation method of the microcrystalline glass plate, aiming at solving the problems of complex production process, difficult control of production conditions, low productivity and the like in the prior art.
In order to achieve the above object, the present application provides a microcrystalline glass sheet and a method for manufacturing the same.
The application provides a microcrystalline glass plate, the main crystal phase of which is stilbite, stilbite NaCa2Si4O10The main crystal phase of F accounts for the mass percent of the material: 20 to 70 percent.
Preferably, the microcrystalline glass plate comprises the following crystalline phases in percentage by mass:
stilbite NaCa2Si4O10F30-50%; calcium fluoride CaF 21 to 10 percent; bulk stevensite Mg3SiO4F20.5 to 5 percent; kaliophilite KAlSiO4 0.5-5％。
The application also provides a preparation method of the microcrystalline glass plate, which comprises the following steps:
s1, preparing a glass frit A by adopting a fusion method;
s2, mixing 65-85% of glass frit A, 10-27% of clay B and 3-15% of bonding additive C uniformly according to mass percentage, homogenizing, and performing dry pressing forming to obtain a microcrystalline glass green body;
s3, firing;
s4, polishing to obtain a microcrystalline glass plate;
the glass frit A contains CaO 8-15%, and Na in terms of chemical oxides2O 3-7％，SiO260-72％，F 3-7％；
The temperature of the sintering is kept at 600-630 ℃ for 30-50min, and the temperature of 880-1000 ℃ for 30-50 min.
Preferably, the glass frit A comprises the following components in percentage by weight in terms of chemical oxides: SiO 22 60-72％，Al2O31.5～6％，CaO 8-15％，K2O 3-7％，Na2O 3-7％，MgO 0-1％，F 3-7％，CeO20-1％，Fe2O3 0-0.1％。
Preferably, clay B is: one or more of bentonite and kaolin.
Preferably, the bonding additive C is: one or more of polyacrylic resin, polyvinyl acetate, polyethylene-vinyl acetate and the above modified resins.
Preferably, the following steps are further included between step S2 and step S3;
s2-1, applying a layer of ground coat on the microcrystalline glass green body obtained in the step S2;
s2-2, decorating the microcrystalline glass green body obtained in the step S2-1;
s2-3, applying a layer of transparent dry particles on the microcrystalline glass green body obtained in the step S2-2;
preferably, the ground glaze comprises the following chemical components in percentage by mass: SiO 2255-65％，Al2O34-9％，B2O3 0.5-2％，CaO 13-22％，ZnO 1-5％，BaO 2-8％，K2O 1-5％，Na2O 3-7％。
Preferably, the chemical composition of the transparent dry granules is as follows by mass percent: SiO 22 35-48％，Al2O3 11-14％，B2O318-22％，CaO 7-10％，ZnO 0.5-1.5％，BaO 5-7％，K2O 3-5％，Na2O 3-5％，Li2O 1-3％。
Preferably, the cloth thickness of the transparent dry particles is 500-1500g/m2。
In the microcrystalline glass plate in the prior art, the main crystal phase is the xonotlite, the crystallization temperature required for producing the crystal phase is 800-900 ℃, the heat preservation crystallization time is more than 60min, and the total crystallization energy consumption is high. The microcrystalline glass using the kenyaite as the main crystal phase has insufficient impact toughness when the light transmittance reaches a certain degree, and has poor processing and cutting performance. Meanwhile, compared with the microcrystalline glass with the main crystalline phase of the sillimanite, the microcrystalline glass plate with the stilbite crystalline phase has lower expansion coefficient, is more beneficial to secondary decoration on the microcrystalline glass plate, and enriches the types of products.
In the technical scheme, a large amount of stilbite NaCa is generated in the sintering process2Si4O10The crystal phase F needs to have proper contents of Ca, Na, Si and F elements in the glass frit and simultaneously has certain nucleation temperature and nucleation time, crystallization temperature and crystallization time, and a large amount of experimental researches show that the stilbite NaCa needs to be prepared2Si4O10The crystal phase of F is 20-70%, the glass frit A contains CaO 8-15% and Na calculated by chemical oxide2O 3-7％，SiO260-72% of F3-7%; the nucleation temperature is within the range of 600-630 ℃, and the optimal nucleation time is within the range of 30-50 min; the crystallization temperature is in the range of 880-1000 ℃, and the optimal crystallization time is in the range of 30-50 min.
Compared with the prior art for producing the microcrystalline glass plate, the forming method in the technical scheme adopts dry pressing forming, the production process conditions of the dry pressing forming are simpler, the yield is higher, more than 20% of stilbite crystal phase needs to be generated on the microcrystalline glass plate, 65% of glass frit is needed and is a barren material, and the problem that the forming can be carried out and the bending strength of a green body is more than 4MPa needs to be solved by performing dry pressing forming on the glass frit with the content of more than 65%; experimental studies have found that this technical problem can be solved by incorporating 10-27% of clay material and 3-15% of a binding additive.
To sum up, the following beneficial effects of this application technical scheme:
(1) the microcrystalline glass plate with stilbite as main crystal phase has proper light transmittance and whiteness, high breaking strength and impact toughness and low expansion coefficient, and is favorable for subsequent further processing.
(2) The invention provides a preparation method of a microcrystalline glass plate, which has the advantages of simple process, high yield and low energy consumption.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a preparation method in an example of the present application.
Fig. 2 is an XRD diffraction pattern of the microcrystalline glass plate of example 1 of the present application.
The implementation, functional features and advantages of the objectives of the present application will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The preparation method of the microcrystalline glass plate comprises the following steps:
s1, preparing a glass frit A by adopting a fusion method;
uniformly mixing 36-46% of quartz sand, 25-32% of potassium feldspar, 15-22% of calcite, 2-6% of potassium carbonate, 5-10% of sodium fluosilicate, 0-2% of soda ash and 0-1% of cerium oxide, feeding the mixture into a frit kiln, controlling the temperature range to be 1500-1600 ℃ for melting, wherein the melting period is 10-20 hours, allowing the formed glass liquid to flow from a discharge port of the frit kiln to a water tank, carrying out water quenching to produce glass frit, and crushing the frit into required particles by using a double-roller crusher to obtain the glass frit A.
S2, stirring and mixing 65-85% of glass frit A, 10-27% of clay B and 3-15% of bonding additive C uniformly in a stirring tank according to mass percentage, homogenizing, and performing dry pressing to obtain a microcrystalline glass green body with the thickness of 2-30 mm;
wherein the clay B is one or two of bentonite and kaolin, and the bonding additive C is one or two of polyacrylic resin, polyvinyl acetate, polyethylene-vinyl acetate and the above modified resins.
S2-1, applying a layer of ground coat on the microcrystalline glass green body obtained in the step S2;
the ground glaze comprises the following raw materials in formula: 45-50 parts of quartz powder, 22-27 parts of calcite, 4-7 parts of soda ash, 5-8 parts of potassium carbonate, 0.5-2.5 parts of borax pentahydrate, 3-5 parts of zinc oxide, 5-8 parts of aluminum oxide and 5-7 parts of barium carbonate. Sending into a frit kiln, controlling the temperature range within 1350-.
S2-2, decorating the microcrystalline glass green body obtained in the step S2-1;
s2-3, applying a layer of transparent dry particles on the microcrystalline glass green body obtained in the step S2-2;
preparation of transparent dry granules: 33-37% of quartz, 5-10% of barium carbonate, 10-15% of calcite, 8-12% of alumina, 0.5-1% of zinc oxide, and borax pentahydrate: 8-12%, boric acid: 18-23 percent of the raw materials and 3-8 percent of the potassium carbonate are evenly mixed and sent into a frit kiln, the temperature is controlled within 1350-.
Distributing by adopting a dry particle distributing machine, wherein the distributing thickness is 500-1500g/m2。
S3, firing;
s31, heating and draining: 2-10min at room temperature of-600-630 ℃;
s32, constant-temperature nucleation: 30-50min at 600-630 ℃;
s33, heating: 2-10min at 600-630-880-1000 ℃;
s34, constant temperature crystallization: 30-50min at 880-1000 ℃;
and S35, cooling and annealing.
S4, polishing to obtain a microcrystalline glass plate;
the glass frit a obtained in the above example was tested to have a composition and content range of components in terms of oxides: SiO 2260-72％，Al2O31.5～6％，CaO 8-15％，K2O 3-7％，Na2O 3-7％，MgO 0-1％，F 3-7％，CeO20-1％，Fe2O3 0-0.1％。
The above examples are examples in which the formulation compositions and temperatures are within ranges, inclusive of the endpoints and any values within the ranges, are implementable, and examples of specific components and temperatures are set forth below in specific point values.
Example 1
A preparation method of a microcrystalline glass plate comprises the following steps:
s1, preparing a glass frit A by adopting a fusion method;
uniformly mixing 43% of quartz sand, 28.8% of potassium feldspar, 17.3% of calcite, 2.9% of potassium carbonate, 6.7% of sodium fluosilicate, 1% of soda ash and 0.3% of cerium oxide, feeding the mixture into a frit kiln, controlling the temperature range to be 1520 ℃ for melting, enabling the firing period to be 15 hours, enabling formed glass liquid to flow from a discharge port of the frit kiln to a water tank, carrying out water quenching to produce glass frit, and crushing the glass frit into required particles to obtain the glass frit A.
S2, according to mass percentage, stirring and mixing 80% of glass frit A, 5% of kaolin, 10% of bentonite and 5% of polyvinyl acetate serving as bonding additive C uniformly in a stirring tank, homogenizing, and performing dry pressing to obtain a microcrystalline glass green body with the thickness of 10 mm;
s3, firing;
s31, heating and draining: 5min, room temperature-620 ℃;
s32, constant-temperature nucleation: 40min, 620 ℃;
s33, heating: at the temperature of 620 ℃ for 5min and 920 ℃;
s34, constant temperature crystallization: 40min, 920 ℃;
and S35, cooling and annealing.
S4, polishing to obtain a microcrystalline glass plate;
the glass frit a obtained in the above example was tested for composition and content of components in terms of oxides: SiO 2267.2％，Al2O33.6％，CaO 12.9％，K2O 3.2％，Na2O 6.25％，MgO 0.12％，F 6.2％，CeO20.52％，Fe2O30.01％。
The microcrystalline glass has the following crystal phase contents in the tests: stilbite NaCa2Si4O10F48%, calcium fluoride CaF23% bulk stevensite Mg3SiO4F21.5 percent of kaliophilite KAlSiO4 0.8％。
Example 2
A preparation method of a microcrystalline glass plate comprises the following steps:
s1, preparing a glass frit A by adopting a fusion method;
uniformly mixing 36% of quartz sand, 30% of potassium feldspar, 18.5% of calcite, 5.2% of potassium carbonate, 9% of sodium fluosilicate, 0.8% of soda ash and 0.5% of cerium oxide, feeding the mixture into a frit kiln, controlling the temperature range to be 1580 ℃ for melting, wherein the firing period is 20 hours, the formed glass liquid flows from a discharge port of the frit kiln to a water tank, water quenching is carried out to produce glass frit, and the frit is crushed into required particles to form the glass frit A.
S2, stirring and mixing 75% of glass frit A, 22% of bentonite and 3% of bonding additive C, namely polyethylene-vinyl acetate, in a stirring tank uniformly, homogenizing, and performing dry pressing to obtain a microcrystalline glass green body with the thickness of 3 mm;
s3, firing;
s31, heating and draining: 3min at room temperature of-610 ℃;
s32, constant-temperature nucleation: 30min, 610 ℃;
s33, heating: 5min, 880 ℃;
s34, constant temperature crystallization: 30min, 880 ℃;
and S35, cooling and annealing.
S4, polishing to obtain a microcrystalline glass plate;
the glass frit a obtained in the above example was tested for composition and content of components in terms of oxides: SiO 2266.68％，Al2O34.2％，CaO 11.21％，K2O 5.62％，Na2O 5.47％，MgO 0.63％，F 5.56％，CeO20.61％，Fe2O30.02％。
Example 3
A preparation method of a microcrystalline glass plate comprises the following steps:
s1, preparing a glass frit A by adopting a fusion method;
uniformly mixing 46% of quartz sand, 26% of potassium feldspar, 15% of calcite, 4.5% of potassium carbonate, 6% of sodium fluosilicate, 1.5% of soda ash and 1% of cerium oxide, feeding the mixture into a frit kiln, controlling the temperature range to be 1500 ℃ for melting, wherein the firing period is 18 hours, the formed glass liquid flows from a discharge port of the frit kiln to a water tank, water quenching is carried out to produce glass frit, and the frit is crushed into required particles to form glass frit A.
S2, according to mass percentage, stirring and mixing a glass frit A70%, kaolin 15% and an adhesive additive C which are 5% of polyacrylic resin, 5% of polyvinyl acetate and 5% of polyethylene-vinyl acetate uniformly in a stirring tank, homogenizing, and performing dry pressing to obtain a microcrystalline glass green compact with the thickness of 25 mm;
s3, firing;
s31, heating and draining: 5min at room temperature of-650 ℃;
s32, constant-temperature nucleation: 50min, 650 ℃;
s33, heating: 8min, 650-980 ℃;
s34, constant temperature crystallization: 50min, 980 ℃;
and S35, cooling and annealing.
S4, polishing to obtain a microcrystalline glass plate;
the glass frit a obtained in the above example was tested for composition and content of components in terms of oxides: SiO 2271.1％，Al2O34.89％，CaO 10.28％，K2O 4.96％，Na2O 3.78％，MgO 0.24％，F 4.39％，CeO20.31％，Fe2O30.05％。
Example 4
The conditions in this example are the same as those in example 1, except that the firing in step S3 is performed with an additional strong nucleation stage, as follows:
s3, firing;
s31, heating and draining: 5min, room temperature-620 ℃;
s32, constant-temperature nucleation: 40min, 620 ℃;
s33, heating: 3min, 620 ℃ and 720 ℃;
s34, constant-temperature strong nucleation: 15min, 720 ℃;
s35, heating: 3min, 720 ℃ and 920 ℃;
s36, constant temperature crystallization: 40min, 920 ℃;
s37, quenching and annealing.
S4, polishing to obtain a microcrystalline glass plate;
example 5
The comparative example was conducted under the same conditions as in example 1 except that a decorative layer was formed on the crystallized glass plate between step S2 and step S3 by the following steps:
s2-1, applying a layer of ground coat on the microcrystalline glass green body obtained in the step S2;
the ground glaze comprises the following raw materials in formula: 47.3 parts of quartz powder, 25 parts of calcite, 6 parts of soda ash, 4 parts of potassium carbonate, 1.2 parts of borax pentahydrate, 4 parts of zinc oxide, 6.5 parts of aluminum oxide and 6 parts of barium carbonate, the quartz powder, the calcite, the soda ash, the potassium carbonate, the borax pentahydrate and the barium carbonate are sent into a frit kiln, the frit kiln is controlled to be melted within 1400 ℃, glass liquid flows to a water tank from an outlet of the frit kiln, water quenching is carried out, the frit is crushed to 200 meshes and 325 meshes, and glaze spraying are adopted after the frit is ball-milled.
S2-2, decorating the microcrystalline glass green body obtained in the step S2-1;
s2-3, applying a layer of transparent dry particles on the microcrystalline glass green body obtained in the step S2-2;
preparation of transparent dry granules: 35.1% of quartz, 6.7% of barium carbonate, 12.1% of calcite, 10.4% of aluminum oxide, 0.8% of zinc oxide, and borax pentahydrate: 10.7%, boric acid: 20.2 percent and 4 percent of potassium carbonate are uniformly mixed, sent into a frit kiln, melted at the temperature controlled within 1400 ℃, flowed into a water tank from the outlet of the frit kiln, quenched with water, crushed to 100-250 meshes and dried to obtain transparent dry frit particles.
Distributing by adopting a dry particle distributing machine, wherein the distributing thickness is 1200g/m2。
The performance of the microcrystalline glass sheets of examples 1 to 5 was tested, and in addition, a commercially available microcrystalline glass sheet with a thickness of 10mm and a main crystal phase of xonotlite prepared by a calendering method was purchased for comparison, and the specific performance test and effect comparison results are shown in the following table:
the transmittance detection method comprises the following steps: and (4) detecting by using a light transmittance measuring instrument.
Whiteness: and detecting by using a whiteness measuring instrument.
Breaking strength: and (4) detecting by using a bending strength measuring instrument.
Impact toughness: and (4) detecting by using an impact toughness measuring instrument.
Coefficient of expansion: and (4) detecting by using an expansion coefficient measuring instrument.
Crystal phase content: obtained by XRD diffraction pattern and component analysis instrument detection.
From the table, the light transmittance of the microcrystalline glass plate prepared by the method is basically up to the level even superior to that of the existing product under the same thickness, the whiteness is whiter than that of the existing product, the breaking strength and the impact toughness are superior to those of the existing product, the expansion coefficient is lower than that of the existing product, and the expansion coefficient of the existing product without stilbite crystal phase is higher.
Comparative example 1
The conditions in this comparative example were the same as those in example 1 except that the composition of the microcrystalline glass sheet in step S2 was:
s2, mixing and ball-milling glass frit A70%, kaolin 15% and bonding additive C which are 5% of polyacrylic resin, 5% of polyvinyl acetate and 5% of polyethylene-vinyl acetate in percentage by mass, homogenizing slurry, spray-drying, and then carrying out dry pressing forming to obtain the microcrystalline glass green body with the thickness of 10 mm.
Comparative example 2
The conditions in this comparative example were the same as those in example 1 except that the composition of the microcrystalline glass sheet in step S2 was:
s2, mixing and ball-milling the glass frit A75%, the bentonite 22% and the bonding additive C which is 3% of polyethylene-vinyl acetate, homogenizing slurry, spray-drying, and then carrying out dry pressing forming to obtain the microcrystalline glass green body with the thickness of 10 mm.
Comparative example 3
The conditions in this comparative example were the same as those in example 1 except that the composition of the microcrystalline glass sheet in step S2 was:
and S2, mixing and ball-milling the glass frit A65%, the kaolin 15%, the bentonite 5% and the bonding additive C which are 5% of polyacrylic resin, 5% of polyvinyl acetate and 5% of polyethylene-vinyl acetate, homogenizing slurry, spray-drying, and performing dry pressing to obtain the 10mm thick microcrystalline glass green body.
Comparative example 4
The conditions in this comparative example were the same as those in example 1 except that the composition of the microcrystalline glass sheet in step S2 was:
s2, mixing and ball-milling the glass frit A85%, kaolin 5%, bentonite 5% and the bonding additive C which is polyacrylic resin 5%, homogenizing slurry, spray-drying, and then carrying out dry pressing forming to obtain the microcrystalline glass green body with the thickness of 10 mm.
The components of the comparative examples are shown in the following table in percentage by mass:
the microcrystalline glass sheets of comparative examples 1 to 4 were subjected to performance tests, and the specific results of the performance tests and the effect comparison are shown in the following table:
from the above table, it can be seen that, under the condition of the same thickness, the light transmittance and the flexural strength of the glass plate are gradually increased along with the increase of the stilbite crystal phase content, the whiteness of the glass plate is the highest between 30 and 40 percent of the stilbite crystal phase content, the impact toughness of the glass plate is the highest between 40 and 50 percent of the stilbite crystal phase content, and the stilbite crystal phase content with the optimal comprehensive performance of the microcrystalline glass plate is 30 to 50 percent by combining the data.
Comparative example 5
The conditions in this comparative example were the same as those in example 1 except that the composition of the microcrystalline glass sheet in step S2 was:
s2, mixing and ball-milling the glass frit A50%, kaolin 25, bentonite 20% and the bonding additive C which is polyvinyl acetate 5% by mass, homogenizing slurry, spray-drying, and then carrying out dry pressing forming to obtain the microcrystalline glass green body with the thickness of 10 mm.
Comparative example 6
The conditions in this comparative example were the same as those in example 1 except that the composition of the microcrystalline glass sheet in step S2 was:
s2, mixing and ball-milling the glass frit A90%, kaolin 5 and the bonding additive C which is 5% of polyvinyl acetate, homogenizing slurry, spray-drying, and then carrying out dry pressing forming to obtain the microcrystalline glass green body with the thickness of 10 mm.
Comparative example 7
The conditions in this comparative example were the same as those in example 1 except that the composition of the microcrystalline glass sheet in step S2 was:
s2, mixing and ball-milling the glass frit A70%, kaolin 15 and bentonite 15% according to the mass percentage, homogenizing slurry, spray-drying, and then carrying out dry pressing forming to obtain a microcrystalline glass green body with the thickness of 10 mm.
Comparative example 8
The conditions in this comparative example were the same as those in example 1 except that the composition of the microcrystalline glass sheet in step S2 was:
s2, mixing and ball-milling the glass frit A70% and the adhesive additive C which is polyvinyl acetate 30% by mass percentage, homogenizing slurry, spray-drying, and then carrying out dry pressing forming to obtain the microcrystalline glass green body with the thickness of 10 mm.
The microcrystalline glass sheets of comparative examples 5 to 8 were subjected to performance tests, wherein comparative example 6, comparative example 7 and comparative example 8 were not subjected to subsequent performance tests because they could not be press-formed or the green strength after forming did not reach 4 or more, and the results of the performance tests and the effect comparison of the other comparative examples are shown in the following table:
as can be seen from the above table, the content of the glass frit needs to be controlled in a reasonable range, and if the content of the glass frit is relatively low, the light transmittance and whiteness of the product are not sufficient, and the visual effect of the suet white jade cannot be generated, if the content of the glass frit is relatively high, the whole glass plate is not easy to mold, cracks are easily generated after molding, the breaking strength and the impact toughness of the product are relatively poor, and if the content of the glass frit is relatively low, the crystalline phase content of the final stilbite of the glass plate is not high, and the light transmittance, the whiteness, the breaking strength and the toughness of the product are relatively poor.
Comparative example 9
The conditions in this comparative example were the same as those in example 1 except that the temperature of nucleation in the firing in step S3 was changed to 400 ℃, specifically:
s3, firing;
s31, heating and draining: 3min at room temperature-400 ℃;
s32, constant-temperature nucleation: 40min, 400 ℃;
s33, heating: at 920 ℃ for 8min and 400-;
s34, constant temperature crystallization: 40min, 920 ℃;
s35, quenching and annealing.
Comparative example 10
The conditions in this comparative example were the same as those in example 1 except for the change in the temperature of nucleation in the firing of step S3. Changing to 800 ℃, specifically:
s3, firing;
s31, heating and draining: 5min at room temperature of-800 ℃;
s32, constant-temperature nucleation: 40min at 800 ℃;
s33, heating: 3min, 800 ℃ and 920 ℃;
s34, constant temperature crystallization: 40min, 920 ℃;
and S35, cooling and annealing.
Comparative example 11
The conditions in this comparative example were the same as those in example 1 except that the change in the nucleation time in the firing of step S3 was changed to 10min, specifically:
s3, firing;
s31, heating and draining: 5min, room temperature-620 ℃;
s32, constant-temperature nucleation: 10min, 620 ℃;
s33, heating: at the temperature of 620 ℃ for 5min and 920 ℃;
s34, constant temperature crystallization: 40min, 920 ℃;
and S35, cooling and annealing.
Comparative example 12
The conditions in this comparative example were the same as those in example 1 except that the change in the nucleation time in the firing of step S3 was changed to 70min, specifically:
s3, firing;
s31, heating and draining: 5min, room temperature-620 ℃;
s32, constant-temperature nucleation: 70min, 620 ℃;
s33, heating: at the temperature of 620 ℃ for 5min and 920 ℃;
s34, constant temperature crystallization: 40min, 920 ℃;
and S35, cooling and annealing.
Comparative example 13
The conditions in this comparative example were the same as those in example 1, except that the crystallization temperature was changed in the firing of step S3, and the crystallization temperature was 700 ℃, specifically:
s3, firing;
s31, heating and draining: 5min, room temperature-620 ℃;
s32, constant-temperature nucleation: 40min, 620 ℃;
s33, heating: 5min, 620 ℃ and 700 ℃;
s34, constant temperature crystallization: 40min, 700 ℃;
and S35, cooling and annealing.
Comparative example 14
The conditions in this comparative example were the same as those in example 1, except that the crystallization temperature was changed in the firing of step S3, and the crystallization temperature was 1100 ℃, specifically:
s3, firing;
s31, heating and draining: 5min, room temperature-620 ℃;
s32, constant-temperature nucleation: 40min, 620 ℃;
s33, heating: 8min, 620 ℃ and 1100 ℃;
s34, constant temperature crystallization: 40min, 1100 ℃;
and S35, cooling and annealing.
Comparative example 15
The conditions in this comparative example were the same as those in example 1, except that the crystallization time in the firing of step S3 was changed to 10min, specifically:
s3, firing;
s31, heating and draining: 5min, room temperature-620 ℃;
s32, constant-temperature nucleation: 40min, 620 ℃;
s33, heating: at the temperature of 620 ℃ for 5min and 920 ℃;
s34, constant temperature crystallization: 10min, 920 ℃;
and S35, cooling and annealing.
Comparative example 16
The conditions in this comparative example were the same as those in example 1, except that the crystallization time was changed in the firing of step S3, the crystallization temperature was 70min, specifically:
s3, firing;
s31, heating and draining: 5min, room temperature-620 ℃;
s32, constant-temperature nucleation: 40min, 620 ℃;
s33, heating: at the temperature of 620 ℃ for 5min and 920 ℃;
s34, constant temperature crystallization: 70min, 920 ℃;
and S35, cooling and annealing.
When the microcrystalline glass plates of the above comparative examples 5 to 12 were subjected to the property test, the sintered crystallization temperature of comparative example 14 was too high, and thus the green body was completely melted into the glass phase, and the related properties could not be tested, and the specific property test and effect comparison results of the other comparative examples are shown in the following table:
as can be seen from the above table, the firing schedule of the microcrystalline glass plate is very important, especially, the generation of stilbite crystal forms is required, and the process is carried out at a certain nucleation temperature and time and a certain crystallization temperature and time, the lower nucleation temperature or the insufficient nucleation time, or the lower crystallization temperature or the insufficient crystallization time both affect the crystal phase content of the last stilbite, and similarly, the formation of stilbite crystal forms cannot be well realized at the higher nucleation temperature or the higher crystallization temperature, and meanwhile, the crystal phase content of stilbite is slightly increased but not significantly increased when the nucleation time is longer or the crystallization time is longer, so that the time can be controlled within a certain range from the viewpoint of energy saving.
The above description is only a preferred embodiment of the present application, and not intended to limit the scope of the present application, and all modifications and equivalents of the subject matter of the present application, which are made by the following claims and their equivalents, or which are directly or indirectly applicable to other related arts, are intended to be included within the scope of the present application.
Claims (10)
1. A glass-ceramic plate characterized in that its main crystal phase is stilbite, said stilbite NaCa2Si4O10The main crystal phase of F accounts for the mass percent of the following components: 20 to 70 percent.
2. The microcrystalline glass sheet according to claim 1, wherein the microcrystalline glass sheet comprises the following crystalline phases in percentage by mass:
stilbite NaCa2Si4O10F 30-50％；
Calcium fluoride CaF2 1-10％；
Bulk stevensite Mg3SiO4F2 0.5-5％；
Kaliophilite KAlSiO4 0.5-5％。
3. The method for producing a crystallized glass sheet according to claim 1, comprising the steps of:
s1, preparing a glass frit A by adopting a fusion method;
s2, uniformly mixing 65-85% of the glass frit A, 10-27% of clay B and 3-15% of bonding additive C by mass percent, homogenizing, and performing dry pressing forming to obtain a microcrystalline glass green body;
s3, firing;
s4, polishing to obtain the microcrystalline glass plate;
the glass frit is prepared byThe chemical oxide contains CaO 8-15% and Na2O 3-7％，SiO2 60-72％，F 3-7％；
The sintering is carried out at the temperature of 600-630 ℃ for 30-50min, and at the temperature of 880-1000 ℃ for 30-50 min.
4. The method according to claim 4, wherein the glass frit A comprises the following components in percentage by weight in terms of chemical oxides: SiO 22 60-72％，Al2O3 1.5～6％，CaO 8-15％，K2O 3-7％，Na2O 3-7％，MgO 0-1％，F 3-7％，CeO2 0-1％，Fe2O30-0.1％。
5. The method for producing a crystallized glass sheet according to claim 4, wherein the clay B is: more than one of bentonite and kaolin.
6. The method for producing a crystallized glass plate according to claim 4, wherein the bonding additive C is: one or more of polyacrylic resin, polyvinyl acetate, polyethylene-vinyl acetate and the above modified resins.
7. The method for producing a crystallized glass sheet according to claims 4 to 6, wherein the following steps are further included between step S2 and step S3;
s2-1, applying a layer of ground coat on the microcrystalline glass green body obtained in the step S2;
s2-2, decorating the microcrystalline glass green body obtained in the step S2-1;
s2-3, applying a layer of transparent dry granules on the glass-ceramic green body obtained in the step S2-2.
8. The method for preparing a microcrystalline glass sheet according to claim 7, wherein the ground coat comprises the following chemical components in percentage by mass: SiO 22 55-65％，Al2O3 4-9％，B2O3 0.5-2％，CaO 13-22％，ZnO 1-5％，BaO 2-8％，K2O 1-5％，Na2O 3-7％。
9. The method for preparing a microcrystalline glass sheet according to claim 7, wherein the chemical composition of the transparent dry particles is as follows by mass percent: SiO 22 35-48％，Al2O3 11-14％，B2O318-22％，CaO 7-10％，ZnO 0.5-1.5％，BaO 5-7％，K2O 3-5％，Na2O 3-5％，Li2O 1-3％。
10. The method for preparing a glass-ceramic plate as claimed in claim 7, wherein the thickness of the cloth of the transparent dry particles is 500-1500g/m2。
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