CN103044082A - Luminescent glaze for enamel painted porcelain and preparation method and application thereof - Google Patents
Luminescent glaze for enamel painted porcelain and preparation method and application thereof Download PDFInfo
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- CN103044082A CN103044082A CN2012105663346A CN201210566334A CN103044082A CN 103044082 A CN103044082 A CN 103044082A CN 2012105663346 A CN2012105663346 A CN 2012105663346A CN 201210566334 A CN201210566334 A CN 201210566334A CN 103044082 A CN103044082 A CN 103044082A
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- glaze
- luminescent
- luminescent material
- enamel
- enamel ceramics
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Links
- 210000003298 dental enamel Anatomy 0.000 title claims abstract description 143
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 136
- 230000004907 flux Effects 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 239000000919 ceramic Substances 0.000 claims description 132
- 239000000843 powder Substances 0.000 claims description 54
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 38
- 239000006063 cullet Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011787 zinc oxide Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 13
- 238000005034 decoration Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 10
- 239000010436 fluorite Substances 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 229910052727 yttrium Inorganic materials 0.000 claims description 10
- 229910021538 borax Inorganic materials 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- 239000010433 feldspar Substances 0.000 claims description 9
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004328 sodium tetraborate Substances 0.000 claims description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 9
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 9
- 239000000454 talc Substances 0.000 claims description 9
- 235000012222 talc Nutrition 0.000 claims description 9
- 229910052623 talc Inorganic materials 0.000 claims description 9
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 7
- 229910003668 SrAl Inorganic materials 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 229960001866 silicon dioxide Drugs 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 5
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910015999 BaAl Inorganic materials 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 238000003701 mechanical milling Methods 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910004481 Ta2O3 Inorganic materials 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 210000000988 bone and bone Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- -1 phosphorus compound Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Inorganic materials [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000000037 vitreous enamel Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
The invention discloses luminescent glaze for enamel painted porcelain and a preparation method and application thereof. The luminescent glaze for enamel painted porcelain comprises basic glaze for the enamel painted porcelain and a protective-glaze luminescent material, wherein the protective-glaze luminescent material is prepared by firstly mixing and then repeatedly braking the flux for the protective-glaze luminescent material and a luminescent material, and the flux for the protective-glaze luminescent material comprises the following components in percentage by weight: 42-48 percent of SiO2, 3-7 percent of SrO, 15-21 percent of B2O3, 0.2-1.2 percent of Al2O3, 3-7 percent of Li2O, 2-7 percent of Na2O, 1-3 percent of K2O, 0.6-3.8 percent of metal fluoride, 2-3.5 percent of P2O5, 0-0.5 percent of Ta2O3, 0-1 percent of Nb2O5, 0-0.5 percent of ZrO2, 0-3 percent of CeO2, 0-0.5 percent of La2O3, 0-2 percent of Y2O3, 5-10 percent of ZnO, and 0-5 percent of MgO. According to the luminescent glaze for the enamel painted porcelain provided by the invention, the thermal stability and luminescence properties of the luminescent material can be guaranteed so as to improve the luminance and luminous time of the prepared painted porcelain after irradiation, while the various characteristics of the traditional enamel painted porcelain can be maintained.
Description
Technical field
The present invention relates to a kind of enamel ceramics with luminescent glaze and glaze slip preparation method and application thereof, belong to technical field of ceramic material.
Background technology
At present, long history is arranged, be called as the enamel ceramics of " faience queen ", " government porcelain kiln in the government porcelain kiln ", come from the romantic kingdom of fashion France, come from artistic old and well-known family Luo Dan family, the faience technique of a kind of uniqueness that is Kangxu in the imperial palace.It is affected and a kind of porcelain over-glaze decoration decorative technique of new wound by the copper painted enamel of European import, to be developed by cloisonne, cloisonne is to form at copper tire enamelling glaze, and enamel ceramics is then to fire at porcelain body enamelling glaze to form, so enamel ceramics claims again " enamel painting on porcelain ", although colour enamels has the characteristics such as porcelain is fine and smooth, color material is dignified, lovely luster is beautiful, the painter is exquisite, it is the elaboration of high production technique in the art pottery, but fabrication techniques luminescent porcelain enamel faience artwork has certain difficulty at present; The also oxidation of luminescent material in ceramic glaze uses of the unstable that luminescent material has when high temperature, decompose and make it lose luminescent properties with glaze composition generation chemical reaction etc.
Summary of the invention
Technical problem to be solved by this invention is the defective that overcomes prior art, a kind of enamel ceramics luminescent glaze is provided, it can guarantee that thereby the thermostability of luminescent material and the characteristics of luminescence improve luminosity and the fluorescent lifetime of faience after illumination of making, and can keep again the various features of traditional enamel ceramics.
The present invention solves the problems of the technologies described above the technical scheme of taking: a kind of enamel ceramics luminescent glaze, comprise enamel ceramics basis glaze and luminescent material protection glaze, resintering made after luminescent material protection glaze was mixed with flux and luminescent material by luminescent material protection glaze, it is characterized in that, component and the weight percent of described enamel ceramics basis glaze are as follows: quartzy 20% ~ 40%, lithionite 10% ~ 20%, feldspar 5% ~ 10%, talcum 2% ~ 3%, borax 10% ~ 25%, boric acid 6% ~ 12%, Strontium carbonate powder 3% ~ 10%, zinc oxide 1% ~ 3%, zirconium silicate 0 ~ 3%, cerium oxide 0.1% ~ 3%, aluminium sesquioxide 0.5% ~ 3%, fluorite 0 ~ 5%; Described luminescent material protection glaze is as follows with component and the weight percent of flux: SiO
2: 42% ~ 48%, SrO:3% ~ 7%, B
2O
3: 15% ~ 21%, Al
2O
3: 0.2% ~ 1.2%, Li
2O:3% ~ 7%, Na
2O:2% ~ 7%, K
2O:1% ~ 3%, metal fluoride: 0.6%～3.8%, P
2O
5: 2% ~ 3.5%, Ta
2O
3: 0 ~ 0.5%, Nb
2O
5: 0～1%, ZrO
2: 0～0.5%, CeO
2: 0～3%, La
2O
3: 0～0.5%, Y
2O
3: 0 ~ 2%, ZnO:5% ~ 10%, MgO:0 ~ 0.5%; Described luminescent material is alkali earth metal aluminate or alkaline earth sulfide.
Further, component and the weight percent of the basic glaze of described enamel ceramics are as follows: quartz 28% ~ 35%, lithionite 15% ~ 18%, feldspar 6% ~ 8%, talcum 2.2% ~ 2.5%, borax 15% ~ 21%, boric acid 8% ~ 10%, Strontium carbonate powder 5% ~ 8%, zinc oxide 1.8% ~ 2.2%, zirconium silicate 0.5 ~ 1.5%, cerium oxide 0.8% ~ 2.6%, aluminium sesquioxide 1.5% ~ 2%, fluorite 2.5 ~ 4%; Described luminescent material protection glaze is as follows with component and the weight percent of flux: SiO
2: 43%～46%, SrO:3.6 ~ 6.2%, B
2O
3: 16%～20%, Al
2O
3: 0.4%～0.8%, Li
2O:4%～6%, Na
2O:3%～5%, K
2O:2%～3%, metal fluoride: 0.9%～2.8%, P
2O
5: 2%～3%, Ta
2O
3: 0.2% ~ 0.5%, Nb
2O
5: 0.6%～1%, ZrO
2: 0.2% ~ 0.5%, CeO
2: 1.2%～2.2%, La
2O
3: 0.2% ~ 0.5%, Y
2O
3: 0.6%～1.5%, ZnO:6% ~ 9%, MgO:0.3%～0.5%.
Further, the weight part ratio of described enamel ceramics basis glaze and luminescent material protection glaze is 1: 1～4; Luminescent material protection glaze is that 2: 1～5 ratio mix afterwards high temperature resintering make with flux and luminescent material according to weight ratio by luminescent material protection glaze, and wherein, the resintering temperature is 700 ° of C ~ 900 ° C, high-temperature holding time 30～150 minutes.
Further, the weight ratio of described enamel ceramics basis glaze and luminescent material protection glaze is 1: 2～3; Described luminescent material protection glaze is 2: 2 ~ 3 with the part by weight of flux and luminescent material.
Further, described metal fluoride is LiF, SrF
2, MgF
2, CaF
2, BaF
2, among the NaF one or more.
Further, described luminescent material is SrAl
2O
6, CaAl
2O
6, BaAl
2O
6, among ZnS, CaS, the CdS one or more.
Further, the enamel ceramics 100% also adds 0.5% ~ 4% additive in luminescent glaze, and described additive is aerosil or ultra-fine precipitates silicon-dioxide or white carbon black or silicon sol.The effect of additive is that enamel ceramics is carried out modification with the luminescent glaze glaze slip, plays the effect of glaze slip dispersion agent, stablizer and thixotropic agent.
The present invention also provides the glaze slip preparation technology of a kind of enamel ceramics with luminescent glaze, and the step of this technique is as follows:
A: the preparation of enamel ceramics basis glaze
(1) gets the quartz 20% ~ 40% that 325 orders or thinner mesh screen sieve, lithionite 10% ~ 20%, feldspar 5% ~ 10%, talcum 2% ~ 3%, borax 10% ~ 25%, boric acid 6% ~ 12%, Strontium carbonate powder 3% ~ 10%, zinc oxide 1% ~ 3%, zirconium silicate 0 ~ 3%, cerium oxide 0.1% ~ 3%, aluminium sesquioxide 0.5% ~ 3%, fluorite 0 ~ 5%;
(2) above-mentioned raw materials is mixed by prescription batching after, ° C fusing 1250 ° of C ~ 1380 is put into the cold water shrend and is made enamel ceramics basis cullet of glaze;
(3) enamel ceramics basis cullet of glaze is packed in the ball mill, add water and the high alumina ballstone grinds to form glaze slip, then through 80 ~ 100 ° of C oven dry, and make powder, cross 250 orders or thinner mesh screen and obtain enamel ceramics basis glaze; Wherein, the weight ratio of water, high aluminium ball, enamel ceramics basis cullet of glaze is 0.35: 1: 1, and it is remaining less than 0.03% that fineness is controlled at 10000-hole sieve;
B: the preparation of luminescent material protection glaze
(1) luminescent material protection glaze is with the preparation of flux: each material of getting 325 orders or thinner mesh screen consists of the composition of its glaze: SiO
2: 42% ~ 48%, SrO:3% ~ 7%, B
2O
3: 15% ~ 21%, Al
2O
3: 0.2% ~ 1.2%, Li
2O:3% ~ 7%, Na
2O:2% ~ 7%, K
2O:1% ~ 3%, metal fluoride: 0.6%～3.8%, P
2O
5: 2% ~ 3.5%, Ta
2O
3: 0 ~ 0.5%, Nb
2O
5: 0～1%, ZrO
2: 0～0.5%, CeO
2: 0～3%, La
2O
3: 0～0.5%, Y
2O
3: 0 ~ 2%, ZnO:5% ~ 10%, MgO:0 ~ 0.5%; After above-mentioned raw materials mixed, again 1220 ℃～1360 ℃ high temperature melting, through the cold water shrend, make luminescent material protection cullet of glaze after the oven dry; Protect cullet of glaze to pack in the ball mill luminescent material, add alcohol and the high alumina ballstone grinds to form glaze slip, drying then, and make powder, cross 250 orders or thinner mesh screen and obtain luminescent material protection glaze flux; Wherein, the weight ratio of alcohol, high aluminium ball and luminescent material protection cullet of glaze is 0.30: 1: 1; It is remaining less than 0.03% that fineness is controlled at 10000-hole sieve;
(2) luminescent material being protected glaze is after 2: 2 ~ 3 ratios mix with flux powder and luminescent material powder according to weight ratio, pack into and send in pushed bat kiln or the roller kiln in the little saggar, the high temperature resintering is 30～150 minutes under ° C temperature of 700 ° of C ~ 900, pack into after the material coarse crushing with resintering in the ball mill, add alcohol and the high alumina ballstone grinds to form glaze slip, then dry through 80 ~ 100 ° of C, and make powder, cross 160 orders～200 purpose mesh screens and obtain luminescent material protection glaze; In the mechanical milling process, the weight ratio of the material that alcohol, high aluminium ball and resintering are crossed is 0.30: 1: 1;
C: enamel ceramics prepares with the glaze slip of luminescent glaze
It is to make enamel ceramics luminescent glaze powder mixture after 1: 2 ~ 3 ratio is mixed according to weight ratio that A process the enamel ceramics basis glaze powder of making and the luminescent material that the B process is made are protected the glaze powder; be that 1: 2.2 ~ 2.6 ratio is mixed with powder mixture and water according to weight ratio; adding proportion is that charging basket that the additive of powder mixture weight 0.5% ~ 4% is put into homogenizer together fully mixes and stirs evenly again, obtains enamel ceramics with the glaze slip of luminescent glaze.
Further, described metal fluoride is LiF, SrF
2, MgF
2, CaF
2, BaF
2, NaF
In one or more.
Further, described luminescent material is SrAl
2O
6, CaAl
2O
6, BaAl
2O
6, among ZnS, CaS, the CdS one or more.
Further, described additive is aerosil or ultra-fine precipitates silicon-dioxide or white carbon black or silicon sol.
The present invention also provides the application of a kind of enamel ceramics with luminescent glaze, and this enamel ceramics is applied to the enamel colored drawing of pottery with luminescent glaze.
Further, described pottery is hard-paste or soft porcelain or Shi porcelain or fine pottery, for example various white clouds porcelain or white clouds soil porcelain or various china or bone china or imitative china or various Shi porcelain or fine pottery; Described colour enamels is depicted as the over-glaze decoration of 760 °～850 ° of C or the in-glaze decoration of 900 °～1050 ° of C is painted.
After having adopted technique scheme, enamel ceramics of the present invention substitutes fluorite and adds P with having introduced the oxide compounds such as phosphorus compound and cerium, lanthanum, yttrium, zirconium in the luminescent glaze
2O
5, ZnO, Ta
2O
3And Nb
2O
3Etc. component composition Partial Replacement PbO, Na
2O and K
2The components such as O, thus CaF, PbO, Na in the high temperature faience process reduced
2O and K
2The components such as O are to the infringement of luminescent material performance, solve the thermostability difficult problem of luminescent material in ceramic glaze, not only protected the luminescent properties after the high temperature grilling of luminescent material but also guaranteed milkiness performance, melting behaviour, acid-proof alkaline, faience grilling sticking power and the glaze surface brightness of traditional enamel ceramics glaze; Namely prepare respectively two kinds of glaze by two clincker process---luminescent material decomposition when enamel ceramics basis glaze and luminescent material protection glaze prevent the enamel ceramics high-temperature firing, oxidation or with glaze in other composition generation chemical reactions, the viscosity of raising enamel ceramics under the high temperature of luminescent glaze, guarantee that enamel ceramics can not lose luminescent properties with the luminescent material in the luminescent glaze, thereby improve enamel ceramics with use range, application of temperature and the luminous efficiency of luminescent glaze, finally effectively solve the high-temperature stability difficult problem of luminescent material when enamel ceramics is used; Pottery after various glaze firing is drawn the enamel ceramics luminescent glaze, then burn till through 760 ℃～1050 ℃ high temperature grillings, pattern through high temperature grilling enamel ceramics luminescent glaze firmly is fixed on the surface of high-temperature enamel, what the various characteristics of its illumination effect and enamel ceramics was desirable presents, existing desirable luminous lightness and the stable and lasting luminous various features that kept traditional enamel ceramics are through sustainable more than luminous ten hours after the illumination; The enamel ceramics product of firing by the glaze slip of technique manufacturing of the present invention, have luminous bright, stable, longer duration, the characteristics such as the characteristics of luminescence can keep for a long time, simultaneously the enamel ceramics luminescent glaze has suitable glaze high temperature viscosity, thermal expansivity, refractive index, glaze milkiness characteristic, and the ceramic glaze surface after can burning till with high temperature firmly combines, do not ftracture, not orange peel glaze, do not come off, gloss is bright.Existing desirable luminous lightness and the stable and lasting luminous various features that kept traditional enamel ceramics are through sustainable more than luminous ten hours after the illumination; The embossment sense of the enamel ceramics that the enamel ceramics luminescent glaze that adopts the present invention to make is produced is strong, and glaze is in conjunction with firmly, and wear resistance is good, and luminescent properties can keep 10 years even more than a century.
Embodiment
Content of the present invention is easier to be expressly understood in order to make, and the below is according to specific embodiment, and the present invention is further detailed explanation,
Embodiment one
A kind of enamel ceramics luminescent glaze comprises enamel ceramics basis glaze and luminescent material protection glaze, and resintering made after luminescent material protection glaze was mixed with flux and luminescent material by luminescent material protection glaze;
Component and the weight percent of enamel ceramics basis glaze are as follows: quartz 28%, lithionite 18%, feldspar 7.5%, talcum 2.5%, borax 19%, boric acid 8.5%, Strontium carbonate powder 7%, zinc oxide 2%, zirconium silicate 1.5%, cerium oxide 2.2%, aluminium sesquioxide 0.8%, fluorite 3%; Luminescent material protection glaze is grouped into (weight percent Wt%) with each one-tenth of flux: SiO
2: 46%, SrO:3.8%, B
2O
3: 20%, Al
2O
3: 0.5%, Li
2O:6.2%, Na
2O:3.9%, K
2O:2.5%, metal fluoride: 2.2%, P
2O
5: 2.5%, Nb
2O
5: 0.4%, ZrO
2: 0.3%, CeO
2: 2.2%, Y
2O
3: 0.8%, ZnO:8.5%, MgO:0.2%;
Luminescent material is 50%ZnS and 50%CdS;
Metal fluoride can be LiF, SrF
2, MgF
2, CaF
2, BaF
2, one or more mixtures among the NaF.
Enamel ceramics prepares with the glaze slip of luminescent glaze:
A: the preparation of enamel ceramics basis glaze
(1) got the above-mentioned each component of the enamel ceramics basis glaze of 325 orders or thinner mesh screen;
(2) above-mentioned raw materials is mixed after, again 1300 ° of C ~ 1350 ° C fusing is put into the cold water shrend and is made enamel ceramics basis cullet of glaze;
(3) enamel ceramics basis cullet of glaze is packed in the ball mill, add water and the high alumina ballstone grinds to form glaze slip, then through 80 ~ 100 ° of C oven dry, and make powder, cross 250 orders or thinner mesh screen and obtain enamel ceramics basis glaze; Wherein, the weight ratio of water, high aluminium ball, enamel ceramics basis cullet of glaze is 0.35: 1: 1, and it is remaining less than 0.03% that fineness is controlled at 10000-hole sieve;
B: the preparation of luminescent material protection glaze
(1) luminescent material protection glaze is with the preparation of flux: the raw material of getting the each component of the above-mentioned luminescent material protection glaze usefulness flux that 325 orders or thinner mesh screen sieve; After above-mentioned raw materials mixed, 1280 ℃～1320 ℃ high temperature melting, through the cold water shrend, make luminescent material protection cullet of glaze after the oven dry; Protect cullet of glaze to pack in the ball mill luminescent material, add alcohol and the high alumina ballstone grinds to form glaze slip, drying then, and make powder, cross 250 orders or thinner mesh screen and obtain luminescent material protection glaze flux; Wherein, the weight ratio of alcohol, high aluminium ball and luminescent material protection cullet of glaze is 0.30: 1: 1; It is remaining less than 0.03% that fineness is controlled at 10000-hole sieve;
(2) luminescent material being protected glaze is after 2: 2 ratios mix with flux and luminescent material (zinc sulphide and Cadmium Sulfide) according to weight ratio, pack into and under ° C temperature of 760 ° of C ~ 790, send in pushed bat kiln or the roller kiln resintering in the little saggar about 1 hour, pack into after the material coarse crushing with resintering in the ball mill, add alcohol and the high alumina ballstone grinds to form glaze slip, then through 80 ~ 100 ° of C oven dry, and make powder, cross 200 order mesh screens and obtain luminescent material protection glaze; Wherein, the weight ratio of the material crossed of alcohol, high aluminium ball and resintering is 0.30: 1: 1;
C: the enamel ceramics preparation of luminescent glaze
It is to make enamel ceramics luminescent glaze powder mixture after 1: 2 ratio is mixed according to weight ratio that A process the enamel ceramics basis glaze powder of making and the luminescent material that the B process is made are protected the glaze powder; be that 1: 2.4 ratio is mixed with powder mixture and water according to weight ratio, adding proportion is that charging basket that the ultra-fine precipitates silicon-dioxide of powder mixture 2% is put into homogenizer together fully mixes to stir evenly and makes good dispersion and stable glaze slip again.
Namely can be applicable to be applied to the enamel ceramics over-glaze decoration of 760 °～850 ° of C in the painted decoration of ceramic surface enamel through A, B, three prepared glaze slips of technological process of C.
Embodiment two
A kind of enamel ceramics luminescent glaze; comprise enamel ceramics basis glaze and luminescent material protection glaze; resintering made after luminescent material protection glaze was mixed with flux and luminescent material by luminescent material protection glaze, and component and the weight percent of enamel ceramics basis glaze are as follows:
Component and the weight percent of enamel ceramics basis glaze are as follows: quartz 29%, lithionite 17%, feldspar 8.5%, talcum 2.0%, borax 18%, boric acid 9.4%, Strontium carbonate powder 7.5%, zinc oxide 2%, zirconium silicate 1.3%, cerium oxide 2.5%, aluminium sesquioxide 0.6%, fluorite 2.2%; Luminescent material protection glaze is as follows with component and the weight percent of flux: SiO
2: 43%, SrO:6.3%, B
2O
3: 18.8%, Al
2O
3: 1.2%, Li
2O:5.7%, Na
2O:4.3%, K
2O:1.2%, SrF
2: 1.5%, P
2O
5: 3.5%, Ta
2O
3: 0.5%, Nb
2O
5: 1%, ZrO
2: 0.5%, CeO
2: 2%, La
2O
3: 0.5%, Y
2O
3: 1%, ZnO:8.5%, MgO:0.5%;
Luminescent material can be SrAl
2O
6
Enamel ceramics is as follows with the glaze slip preparation technology of luminescent glaze:
A: the preparation of enamel ceramics basis glaze
(1) got the above-mentioned each component of the enamel ceramics basis glaze of 325 orders or thinner mesh screen;
(2) above-mentioned raw materials is mixed after, again 1280 ° of C ~ 1350 ° C fusing is put into the cold water shrend and is made enamel ceramics basis cullet of glaze;
(3) enamel ceramics basis cullet of glaze is packed in the ball mill, add water and the high alumina ballstone grinds to form glaze slip, then through 80 ~ 100 ° of C oven dry, and make powder, cross 250 orders or thinner mesh screen and obtain enamel ceramics basis glaze; Wherein, the weight ratio of water, high aluminium ball, enamel ceramics basis cullet of glaze is 0.35: 1: 1, and it is remaining less than 0.03% that fineness is controlled at 10000-hole sieve;
B: the preparation of luminescent material protection glaze
(1) luminescent material protection glaze is with the preparation of flux: the each component of getting the above-mentioned luminescent material protection glaze usefulness flux of 325 orders or thinner mesh screen; After above-mentioned raw materials mixed, 1260 ℃～1300 ℃ high temperature melting, through the cold water shrend, make luminescent material protection cullet of glaze after the oven dry; Protect cullet of glaze to pack in the ball mill luminescent material, add alcohol and the high alumina ballstone grinds to form glaze slip, drying then, and make powder, cross 250 orders or thinner mesh screen and obtain luminescent material protection glaze flux; Wherein, the weight ratio of alcohol, high aluminium ball and luminescent material protection cullet of glaze is 0.30: 1: 1;
(2) luminescent material being protected glaze is after 2: 2 or 2:3 ratio mix with flux and luminescent material according to weight ratio, pack in the little saggar respectively and under 780 ° of C ~ 820 ° C or 850 ° of C ~ 900 ° C temperature, to send in pushed bat kiln or the roller kiln resintering 2 hours, obtain respectively A resintering material or B resintering material, in the ball mill of packing into after A resintering material or the coarse crushing of B resintering material, add alcohol and the high alumina ballstone grinds to form glaze slip, then 80 ~ 100 ° of C oven dry, and make powder, cross 180 order mesh screens and obtain respectively luminescent material protection glaze A or luminescent material protection glaze B; Wherein, the weight ratio of the material crossed of alcohol, high aluminium ball and resintering is 0.30: 1: 1;
C: the enamel ceramics preparation of luminescent glaze
The luminescent material protection glaze A that the enamel ceramics basis glaze powder that the A process is made and B process are made is to make enamel ceramics luminescent glaze powder mixture A after 1: 2 ratio is mixed according to weight ratio; be that 1: 2.4 ratio is mixed with powder mixture A and water according to weight ratio; adding proportion is that the charging basket that 0.5% the aerosil of powder mixture A is put into homogenizer together as additive fully mixes again, stirs evenly and makes scattered and stable enamel ceramics glaze slip A.The luminescent material protection glaze B that the enamel ceramics basis glaze powder that same method is made the A process and B process are made is to make enamel ceramics luminescent glaze powder mixture B after 1: 3 ratio is mixed according to weight ratio; be that 1: 2.5 ratio is mixed with powder mixture B and water according to weight ratio, adding proportion is that charging basket that 1.5% the aerosil of powder mixture B is put into homogenizer together as additive fully mixes to stir evenly and makes scattered and stable enamel ceramics with luminous glaze slip B again.
Namely can be applicable in the painted decoration of ceramic surface enamel through A, B, three prepared glaze slips of technological process of C, pottery is hard-paste or soft porcelain or Shi porcelain or fine pottery, for example various white clouds porcelain or white clouds soil porcelain or various china or bone china or imitative china or various Shi porcelain or fine pottery; Enamel ceramics luminescent glaze A can be used for the over-glaze decoration of 760 ° of enamel ceramics～850 ° of C; Enamel ceramics luminescent glaze B can be used for the in-glaze decoration of 900 ° of enamel ceramics～1050 ° of C and paints.
Embodiment three
A kind of enamel ceramics luminescent glaze, comprise enamel ceramics basis glaze and luminescent material protection glaze, resintering made after luminescent material protection glaze was mixed with flux and luminescent material by luminescent material protection glaze, component and the weight percent of enamel ceramics basis glaze are as follows: component and the weight percent of described enamel ceramics basis glaze are as follows: quartzy 25%, lithionite 19%, feldspar 8.5%, talcum 3.0%, borax 18%, boric acid 9.4%, Strontium carbonate powder 5.5%, zinc oxide 3%, zirconium silicate 1.3%, cerium oxide 2.5%, aluminium sesquioxide 0.6%, fluorite 3.2%;
Luminescent material protection glaze is as follows with component and the weight percent of flux: SiO
2: 44.9%, SrO:4.1%, B
2O
3: 17.7%, Al
2O
3: 0.5%, Li
2O:4.1%, Na
2O:5.7%, K
2O:2.6%, SrF
2: 1.1%, LiF:2.7%, P
2O
5: 2.6%, Ta
2O
3: 0.5%, Nb
2O
5: 0.5%, ZrO
2: 0.5%, CeO
2: 2.0%, La
2O
3: 0.5%, Y
2O
3: 0.5%, ZnO:9.0%, MgO:0.5%;
Luminescent material is SrAl
2O
6: 70% and CdS:30%.
Enamel ceramics is as follows with the glaze slip preparation technology of luminescent glaze:
A: the preparation of enamel ceramics basis glaze
(1) got the above-mentioned each component of the enamel ceramics basis glaze of 325 orders or thinner mesh screen;
(2) above-mentioned raw materials is mixed after, again 1280 ° of C ~ 1350 ° C fusing is put into the cold water shrend and is made enamel ceramics basis cullet of glaze;
(3) enamel ceramics basis cullet of glaze is packed in the ball mill, add water and the high alumina ballstone grinds to form glaze slip, then through 80 ~ 100 ° of C oven dry, and make powder, cross 250 orders or thinner mesh screen and obtain enamel ceramics basis glaze; Wherein, the weight ratio of water, high aluminium ball, enamel ceramics basis cullet of glaze is 0.35: 1: 1, and it is remaining less than 0.03% that fineness is controlled at 10000-hole sieve;
B: the preparation of luminescent material protection glaze
(1) luminescent material protection glaze is with the preparation of flux: the each component of getting the above-mentioned luminescent material protection glaze usefulness flux of 325 orders or thinner mesh screen; After above-mentioned raw materials mixed, 1250 ℃ again～1300 ℃ high temperature melting through the cold water shrend, were made luminescent material protection cullet of glaze after the oven dry; Protect cullet of glaze to pack in the ball mill luminescent material, add alcohol and the high alumina ballstone grinds to form glaze slip, drying then, and make powder, cross 250 orders or thinner mesh screen and obtain luminescent material protection glaze flux; Wherein, the weight ratio of alcohol, high aluminium ball and luminescent material protection cullet of glaze is 0.30: 1: 1;
(2) luminescent material being protected glaze is after 2: 3 ratios mix with flux and luminescent material according to weight ratio, pack into and under ° C temperature of 800 ° of C ~ 850, send in pushed bat kiln or the roller kiln resintering in the little saggar about 1.5 hours, pack into after the material coarse crushing with resintering in the ball mill, add alcohol and the high alumina ballstone grinds to form glaze slip, then through 80 ~ 100 ° of C oven dry, and make powder, cross 200 order mesh screens and obtain luminescent material protection glaze; Wherein, the weight ratio of the material crossed of alcohol, high aluminium ball and resintering is 0.30: 1: 1;
C: the enamel ceramics preparation of luminescent glaze
It is to make enamel ceramics luminescent glaze powder mixture after 2: 5 ratio is mixed according to weight ratio that A process the enamel ceramics basis glaze powder of making and the luminescent material that the B process is made are protected the glaze powder; be that 1: 2.5 ratio is mixed with powder mixture and water according to weight ratio, adding proportion is that charging basket that 1.2% additive of powder mixture is put into homogenizer together fully mixes to stir evenly and makes so that glaze slip again.Additive can be aerosil or ultra-fine precipitates silicon-dioxide or white carbon black or silicon sol.
Namely can be applicable in the painted decoration of ceramic surface enamel through A, B, three prepared glaze slips of technological process of C, pottery is hard-paste or soft porcelain or Shi porcelain or fine pottery, for example various white clouds porcelain or white clouds soil porcelain or various china or bone china or imitative china or various Shi porcelain or fine pottery; The enamel ceramics luminescent glaze that the present embodiment makes can be used for the in-glaze decoration of 900 ° of enamel ceramics～1050 ° of C and paints.
Through detecting, the enamel ornamental ceramics of above-mentioned three embodiment preparation through an illumination after, not only its luminous bright but also its fluorescent lifetime can reach more than tens hours.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (13)
1. enamel ceramics luminescent glaze, comprise enamel ceramics basis glaze and luminescent material protection glaze, resintering made after luminescent material protection glaze was mixed with flux and luminescent material by luminescent material protection glaze, it is characterized in that, component and the weight percent of described enamel ceramics basis glaze are as follows: quartzy 20% ~ 40%, lithionite 10% ~ 20%, feldspar 5% ~ 10%, talcum 2% ~ 3%, borax 10% ~ 25%, boric acid 6% ~ 12%, Strontium carbonate powder 3% ~ 10%, zinc oxide 1% ~ 3%, zirconium silicate 0 ~ 3%, cerium oxide 0.1% ~ 3%, aluminium sesquioxide 0.5% ~ 3%, fluorite 0 ~ 5%; Described luminescent material protection glaze is as follows with component and the weight percent of flux: SiO
2: 42% ~ 48%, SrO:3% ~ 7%, B
2O
3: 15% ~ 21%, Al
2O
3: 0.2% ~ 1.2%, Li
2O:3% ~ 7%, Na
2O:2% ~ 7%, K
2O:1% ~ 3%, metal fluoride: 0.6%～3.8%, P
2O
5: 2% ~ 3.5%, Ta
2O
3: 0 ~ 0.5%, Nb
2O
5: 0～1%, ZrO
2: 0～0.5%, CeO
2: 0～3%, La
2O
3: 0～0.5%, Y
2O
3: 0 ~ 2%, ZnO:5% ~ 10%, MgO:0 ~ 0.5%; Described luminescent material is alkali earth metal aluminate or alkaline earth sulfide.
2. enamel ceramics luminescent glaze according to claim 1 is characterized in that: component and the weight percent of described enamel ceramics basis glaze are as follows: quartzy 28% ~ 35%, and lithionite 15% ~ 18%, feldspar 6% ~ 8%, talcum 2.2% ~ 2.5%, borax 15% ~ 21%, boric acid 8% ~ 10%, Strontium carbonate powder 5% ~ 8%, zinc oxide 1.8% ~ 2.2%, zirconium silicate 0.5% ~ 1.5%, cerium oxide 0.8% ~ 2.6%, aluminium sesquioxide 1.5% ~ 2%, fluorite 2.5 ~ 4%; Described luminescent material protection glaze is as follows with component and the weight percent of flux: SiO
2: 43%～46%, SrO:3.6% ~ 6.2%, B
2O
3: 16%～20%, Al
2O
3: 0.4%～0.8%, Li
2O:4%～6%, Na
2O:3%～5%, K
2O:2%～3%, metal fluoride: 0.9%～2.8%, P
2O
5: 2%～3%, Ta
2O
3: 0.2% ~ 0.5%, Nb
2O
5: 0.6%～1%, ZrO
2: 0.2% ~ 0.5%, CeO
2: 1.2%～2.2%, La
2O
3: 0.2% ~ 0.5%, Y
2O
3: 0.6%～1.5%, ZnO:6% ~ 9%, MgO:0.3%～0.5%.
3. enamel ceramics luminescent glaze according to claim 1 and 2 is characterized in that: the weight part ratio of described enamel ceramics basis glaze and luminescent material protection glaze is 1: 1～4; Luminescent material protection glaze is that 2: 1～5 ratio mix afterwards high temperature resintering make with flux and luminescent material according to weight ratio by luminescent material protection glaze, and wherein, the resintering temperature is 700 ° of C ~ 900 ° C, high-temperature holding time 30～150 minutes.
4. enamel ceramics luminescent glaze according to claim 3 is characterized in that: the part by weight of described enamel ceramics basis glaze and luminescent material protection glaze is 1: 2～3; Described luminescent material protection glaze is 2: 2 ~ 3 with the part by weight of flux and luminescent material.
5. enamel ceramics luminescent glaze according to claim 1 and 2, it is characterized in that: described metal fluoride is LiF, SrF
2, MgF
2, CaF
2, BaF
2, among the NaF one or more.
6. enamel ceramics luminescent glaze according to claim 1 and 2, it is characterized in that: described luminescent material is SrAl
2O
6, CaAl
2O
6, BaAl
2O
6, among ZnS, CaS, the CdS one or more.
7. enamel ceramics luminescent glaze according to claim 1 and 2, it is characterized in that: the enamel ceramics 100% also adds 0.5% ~ 4% additive in luminescent glaze, and described additive is aerosil or ultra-fine precipitates silicon-dioxide or white carbon black or silicon sol.
8. an enamel ceramics as claimed in claim 1 is characterized in that the step of this technique is as follows with the glaze slip preparation technology of luminescent glaze:
A: the preparation of enamel ceramics basis glaze
(1) gets the quartz 20% ~ 40% that 325 orders or thinner mesh screen sieve, lithionite 10% ~ 20%, feldspar 5% ~ 10%, talcum 2% ~ 3%, borax 10% ~ 25%, boric acid 6% ~ 12%, Strontium carbonate powder 3% ~ 10%, zinc oxide 1% ~ 3%, zirconium silicate 0 ~ 3%, cerium oxide 0.1% ~ 3%, aluminium sesquioxide 0.5% ~ 3%, fluorite 0 ~ 5%;
(2) above-mentioned raw materials is mixed by prescription batching after, ° C fusing 1250 ° of C ~ 1380 is put into the cold water shrend and is made enamel ceramics basis cullet of glaze;
(3) enamel ceramics basis cullet of glaze is packed in the ball mill, add water and the high alumina ballstone grinds to form glaze slip, then through 80 ~ 100 ° of C oven dry, and make powder, cross 250 orders or thinner mesh screen and obtain enamel ceramics basis glaze; Wherein, the weight ratio of water, high aluminium ball, enamel ceramics basis cullet of glaze is 0.35: 1: 1, and it is remaining less than 0.03% that fineness is controlled at 10000-hole sieve;
B: the preparation of luminescent material protection glaze
(1) luminescent material protection glaze is with the preparation of flux: the SiO that got 325 orders or thinner mesh screen
2: 42% ~ 48%, SrO:3% ~ 7%, B
2O
3: 15% ~ 21%, Al
2O
3: 0.2% ~ 1.2%, Li
2O:3% ~ 7%, Na
2O:2% ~ 7%, K
2O:1% ~ 3%, metal fluoride: 0.6%～3.8%, P
2O
5: 2% ~ 3.5%, Ta
2O
3: 0 ~ 0.5%, Nb
2O
5: 0～1%, ZrO
2: 0～0.5%, CeO
2: 0～3%, La
2O
3: 0～0.5%, Y
2O
3: 0 ~ 2%, ZnO:5% ~ 10%, MgO:0 ~ 0.5%; After above-mentioned raw materials mixed, again 1220 ℃～1360 ℃ high temperature melting, through the cold water shrend, make luminescent material protection cullet of glaze after the oven dry; Protect cullet of glaze to pack in the ball mill luminescent material, add alcohol and the high alumina ballstone grinds to form glaze slip, drying then, and make powder, cross 250 orders or thinner mesh screen and obtain luminescent material protection glaze flux; Wherein, the weight ratio of alcohol, high aluminium ball and luminescent material protection cullet of glaze is 0.30: 1: 1; It is remaining less than 0.03% that fineness is controlled at 10000-hole sieve;
(2) luminescent material being protected glaze is after 2: 2 ~ 3 ratios mix with flux and luminescent material according to weight ratio, pack into and send in pushed bat kiln or the roller kiln in the little saggar, the high temperature resintering is 30～150 minutes under ° C temperature of 700 ° of C ~ 900, pack into after the material coarse crushing with resintering in the ball mill, add alcohol and the high alumina ballstone grinds to form glaze slip, then dry through 80 ~ 100 ° of C, and make powder, cross 160 orders～200 purpose mesh screens and obtain luminescent material protection glaze; In the mechanical milling process, the weight ratio of the material that alcohol, high aluminium ball and resintering are crossed is 0.30: 1: 1;
C: enamel ceramics prepares with the glaze slip of luminescent glaze
It is to make enamel ceramics luminescent glaze powder mixture after 1: 2 ~ 3 ratio is mixed according to weight ratio that A process the enamel ceramics basis glaze powder of making and the luminescent material that the B process is made are protected the glaze powder; be that 1: 2.2 ~ 2.6 ratio is mixed with powder mixture and water according to weight ratio; adding proportion is that charging basket that the additive of powder mixture weight 0.5% ~ 4% is put into homogenizer together fully mixes and stirs evenly again, obtains enamel ceramics with the glaze slip of luminescent glaze.
9. enamel ceramics according to claim 8 is with the glaze slip preparation technology of luminescent glaze, and it is characterized in that: described metal fluoride is LiF, SrF
2, MgF
2, CaF
2, BaF
2, among the NaF one or more.
10. enamel ceramics according to claim 8 is with the glaze slip preparation technology of luminescent glaze, and it is characterized in that: described luminescent material is SrAl
2O
6, CaAl
2O
6, BaAl
2O
6, among ZnS, CaS, the CdS one or more.
11. the enamel ceramics according to claim 8 glaze slip preparation technology of luminescent glaze, it is characterized in that: described additive is aerosil or ultra-fine precipitates silicon-dioxide or white carbon black or silicon sol.
12. an enamel ceramics as claimed in claim 4 application of luminescent glaze is characterized in that: this enamel ceramics is applied to the enamel colored drawing of pottery with luminescent glaze.
13. the enamel ceramics according to claim 12 application of luminescent glaze, it is characterized in that: described pottery is hard-paste or soft porcelain or Shi porcelain or fine pottery, and described colour enamels is depicted as the over-glaze decoration of 760 °～850 ° of C or the in-glaze decoration of 900 °～1050 ° of C is painted.
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