CN115947541B - Cerium-tin-zinc system crystal glaze rich in colored particles, ceramic tile and preparation method thereof - Google Patents
Cerium-tin-zinc system crystal glaze rich in colored particles, ceramic tile and preparation method thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 143
- 239000002245 particle Substances 0.000 title claims abstract description 134
- WVCWZRQYDQZQHD-UHFFFAOYSA-N [Zn].[Sn].[Ce] Chemical compound [Zn].[Sn].[Ce] WVCWZRQYDQZQHD-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000000919 ceramic Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 30
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 50
- 238000010304 firing Methods 0.000 claims description 37
- 239000011734 sodium Substances 0.000 claims description 37
- 239000011449 brick Substances 0.000 claims description 26
- 239000011787 zinc oxide Substances 0.000 claims description 25
- 238000005507 spraying Methods 0.000 claims description 22
- 230000005484 gravity Effects 0.000 claims description 19
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 15
- 239000005995 Aluminium silicate Substances 0.000 claims description 13
- 235000012211 aluminium silicate Nutrition 0.000 claims description 13
- 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 13
- 238000005245 sintering Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000007641 inkjet printing Methods 0.000 claims description 10
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- 239000010436 fluorite Substances 0.000 claims description 8
- 239000005350 fused silica glass Substances 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 7
- 239000008188 pellet Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 description 29
- 238000000034 method Methods 0.000 description 20
- 238000001035 drying Methods 0.000 description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 10
- 238000007688 edging Methods 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000003086 colorant Substances 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 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 5
- 229910052656 albite Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000375 suspending agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910008284 Si—F Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- NZYYYKTZOWEGLS-UHFFFAOYSA-N [Sn].[Ce] Chemical compound [Sn].[Ce] NZYYYKTZOWEGLS-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000003238 silicate melt Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- Glass Compositions (AREA)
Abstract
The invention relates to a cerium-tin-zinc system crystal glaze rich in colored particles, a ceramic tile and a preparation method thereof. The cerium-tin-zinc system crystal glaze rich in color particles comprises the following raw materials in parts by weight: 90-95% of cerium tin zinc crystalline glaze and 5-10% of one or more colored dry particles; wherein the chemical composition of the cerium tin zinc crystal glaze comprises: in mass percent, siO 2 ：46～50％、Al 2 O 3 ：6～9％、CaO：4.0～6.0％、MgO：1.0～2.0％、K 2 O：0.5～1.5％、Na 2 O：4.0～6.0％、ZnO：23～27％、F：1.5～3.5％、CeO 2 ：0.5～3.5％、SnO 2 ：0.5～3.5％。
Description
Technical Field
The invention relates to a cerium-tin-zinc system crystal glaze rich in color particles, a ceramic tile and a preparation method thereof, belonging to the technical field of ceramic tile production and manufacturing.
Background
The crystal glaze is taken as a noble ceramic artistic glaze and is derived from ancient color glaze in China. The crystal glaze is separated out of a plurality of crystal flowers with various shapes in the glaze or on the surface of the glaze, the crystal flowers are approximately and naturally changed, the beautiful feeling is given to people, and the special artistic decorative effect is very high in ornamental value and is favored by consumers. The traditional crystal glaze is mainly used for artware and daily ceramic, and has late application development and less occurrence on building ceramic.
Chinese patent CN104311155 a discloses a crystalline glaze tile and a production method thereof, wherein crystalline frit and seed crystal are applied on a conventional porcelain tile blank, the temperature is raised to 1130-1200 ℃, the temperature is kept for 10-30 min, then the temperature is lowered to 1000-1080 ℃, and the temperature is kept for 1-2 h, thus obtaining the crystalline glaze tile with obvious crystal flower effect. The crystal tile produced by the process has long firing time, harsh firing conditions, difficult mass production under the current firing system conditions of the building ceramic and high production cost. Chinese patent CN102936156B discloses a glaze material for high-temperature quick-firing crystalline glaze archaizing brick and a preparation process, wherein the process adopts a silk screen to print dry grains of a crystallization agent frit after spraying crystalline colored base glaze, and adopts a silk screen to print transparent or colored dry grains and then quick-firing in a roller kiln to obtain the archaizing brick with different colors of crystal flower effects. However, the process cannot combine the crystal pattern effect with the modern ink-jet printing technology, the glaze decoration effect is single, and the texture effect of the modern ceramic tile is difficult to be reflected.
Disclosure of Invention
Aiming at the problems, the invention aims to provide cerium-tin-zinc system crystal glaze rich in color particles, a ceramic tile and a preparation method thereof. The invention develops the cerium-tin-zinc system crystal glaze rich in color particles, which meets the low-temperature rapid firing requirement of modern building ceramic products, on the basis of the traditional crystal glaze formula, and applies the cerium-tin-zinc system crystal glaze rich in color particles with unique artistic decoration effect to building ceramics.
In a first aspect, the present invention provides a cerium tin zinc based crystalline glaze enriched in coloured particles.The cerium-tin-zinc system crystal glaze rich in color particles comprises the following raw materials in parts by weight: 90-95% of cerium tin zinc crystalline glaze and 5-10% of one or more colored dry particles; wherein the chemical composition of the cerium tin zinc crystal glaze comprises: in mass percent, siO 2 ：46～50％、Al 2 O 3 ：6～9％、CaO：4.0～6.0％、MgO：1.0～2.0％、K 2 O：0.5～1.5％、Na 2 O：4.0～6.0％、ZnO：23～27％、F：1.5～3.5％、CeO 2 ：0.5～3.5％、SnO 2 ：0.5～3.5％。
Preferably, the cerium tin zinc crystal glaze comprises the following raw materials in parts by weight: the fluorite comprises the following components in percentage by mass: 6-8% of kaolin: 4-6%, fused quartz: 17-23%, zinc oxide: 23-27%, cerium oxide: 0.5 to 3.5 percent, tin dioxide: 0.5 to 3.5 percent.
Preferably, the cerium tin zinc crystal glaze further comprises the following raw materials in percentage by weight: the frit A comprises the following components in percentage by mass: 7-13%; the frit A is a low-temperature transparent frit, and comprises the following chemical components: in mass percent, siO 2 ：65.0～69.0％、Al 2 O 3 ：3.0～5.0％、CaO：14.0～16.0％、MgO：1.0～3.0％、K 2 O and/or Na 2 O：3.0～5.0％、ZnO：7.0～9.0％。
Preferably, the cerium tin zinc crystal glaze further comprises the following raw materials in percentage by weight: the frit B comprises the following components in percentage by mass: 24-34%; the frit B is a high-sodium frit, and comprises the following chemical components: in mass percent, siO 2 ：59.0～63.0％、Al 2 O 3 ：14.5～16.5％、MgO：4.0～6.0％、K 2 O：1.5～2.5％、Na 2 O：12.5～14.5％。
Preferably, the colored dry particles include at least one of red dry particles, blue dry particles, and black dry particles.
Preferably, the chemical composition of the red dry particles comprises: in mass percent, siO 2 ：46～50％，Al 2 O 3 ：14～18％，CaO：3.0～5.0％，MgO：0.5～1.5％，K 2 O：2.5～4.5％，Na 2 O：2.5～4.5％，ZrO 2 ：8.0～12.0％，ZnO：5.0～8.0％，SrO：3.0～5.0％，CdO：0.5～1.0％，SeO 2 :0.1 to 0.6 percent, loss on ignition: 0.5 to 1.5 percent.
Preferably, the chemical composition of the blue dry particles includes: in mass percent, siO 2 ：55～60％，Al 2 O 3 ：7.0～10.0％，CaO：20.0～24.0％，MgO：0.01～0.5％，K 2 O：0.5～1.5％，Na 2 O：3.5～4.5％，Fe 2 O 3 :0.5 to 1.5 percent of MnO:2.0 to 3.0 percent, coO:0.01 to 0.5 percent, loss on ignition: 0.5 to 1.5 percent.
Preferably, the chemical composition of the black dry particles includes: in mass percent, siO 2 ：44.0～48.0％，Al 2 O 3 ：14.0～18.0％，TiO 2 ：0.01～0.5％，CaO：12.0～15.0％，MgO：0.01～0.5％，K 2 O：1.0～2.0％，Na 2 O：2.5～4.5％，ZrO 2 ：4.5～6.5％，ZnO：3.0～5.0％，Fe 2 O 3 ：0.5～1.5％，CoO：1.0～2.0％，MnO：5.5～7.5％，MoO 3 :0.1 to 0.5 percent, loss on ignition: 0.5 to 1.5 percent.
In a second aspect, the invention provides a cerium-tin-zinc system crystal glaze ceramic tile rich in colored particles, which sequentially comprises a crystal glaze layer formed by the cerium-tin-zinc system crystal glaze rich in colored particles, an inkjet pattern layer, an overglaze layer and a blank layer from top to bottom.
In a third aspect, the invention provides a method for preparing a cerium-tin-zinc-based crystal glazing ceramic tile enriched in colored particles, comprising the steps of:
applying surface glaze on the surface of the green brick; preferably, the overglaze is a chromophoric overglaze; more preferably, the overglaze is applied by spraying; further preferably, the specific gravity of the overglaze is 1.44-1.46, and the glazing amount is 450-550 g/m 2 ；
Ink-jet printing a design pattern on the surface of the green brick after the surface glaze is applied;
applying the above-mentioned materials on the surface of the green brick after the designed pattern is printed by means of ink-jet printingCerium tin zinc crystal glaze rich in color particles; preferably, the application mode of the cerium-tin-zinc system crystal glaze rich in the color particles is glazing; more preferably, the specific gravity of the cerium-tin-zinc system crystal glaze rich in colored particles is 1.80-1.90, and the glazing quantity is 650-850 g/m 2 ；
Sintering the green bricks after the cerium-tin-zinc system crystal glaze rich in color particles is applied; preferably, the highest firing temperature is 1180-1200 ℃ and the firing period is 60-100 min;
polishing the ceramic tile after firing to obtain the cerium-tin-zinc series crystal glaze ceramic tile rich in colored particles.
Advantageous effects
The cerium-tin-zinc system crystal glaze rich in the colored particles not only separates out white cerium-tin-zinc system crystal flowers in the firing process, but also is rich in crystal flower-shaped colored particles, the glaze surface presents crystal flower patterns and crystal flower-shaped particles with various colors, the unique artistic decorative effect of the cerium-tin-zinc system crystal glaze has great ornamental value, and the cerium-tin-zinc system crystal glaze can be applied to building ceramics as the decorative effect to improve the grade of ceramic tiles.
Drawings
Fig. 1 is a flowchart of an exemplary preparation process of a cerium-tin-zinc-based crystal glazing ceramic tile rich in colored particles provided by the invention.
Detailed Description
The invention is further illustrated by the following detailed description, which is to be understood as being merely illustrative of the invention and not limiting thereof. Unless otherwise specified, each percentage refers to a mass percent.
First, the invention provides a cerium-tin-zinc system crystal glaze rich in colored particles. The raw material composition of the cerium tin zinc crystal glaze rich in the colored particles comprises cerium tin zinc crystal glaze and colored dry particles.
The chemical composition of the cerium tin zinc crystal glaze comprises: in mass percent, siO 2 ：46～50％、Al 2 O 3 ：6～9％、CaO：4.0～6.0％、MgO：1.0～2.0％、K 2 O：0.5～1.5％、Na 2 O：4.0～6.0％、ZnO：23～27％、F：1.5～3.5％、CeO 2 ：0.5～3.5％、SnO 2 ：0.5～3.5％。
The technical proposal disclosed by the invention is that SnO is simultaneously introduced into cerium tin zinc crystal glaze 2 、CeO 2 The crystal nucleus agent such as fluoride and the like can realize stable crystallization under the low-temperature rapid-sintering process condition, and simultaneously the sintered glaze has the three-dimensional effect of white crystal flowers and colored particles. SnO (SnO) 2 、CeO 2 Higher coordination number of the iso-oxide and Sn 4+ 、Ce 4+ The cation field is strong, and tin oxide and cerium oxide are easy to be separated out from silicate network in the cooling process or SnO rich with about 5nm is generated 2 、CeO 2 Thereby inducing nucleation of silicate melt. At the same time, the fluoride will also separate from the melt during cooling, forming a fine crystalline precipitate that introduces glass opacification. The principle of fluoride emulsion glass is utilized to promote glass nucleation, wherein fluoride microcrystal is the nucleation center of the glass. At the same time due to two F - Ion-substituted O 2- The ion reaches electrical neutrality, reflecting that it is structurally equivalent to the substitution of one silicon-fluorine bond (≡Si-O-Si≡) with two silicon-fluorine bonds (≡Si-F). The presence of Si-F groups means that the breakage of the silica network leads to weakening of the glass structure, inducing devitrification of the glass. In some embodiments, the initial melting temperature of the cerium tin zinc crystalline glaze is 950 to 1000 ℃.
As an example, the chemical composition of the cerium tin zinc crystalline glaze includes: in mass percent, siO 2 ：46～50％，Al 2 O 3 ：6～9％，Fe 2 O 3 ：0.01～0.5％，TiO 2 ：0.01～0.1％，CaO：4.0～6.0％，MgO：1.0～2.0％，K 2 O：0.5～1.5％，Na 2 O：4.0～6.0％，ZnO：23.0～27.0％，F：1.5～3.5％，CeO 2 ：0.5～3.5％，SnO 2 :0.5 to 3.5 percent, loss of burning: 0.5 to 2.0 percent.
The cerium tin zinc crystal glaze comprises the following raw materials in parts by weight: the fluorite comprises the following components in percentage by mass: 6-8% of kaolin: 4-6%, fused quartz: 17-23%, zinc oxide: 23-27%, cerium oxide: 0.5 to 3.5 percent, tin dioxide: 0.5 to 3.5 percent.
Preferably, the cerium tin zinc crystal glaze further comprises the following raw materials in percentage by weight: frit a (low temperature transparent frit): 7-13%.
The chemical composition of the frit A comprises: in mass percent, siO 2 ：65.0～69.0％、Al 2 O 3 ：3.0～5.0％、CaO：14.0～16.0％、MgO：1.0～3.0％、K 2 O and/or Na 2 O：3.0～5.0％、ZnO：7.0～9.0％。
Preferably, the cerium tin zinc crystal glaze further comprises the following raw materials in percentage by weight: frit B (high sodium frit) in mass percent: 24-34%.
The chemical composition of the frit B comprises: in mass percent, siO 2 ：59.0～63.0％、Al 2 O 3 ：14.5～16.5％、MgO：4.0～6.0％、K 2 O：1.5～2.5％、Na 2 O：12.5～14.5％。
In an alternative embodiment, the raw material composition of the cerium tin zinc crystalline glaze comprises: the fluorite comprises the following components in percentage by mass: 6-8% of kaolin: 4-6%, fused quartz: 17-23%, zinc oxide: 23-27%, cerium oxide: 0.5 to 3.5 percent, tin dioxide: 0.5 to 3.5 percent, and the low-temperature transparent frit: 7-13% of high-sodium frit: 24-34%.
The colored dry particles comprise at least one of red dry particles, blue dry particles and black dry particles. The colored dry particles form crystal flowers in the sintering process. In some embodiments, the onset temperature of the colored dry particles is 1000 to 1050 ℃.
In an alternative embodiment, the chemical composition of the red dry particles may include: in mass percent, siO 2 ：46～50％，Al 2 O 3 ：14～18％，Fe 2 O 3 ：0.01～0.5％，TiO 2 ：0.01～0.1％，CaO：3.0～5.0％，MgO：0.5～1.5％，K 2 O：2.5～4.5％，Na 2 O：2.5～4.5％，ZrO 2 ：8.0～12.0％，ZnO：5.0～8.0％，SrO：3.0～5.0％，CdO：0.5～1.0％，SeO 2 :0.1 to 0.6 percent, loss on ignition: 0.5 to 1.5 percent. The chemical composition of the red dry particles specifically used in the examples and comparative examples includes: in mass percent, siO 2 ：48.0％，Al 2 O 3 ：15.0％，Fe 2 O 3 ：0.1％，TiO 2 ：0.1％，CaO：4.0％，MgO：1.0％，K 2 O：3.0％，Na 2 O：4.0％，ZrO 2 ：10.0％，ZnO：7.0％，SrO：4.0％，CdO：1.0％，SeO 2 :0.1%, loss on ignition: 0.5%.
In an alternative embodiment, the chemical composition of the blue dry particles may include: in mass percent, siO 2 ：55～60％，Al 2 O 3 ：7.0～10.0％，TiO 2 ：0.01～0.1％，CaO：20.0～24.0％，MgO：0.01～0.5％，K 2 O：0.5～1.5％，Na 2 O：3.5～4.5％，Fe 2 O 3 :0.5 to 1.5 percent of MnO:2.0 to 3.0 percent, coO:0.01 to 0.5 percent, loss on ignition: 0.5 to 1.5 percent.
In an alternative embodiment, the chemical composition of the black dry particles may include: in mass percent, siO 2 ：44.0～48.0％，Al 2 O 3 ：14.0～18.0％，TiO 2 ：0.01～0.5％，CaO：12.0～15.0％，MgO：0.01～0.5％，K 2 O：1.0～2.0％，Na 2 O：2.5～4.5％，ZrO 2 ：4.5～6.5％，ZnO：3.0～5.0％，Fe 2 O 3 ：0.5～1.5％，CoO：1.0～2.0％，MnO：5.5～7.5％，MoO 3 :0.1 to 0.5 percent, loss on ignition: 0.5 to 1.5 percent.
In some technical schemes, the cerium-tin-zinc system crystal glaze rich in color particles comprises the following raw materials: the weight percentage of the cerium tin zinc crystalline glaze is 90-95%, and the weight percentage of one or more colored dry grains is 5-10%. As an example, the cerium-tin-zinc-based crystalline glaze rich in colored particles consists of 90wt% cerium-tin-zinc crystalline glaze and 10wt% colored dry particles.
The composition of the raw materials of the cerium-tin-zinc system crystal glaze rich in the color particles is controlled in the range, so that white crystal flowers can be separated out from the glaze surface and the three-dimensional effect of the color particles can be presented. If the content of the colored dry particles exceeds 10%, more small crystal flowers which are invisible to the naked eyes are precipitated on the glaze surface, so that the glaze layer presents an opaque and opaque state; in addition, the color dry particle content is too high, which can cause the glaze layer to cover the color and texture of the ink-jet pattern, and the artistic effect of combining the ink-jet pattern with crystal flowers and color particles cannot be presented. If the content of the colored dry particles is less than 5%, white crystal flowers with larger sizes can be precipitated on the glaze, but the crystal flowers are overlapped to cover the colors and textures of the ink-jet patterns, and the artistic effect of combining the ink-jet patterns with the crystal flowers and the colored particles can not be fully exhibited.
The cerium tin zinc crystalline glaze and the color dry particles with the formula are not easy to react with each other, and the color dry particles are wrapped in the cerium tin zinc crystalline glaze. Only the area containing the colored dry particles presents the effect of the colored particles, and no crystal flower effect is visible to naked eyes; the regions containing the cerium tin zinc crystalline glaze separate out macroscopic crystal flowers of the cerium tin zinc component.
The following is an exemplary description of a preparation method of the cerium-tin-zinc-based crystal glazing ceramic tile rich in colored particles, which mainly comprises the following steps, with reference to fig. 1.
(1) And pressing the green bricks. The green body of the crystal glaze ceramic tile can be obtained by pressing a ceramic base material which is conventional in the field. The ceramic base material is prepared by adopting a blank formula commonly used in the field.
(2) And (5) drying the green body. Drying the ceramic body obtained in the step (1) at 120-150 ℃ for 50-75 min, and controlling the moisture content of the dried body to be within 0.5wt%.
(3) And (5) spraying surface glaze. And (3) applying overglaze on the surface of the dried green brick in the step (2) in a glaze spraying mode. The overglaze formula commonly used in the art is adopted. As an example, the raw material composition of the overglaze includes: the potassium feldspar comprises the following components in percentage by mass: 35%, albite: 25%, kaolin: 25% of zirconium silicate: 10% of calcined alumina: 5%. The chemical composition of the overglaze comprises: in mass percent, siO 2 ：55.45％、Al 2 O 3 ：25.77％、Fe 2 O 3 ：0.31％、TiO 2 ：0.14％、CaO：0.26％、MgO：0.20％、K 2 O：4.36％、Na 2 O：2.74％、ZrO 2 :6.31%, loss on ignition: 4.22%. The effect of applying the overglaze is to mask the base color and imperfections of the blank and promote the color development of the inkjet pattern.
In some embodiments, the specific gravity of the glaze of the colored overglaze can be controlled to be 1.44 to 1.46, and the glazing amount is 450 to 550g/m 2 . The specific gravity of the overglaze is too high, the uniformity of glaze spraying is poor, and the smoothness of the glaze is poor; the specific gravity of the overglaze is too low, the uniformity of glaze spraying is better, but the introduced moisture content is too high, and the broken brick of the glaze line is easy to generate. The overglaze glazing amount is too high, the effect of covering the blank body is in a supersaturated state, and no obvious gain effect exists; the overglaze is too low in glazing quantity, the effect of covering the base color of the green body is poor, and the color development of ceramic ink is not utilized.
(4) And (3) ink-jet printing the pattern. Spraying the surface of the blank body of the color development overglaze in the step (3), and carrying out ink-jet printing on the design pattern by using a digital ink-jet machine.
(5) Applying cerium tin zinc crystal glaze rich in color particles. And (3) spraying cerium-tin-zinc system crystal glaze rich in color particles on the surface of the blank body after the pattern is printed by the ink jet method in the step (4).
Preparing the glaze slip of the cerium-tin-zinc crystal glaze rich in color particles. Weighing the raw materials according to the raw material composition of the cerium-tin-zinc system crystal glaze rich in the color particles, adding water for ball milling, and sieving to obtain the glaze slip of the cerium-tin-zinc system crystal glaze rich in the color particles. In some embodiments, the ball milling may also be performed with the addition of additives such as suspending agents, binders, and the like. The suspending agent and the binder are suspending agents and binders commonly used for slurry in the ceramic field. The suspending agent and the binder are used in an amount to satisfy the specific gravity and the flow rate required by the final glazing. When the cerium tin zinc crystal glaze is used, the cerium tin zinc crystal glaze can be used in the form of glaze slip, or can be used in the form of dry grains. When the cerium-tin-zinc crystal glaze is used in the form of glaze slip, the cerium-tin-zinc crystal glaze in the raw material composition of the cerium-tin-zinc crystal glaze rich in color particles refers to dry materials. When the cerium tin zinc crystal glaze is used in the form of glaze slurry, water is added into the cerium tin zinc crystal glaze raw material, and then the cerium tin zinc crystal glaze raw material (dry material) is ball-milled in a ball mill: the mass ratio of water may be 75:25, the screen residue of the ball-milled and sieved 325 mesh screen can be 0.3 to 0.5 weight percent.
The method can be used for glazing by adopting a bell jar glazing wet process, and the mode of glazing can lead the fired glaze to show the three-dimensional effect of white crystal flowers and colored particles, and can fully show the three-dimensional effect of stone textures after being combined with ink-jet colors and pattern textures.
The technological parameters of the cerium-tin-zinc system crystal glaze rich in color particles are as follows: the specific gravity is 1.80-1.90, and the glazing quantity is 650-850 g/m 2 Flow rate: 25 to 55S. The specific weight and the flow rate of the cerium-tin-zinc system crystal glaze rich in colored particles can influence the quality of the sintered glaze, and the glazing quantity can obviously influence the crystal pattern effect of the glaze. The specific gravity and the flow rate are too low, and the fluidity of the glaze slurry is too good, so that the glaze curtain for spraying glaze is easy to drift, and the glazing quantity is uneven and unstable; the specific gravity and the flow rate are too high, the fluidity of the glaze slurry is too poor, and the glaze is easy to have egg-shaped lack of glaze in the process of glazing. The glazing quantity is too low, and the crystal flowers formed after firing are smaller and the quantity is small; the glazing quantity is too high, the crystal flowers formed after firing are large and large in quantity, the crystal flowers are easy to be overlapped together, the color and the texture of the ink-jet pattern are covered, and the artistic effect of the combined ink-jet pattern and crystal flowers cannot be fully displayed. The flow rate is measured by a coating-4 flow rate cup.
(6) And (5) sintering. And (3) drying the blank body subjected to the cerium-tin-zinc system crystal glaze rich in the color particles in the step (5) through a glaze line, and then placing the blank body in a roller kiln for quick firing to obtain the cerium-tin-zinc system crystal glaze ceramic tile rich in the color particles. The sintering period can be 60-100 min, and the highest sintering temperature is 1180-1200 ℃. The cerium-tin-zinc system crystal glaze rich in the colored particles can be realized under the existing low-temperature quick firing process condition of the building ceramic, the firing time is not required to be prolonged, and a complex heat preservation system and a cooling system are not required to be formulated. The firing period is too short, and the glaze surface after firing presents small crystal flowers which are invisible to naked eyes and have a large number; the firing period is too long, the crystal flowers formed after firing are larger and more in number and are easy to be overlapped together, the colors and textures of the ink-jet patterns are covered, and the artistic effect of the crystal flowers combined with the ink-jet patterns cannot be fully shown. Meanwhile, the sintering temperature is too high, the crystal flowers are easy to be secondarily melted after sintering, and the crystal flowers are smaller in number; the firing temperature is too low, so that small crystal flowers which are invisible to naked eyes and have a large number are formed by firing, and a good decorative effect cannot be achieved.
(7) And (5) edging and upgrading. Polishing and edging the fired ceramic bricks, and then grading and packaging.
The cerium-tin-zinc system crystal glaze rich in colored particles not only separates out white cerium-tin-zinc system crystal flowers in the firing process, but also is rich in crystal flower-shaped colored particles, the glaze surface presents crystal flower patterns and crystal flower-shaped particles with various colors, the unique artistic decorative effect has great ornamental value, and the cerium-tin-zinc system crystal glaze can be applied to building ceramics as the decorative effect, and improves the grade of ceramic tiles.
The present invention will be described in more detail by way of examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
(1) And pressing the green bricks.
(2) And (5) drying the green body. Drying the ceramic body obtained in the step (1) at 150 ℃ for 60min, and controlling the moisture content of the dried body to be within 0.5wt%.
(3) And (5) spraying a color overglaze. And (3) spraying color overglaze on the surface of the dried green brick in the step (2). Wherein, the raw materials of the color development overglaze comprise: potassium feldspar: 35%, albite: 25%, kaolin: 25% of zirconium silicate: 10% of calcined alumina: 5%. The chemical composition of the chromophoric overglaze comprises: in mass percent, siO 2 ：55.45％、Al 2 O 3 ：25.77％、Fe 2 O 3 ：0.31％、TiO 2 ：0.14％、CaO：0.26％、MgO：0.20％、K 2 O：4.36％、Na 2 O：2.74％、ZrO 2 :6.31%, IL:4.22%. Controlling the specific gravity of the glaze to be 1.44, and applyingThe glaze amount is 550g/m 2 。
(4) And (3) ink-jet printing the pattern.
(5) Preparing the cerium tin zinc crystal glaze rich in color particles. The cerium-tin-zinc system crystal glaze rich in color particles comprises the following raw materials: the mass ratio of the cerium tin zinc crystalline glaze to the red dry particles is 90 percent: 10%. Wherein, the raw materials of the cerium tin zinc crystal glaze comprise: the fluorite comprises the following components in percentage by mass: 7%, kaolin: 5%, fused silica: 20%, zinc oxide: 25%, cerium oxide: 2%, tin dioxide: 2%, low temperature transparent frit: 10%, high sodium frit: 29%. The chemical composition of the cerium tin zinc crystal glaze comprises: in mass percent, siO 2 ：47.84％，Al 2 O 3 ：7.39％，Fe 2 O 3 ：0.40％，TiO 2 ：0.03％，CaO：5.20％，MgO：1.57％，K 2 O：1.14％，Na 2 O：4.04％，ZnO：25.42％，F：2.17％，CeO 2 ：1.96％，SnO 2 :1.98%, loss on ignition: 0.8%.
(6) And (3) spraying cerium-tin-zinc system crystal glaze rich in color particles on the surface of the blank body after the pattern is printed by the ink jet method in the step (4). Glazing by adopting a bell jar glazing mode, wherein the glazing technological parameters of the cerium-tin-zinc series crystalline glaze rich in color particles are as follows: specific gravity 1.85, glazing amount 750g/m 2 。
(7) And (5) sintering. And (3) drying the blank body subjected to the cerium-tin-zinc system crystal glaze rich in the color particles in the step (6) through a glaze line, and then placing the blank body in a roller kiln for quick firing to obtain the cerium-tin-zinc system crystal glaze ceramic tile rich in the color particles. The firing period was 60 minutes and the maximum firing temperature was 1200 ℃.
(8) And (5) edging and upgrading. And polishing and edging the baked ceramic bricks, and then grading and packaging.
Comparative example 1
(1) And pressing the green bricks.
(2) And (5) drying the green body. Drying the ceramic body obtained in the step (1) at 150 ℃ for 60min, and controlling the moisture content of the dried body to be within 0.5wt%.
(3) And (5) spraying a color overglaze. And (3) spraying color overglaze on the surface of the dried green brick in the step (2). Wherein,the raw materials of the chromophoric overglaze comprise: potassium feldspar: 35%, albite: 25%, kaolin: 25% of zirconium silicate: 10% of calcined alumina: 5%. The chemical composition of the chromophoric overglaze comprises: in mass percent, siO 2 ：55.45％、Al 2 O 3 ：25.77％、Fe 2 O 3 ：0.31％、TiO 2 ：0.14％、CaO：0.26％、MgO：0.20％、K 2 O：4.36％、Na 2 O：2.74％、ZrO 2 :6.31%, IL:4.22%. The specific gravity of the glaze is controlled to be 1.44, and the glazing quantity is 550g/m 2 。
(4) And (3) ink-jet printing the pattern.
(5) Preparing the cerium-tin-free zinc-based crystalline glaze rich in colored particles. The zinc-based crystalline glaze material rich in colored particles and free of cerium and tin comprises the following components: the mass ratio of the cerium-tin-free zinc-based crystalline glaze to the red dry particles is 90 percent: 10%. Wherein, the zinc system crystal glaze raw material composition without cerium tin comprises: the fluorite comprises the following components in percentage by mass: 7%, kaolin: 5%, fused silica: 22%, zinc oxide: 27%, low temperature transparent frit: 10%, high sodium frit: 29%. The chemical composition of the zinc-based zinc crystalline glaze without cerium tin comprises the following components: in mass percent, siO 2 ：49.78％，Al 2 O 3 ：7.39％，Fe 2 O 3 ：0.40％，TiO 2 ：0.03％，CaO：5.20％，MgO：1.57％，K 2 O：1.14％，Na 2 O:4.04%, znO:27.38%, F:2.17%, loss on burning: 0.90%.
(6) And (3) spraying cerium-tin-free zinc-based crystalline glaze rich in color particles on the surface of the blank body after the pattern is printed by the ink jet method in the step (4). Glazing by adopting a bell jar glazing mode, wherein the glazing process parameters of the zinc-based crystalline glaze rich in the color particles and containing no cerium and tin are as follows: specific gravity 1.85, glazing amount 750g/m 2 。
(7) And (5) sintering. And (3) drying the blank body after the cerium-tin-free zinc-based crystal glaze rich in the colored particles is applied in the step (6) through a glaze line, and then placing the blank body in a roller kiln for quick firing to obtain the cerium-tin-free zinc-based crystal glaze ceramic tile rich in the colored particles. The firing period was 60 minutes and the maximum firing temperature was 1200 ℃.
(8) And (5) edging and upgrading. And polishing and edging the baked ceramic bricks, and then grading and packaging.
The ceramic tile prepared in the comparative example 1 has only colored particles, the areas of the non-colored particles have a glass transparent non-crystal effect, and the polished ceramic tile has more pinholes and pores in the areas of the non-colored particles and has poor antifouling performance.
Comparative example 2
(1) And pressing the green bricks.
(2) And (5) drying the green body. Drying the ceramic body obtained in the step (1) at 150 ℃ for 60min, and controlling the moisture content of the dried body to be within 0.5wt%.
(3) And (5) spraying a color overglaze. And (3) spraying color overglaze on the surface of the dried green brick in the step (2). Wherein, the raw materials of the color development overglaze comprise: potassium feldspar: 35%, albite: 25%, kaolin: 25% of zirconium silicate: 10% of calcined alumina: 5%. The chemical composition of the chromophoric overglaze comprises: in mass percent, siO 2 ：55.45％、Al 2 O 3 ：25.77％、Fe 2 O 3 ：0.31％、TiO 2 ：0.14％、CaO：0.26％、MgO：0.20％、K 2 O：4.36％、Na 2 O：2.74％、ZrO 2 :6.31%, IL:4.22%. The specific gravity of the glaze is controlled to be 1.44, and the glazing quantity is 550g/m 2 。
(4) And (3) ink-jet printing the pattern.
(5) Preparing the cerium tin zinc crystal glaze rich in color particles. The cerium-tin-zinc system crystal glaze rich in color particles comprises the following raw materials: cerium tin zinc crystal glaze and red dry particles, wherein the mass ratio of the cerium tin zinc crystal glaze to the red dry particles is 80 percent: 20%. Wherein, the raw materials of the cerium tin zinc crystal glaze comprise: the fluorite comprises the following components in percentage by mass: 7%, kaolin: 5%, fused silica: 20%, zinc oxide: 25%, cerium oxide: 2%, tin dioxide: 2%, low temperature transparent frit: 10%, high sodium frit: 29%. The chemical composition of the cerium tin zinc crystal glaze comprises: in mass percent, siO 2 ：47.84％，Al 2 O 3 ：7.39％，Fe 2 O 3 ：0.40％，TiO 2 ：0.03％，CaO：5.20％，MgO：1.57％，K 2 O：1.14％，Na 2 O：4.04％，ZnO：25.42％，F：2.17％，CeO 2 ：1.96％，SnO 2 :1.98%, loss on ignition: 0.8%.
(6) And (3) spraying cerium-tin-zinc system crystal glaze rich in color particles on the surface of the blank body after the pattern is printed by the ink jet method in the step (4). Glazing by adopting a bell jar glazing mode, wherein the glazing technological parameters of the cerium-tin-zinc series crystalline glaze rich in color particles are as follows: specific gravity 1.85, glazing amount 750g/m 2 。
(7) And (5) sintering. And (3) drying the blank body subjected to the cerium-tin-zinc system crystal glaze rich in the color particles in the step (6) through a glaze line, and then placing the blank body in a roller kiln for quick firing to obtain the cerium-tin-zinc system crystal glaze ceramic tile rich in the color particles. The firing period was 60 minutes and the maximum firing temperature was 1200 ℃.
(8) And (5) edging and upgrading. And polishing and edging the baked ceramic bricks, and then grading and packaging.
The ceramic tile prepared in comparative example 2 has a large number of colored particles on the polished glaze, the glaze is in a discontinuous flaky colored glaze layer area, and simultaneously, the area without the colored particles has a large number of white small crystal flowers which are invisible to naked eyes, so that the glaze layer is in an opaque state. Furthermore, the discontinuous sheet-like colored glaze areas and opaque glaze areas mask the color and texture of the inkjet pattern.
Comparative example 3
(1) And pressing the green bricks.
(2) And (5) drying the green body. Drying the ceramic body obtained in the step (1) at 150 ℃ for 60min, and controlling the moisture content of the dried body to be within 0.5wt%.
(3) And (5) spraying a color overglaze. And (3) spraying color overglaze on the surface of the dried green brick in the step (2). Wherein, the raw materials of the color development overglaze comprise: potassium feldspar: 35%, albite: 25%, kaolin: 25% of zirconium silicate: 10% of calcined alumina: 5%. The chemical composition of the chromophoric overglaze comprises: in mass percent, siO 2 ：55.45％、Al 2 O 3 ：25.77％、Fe 2 O 3 ：0.31％、TiO 2 ：0.14％、CaO：0.26％、MgO：0.20％、K 2 O：4.36％、Na 2 O：2.74％、ZrO 2 :6.31%, IL:4.22%. The specific gravity of the glaze is controlled to be 1.44, and the glazing quantity is 550g/m 2 。
(4) And (3) ink-jet printing the pattern.
(5) Preparing the cerium tin zinc crystal glaze rich in color particles. The cerium-tin-zinc system crystal glaze rich in color particles comprises the following raw materials: the mass ratio of the cerium tin zinc crystalline glaze to the red dry particles is 90 percent: 10%. Wherein, the raw materials of the cerium tin zinc crystal glaze comprise: the fluorite comprises the following components in percentage by mass: 7%, kaolin: 5%, fused silica: 20%, zinc oxide: 25%, cerium oxide: 2%, tin dioxide: 2%, low temperature transparent frit: 10%, high sodium frit: 29%. The chemical composition of the cerium tin zinc crystal glaze comprises: in mass percent, siO 2 ：47.84％，Al 2 O 3 ：7.39％，Fe 2 O 3 ：0.40％，TiO 2 ：0.03％，CaO：5.20％，MgO：1.57％，K 2 O：1.14％，Na 2 O：4.04％，ZnO：25.42％，F：2.17％，CeO 2 ：1.96％，SnO 2 :1.98%, loss on ignition: 0.8%.
(6) And (3) spraying cerium-tin-zinc system crystal glaze rich in color particles on the surface of the blank body after the pattern is printed by the ink jet method in the step (4). Glazing by adopting a bell jar glazing mode, wherein the glazing technological parameters of the cerium-tin-zinc series crystalline glaze rich in color particles are as follows: specific gravity 1.85, glazing amount 750g/m 2 。
(7) And (5) sintering. And (3) drying the blank body subjected to the cerium-tin-zinc system crystal glaze rich in the color particles in the step (6) through a glaze line, and then placing the blank body in a roller kiln for quick firing to obtain the cerium-tin-zinc system crystal glaze ceramic tile rich in the color particles. The firing period was 35min and the maximum firing temperature was 1200 ℃.
(8) And (5) edging and upgrading. And polishing and edging the baked ceramic bricks, and then grading and packaging.
The ceramic tile prepared in comparative example 3 had colored particles in the polished glaze, while the areas where there were a large number of white small crystal flowers that were invisible to the naked eye, and the glaze appeared opaque and opaque, covering the color and texture of the inkjet pattern.
Claims (10)
1. The cerium-tin-zinc system crystal glaze rich in colored particles is characterized by comprising the following raw materials in percentage by weight: 90-95% of cerium tin zinc crystalline glaze and 5-10% of one or more colored dry particles; wherein the chemical composition of the cerium tin zinc crystal glaze comprises: in mass percent, siO 2 ：46～50%、Al 2 O 3 ：6～9%、CaO：4.0～6.0%、MgO：1.0～2.0%、K 2 O：0.5～1.5%、Na 2 O：4.0～6.0%、ZnO：23～27%、F：1.5～3.5%、CeO 2 ：0.5～3.5%、SnO 2 ：0.5～3.5%；
The specific gravity of the cerium-tin-zinc system crystal glaze rich in the color particles is 1.80-1.90, and the glazing quantity is 650-850 g/m 2 The flow rate is 25-55S;
the highest firing temperature of the cerium-tin-zinc series crystal glaze rich in the color particles is 1180-1200 ℃, and the firing period is 60-100 min.
2. The color particle-rich cerium-tin-zinc-based crystalline glaze according to claim 1, wherein the raw material composition of the cerium-tin-zinc crystalline glaze comprises: the fluorite comprises the following components in percentage by mass: 6-8% of kaolin: 4-6%, fused quartz: 17-23%, zinc oxide: 23-27%, cerium oxide: 0.5 to 3.5 percent, tin dioxide: 0.5 to 3.5 percent.
3. The color particle-rich cerium-tin-zinc-based crystalline glaze according to claim 2, wherein the raw material composition of the cerium-tin-zinc crystalline glaze further comprises: the frit A comprises the following components in percentage by mass: 7-13%; the frit A is a low-temperature transparent frit, and comprises the following chemical components: in mass percent, siO 2 ：65.0～69.0%、Al 2 O 3 ：3.0～5.0%、CaO：14.0～16.0%、MgO：1.0～3.0%、K 2 O and/or Na 2 O：3.0～5.0%、ZnO：7.0～9.0%。
4. The color-rich pellet of claim 2The grain cerium tin zinc system crystal glaze is characterized by further comprising the following raw materials in percentage by weight: the frit B comprises the following components in percentage by mass: 24-34%; the frit B is a high-sodium frit, and comprises the following chemical components: in mass percent, siO 2 ：59.0～63.0%、Al 2 O 3 ：14.5～16.5%、MgO：4.0～6.0%、K 2 O：1.5～2.5%、Na 2 O：12.5～14.5%。
5. The cerium-tin-zinc-based crystalline glaze enriched in colored particles according to claim 1, wherein the colored dry particles comprise at least one of red dry particles, blue dry particles, black dry particles.
6. The color particle-rich cerium tin zinc based crystalline glaze according to claim 5, wherein the chemical composition of the red dry particles comprises: in mass percent, siO 2 ：46～50%，Al 2 O 3 ：14～18%，CaO：3.0～5.0%，MgO：0.5～1.5%，K 2 O：2.5～4.5%，Na 2 O：2.5～4.5%，ZrO 2 ：8.0～12.0%，ZnO：5.0～8.0%，SrO：3.0～5.0%，CdO：0.5～1.0%，SeO 2 :0.1 to 0.6 percent, loss on ignition: 0.5 to 1.5 percent.
7. The color particle-rich cerium tin zinc based crystalline glaze according to claim 5, wherein the chemical composition of the blue dry particles comprises: in mass percent, siO 2 ：55～60%，Al 2 O 3 ：7.0～10.0%，CaO：20.0～24.0%，MgO：0.01～0.5%，K 2 O：0.5～1.5%，Na 2 O：3.5～4.5%，Fe 2 O 3 :0.5 to 1.5 percent of MnO:2.0 to 3.0 percent, coO:0.01 to 0.5 percent, loss on ignition: 0.5 to 1.5 percent.
8. The color particle-rich cerium tin zinc-based crystalline glaze according to claim 5, wherein the chemical composition of the black dry particles comprises: in mass percent, siO 2 ：44.0～48.0%，Al 2 O 3 ：14.0～18.0%，TiO 2 ：0.01～0.5%，CaO：12.0～15.0%，MgO：0.01～0.5%，K 2 O：1.0～2.0%，Na 2 O：2.5～4.5%，ZrO 2 ：4.5～6.5%，ZnO：3.0～5.0%，Fe 2 O 3 ：0.5～1.5%，CoO：1.0～2.0%，MnO：5.5～7.5%，MoO 3 :0.1 to 0.5 percent, loss on ignition: 0.5 to 1.5 percent.
9. The cerium-tin-zinc system crystal glaze ceramic tile rich in colored particles is characterized by sequentially comprising a crystal glaze layer formed by the cerium-tin-zinc system crystal glaze rich in colored particles, an inkjet pattern layer, an overglaze layer and a blank layer from top to bottom.
10. A preparation method of a cerium-tin-zinc system crystal glaze ceramic tile rich in colored particles, which is characterized by comprising the following steps:
applying surface glaze on the surface of the green brick; the overglaze is a chromophoric overglaze; the overglaze is sprayed; the specific gravity of the overglaze is 1.44-1.46, and the glazing quantity is 450-550 g/m 2 ；
Ink-jet printing a design pattern on the surface of the green brick after the surface glaze is applied;
applying the cerium-tin-zinc crystal glaze rich in color particles as set forth in claim 1 on the surface of the green brick after the design pattern is printed by ink-jet printing; the application mode of the cerium-tin-zinc system crystal glaze rich in the color particles is glaze spraying;
sintering the green bricks after the cerium-tin-zinc system crystal glaze rich in color particles is applied;
polishing the ceramic tile after firing to obtain the cerium-tin-zinc series crystal glaze ceramic tile rich in colored particles.
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