CN101768016A - Enamel color ceramic glaze and production process and application thereof - Google Patents

Enamel color ceramic glaze and production process and application thereof Download PDF

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Publication number
CN101768016A
CN101768016A CN200910189328A CN200910189328A CN101768016A CN 101768016 A CN101768016 A CN 101768016A CN 200910189328 A CN200910189328 A CN 200910189328A CN 200910189328 A CN200910189328 A CN 200910189328A CN 101768016 A CN101768016 A CN 101768016A
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oxide
glaze
ceramic glaze
color ceramic
enamel color
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刘权辉
曾学富
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SHENZHEN AURATIC INDUSTRY Co Ltd
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SHENZHEN AURATIC INDUSTRY Co Ltd
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Abstract

The invention discloses an enamel color ceramic glaze, which belongs to the technical field of ceramic materials and comprises a substrate and a coloring oxide of the enamel color ceramic glaze; the weight ratio of the substrate to the coloring oxide of the enamel color ceramic glaze is 0.5-1: 1; and the substrate of the enamel color ceramic glaze comprises the following components by weight percentage: 44-63% of SiO2, 5-12% of Al2O3, 5-12% of CaO, 0-5% of MgO, 0-5% of P2O5, 0.5-5% of SrO, 2-8% of ZnO, 1-6.5% of K2O, 1-5% of Na2O, 0.5-5% of Li2O, 1-8% of B2O3, 0-4% of ZrO2 and 2-4% of Y2O3. The enamel color ceramic glaze optimizes the formula of the enamel color ceramic glaze and introduces a rare earth compound of yttrium oxide (Y2O3) for replacing part of zinc oxide and CaF2, thereby having reasonable chemical composition and better physical performance indices, improving the sintering temperature of base glaze, increasing the high-temperature viscosity of the base glaze and being more applicable to color development of the coloring metal oxide.

Description

A kind of enamel color ceramic glaze and manufacture craft thereof and application
Technical field
The present invention relates to technical field of ceramic material, especially relate to a kind of enamel color ceramic glaze and manufacture craft thereof and application.
Background technology
Colour enamels is to add different colour generation metal oxides to make in glass powder, glass powder is basic glaze, be to form by glass grinding, main raw material is that quartz, feldspar, borax, fluorochemical etc. are according to certain mixed, the main effect of colour generation metal oxide is to be blended in to make it produce different color development effects in the basic glaze, and it is the same with making ceramic color glaze to play principle.The color development of metal oxide depends on adding wherein and help the basic glaze of color development, and basic glaze has extremely important effect to visual appearancies such as the tone of ceramic color glaze, lightness, aberration.Long history is arranged, the enamel faience that is called as " faience queen " " government porcelain kiln in the government porcelain kiln ", though it has the porcelain exquisiteness, color material is dignified, bright in colour beautiful, characteristics such as painter's exquisiteness, but manufacture craft is still continued to use traditional low temperature over-glaze decoration technology at present, it is low to add fusing point, Young's modulus is big, the colour enamels glass-based glaze that the coefficient of expansion is big, because of containing quartz in the glass-based glaze, quartzy melt temperature height own, up to more than 1,700 degree, in order to reduce the fusing point of glass-based glaze, will add feldspar as fusing assistant, feldspar can be introduced potassium again, sodium element, potassium, sodium can increase the coefficient of expansion of basic glaze, reduce the sticking power of enamel glaze and porcelain body, cause the enamel colored glaze to come off, simultaneously from porcelain body, colour enamels requires that the embossment feel will be arranged, when the enamelling colored glaze, require to reach certain thickness, the coefficient of expansion because of porcelain body glaze and colour enamels base glaze does not match again, cause the be full of cracks of enamel colored glaze glaze, add CaF in addition 2Reduce the viscosity of basic glaze, be easy to flow after making basic glaze fusion, because of basic glaze temperature flowing good, easily cause the irregular diffusion of the painted oxidation color of part, make its dim pattern unclear, traditional colour enamels relies on the bright-coloured heavy metal of color development, such as: " arsenic ", it is deleterious material to human body and environment.Along with the raising of people's living standard, health care consciousness strengthens, and heavy metal such as lead, cadmium and toxicity of compound thereof further are familiar with, and countries in the world all propose the more and more requirement of strictness to the use that contains heavy metal material.
ZL99114480.5 has invented low temperature enamel frit and low temperature enamel slurry, has following component (weight) to be: base stock SiO 245 parts of base stocks fusing assistant B that holds concurrently 2O 317~23 parts, fusing assistant Li 210~12 parts of O, fusing assistant Na 26~12 parts of O, fusing assistant Ti 28~26 parts of O, emulsion CaF 225~30 parts, molten adding, transferred 8~25 parts of thing ZnO, and molten adding transferred thing Al 2O 31~12 part, molten adding, transferred 6~8 parts of thing BaO, and its firing range is 500 ℃~650 ℃.This invention is obtaining effect preferably aspect the problem that solves heavy metal contamination.
But this base glaze still belongs to the low temperature glaze category, and ZnO content is higher in its glaze composition, cause hardness of glaze surface lower, easily scratch, the high glaze of ZnO content to cobalt black look, blue-greenish colour, pink, agate red, brown, coffee-like, sapphire blue, the cobalt blue color development is very unfavorable, CaF in its composition of while 2The content height, the temperature flowing of glaze is good, is prone to the phenomenon of color diffusion, dim pattern, is not suitable for producing the colour enamels of above-mentioned color, thereby has limited the rich of product colour; Also has its firing range Zuo, the product base glaze underburnt and the burning defective that easily cause; According to the goods that its method is made, because of firing temperature is low, the color in the enamel glaze contacts with air for a long time, can cause the coloring metal oxide compound oxidized, thereby causes the product colour variable color or fade, even comes off.
Summary of the invention
One of purpose of the present invention is to provide a kind of base-material of enamel color ceramic glaze, solves the defective that prior art exists.
For achieving the above object, the present invention adopts following technical scheme:
A kind of base-material of enamel color ceramic glaze comprises following component and content (WT% all represents weight percentage in full):
SiO 244~63%,Al 2O 35~12%,CaO?5~12%,MgO0~5%,P 2O 50~5%,SrO?0.5~5%,ZnO2~8%,K 2O1~6.5%,Na 2O1~5%,Li 2O0.5~5%,B 2O 31~8%,ZrO 20~4%,Y 2O 30.2~4%。
Preferred scheme is: comprise following component and content (WT%):
SiO 245~55%,Al 2O 37~10%,CaO5~10%,MgO?0~3%,P 2O 50.5~2%,SrO0.5~3%,ZnO3~6%,K 2O1~4%,Na 2O2~4%,Li 2O0.5~3%,B 2O 35~8%,ZrO 20~2%,Y 2O 30.5~3%。
Two of purpose of the present invention is to provide a kind of enamel color ceramic glaze, adopts following technical scheme:
A kind of enamel color ceramic glaze comprises the base-material and the coloring oxide of the enamel color ceramic glaze of the described arbitrary technical scheme of one of the object of the invention; The volume ratio of described enamel color ceramic glaze base-material and coloring oxide is 0.5~1: 1.
Preferred scheme is: described coloring oxide is one or several mixtures in ferric oxide, chromic oxide, cupric oxide, weisspiessglanz, nickel oxide, cobalt oxide, stannic oxide, the manganese oxide.
More preferred scheme is: also comprise additive, described additive accounts for 0.5~3WT% of the weight percentage ratio of total glaze.
More preferred scheme is: described additive is polyvinyl alcohol, carboxymethyl cellulose, organic gel class.
The main effect that adds additive is: increase the water retention property of enamel glaze, increase the sticking power or the bonding force of enamel glaze and ceramic body simultaneously.
Three of purpose of the present invention is to provide a kind of technology for preparing enamel color ceramic glaze, adopts following technical scheme:
A kind of technology for preparing enamel color ceramic glaze comprises the steps:
(1) gets the silica powder 25~45% that 325 orders or thinner mesh screen sieve, get the nepheline powder 20~40% that 325 orders or thinner mesh screen sieve, borax 2~20%, zinc oxide 2~7%, zirconium silicate 0~5%, yttrium oxide 0.1~3%, lime carbonate 6~16%, magnesiumcarbonate 0~8%, Vanadium Pentoxide in FLAKES 0~5%, Strontium carbonate powder 0.5~6%, Quilonum Retard 2~10%;
(2) above-mentioned raw materials is mixed after, 1360 ℃~1480 ℃ fusings, put into the cold water shrend and make frit;
(3) frit is packed in the ball mill, add the kaolin that water, high alumina ballstone and 0~15%325 order or thinner mesh screen sieve, or other glaze slip properties modifier grinds to form glaze slip, it is surplus less than 0.03% that fineness is controlled at 10000-hole sieve, then through 80~100 ℃ of oven dry, and make that powder is crossed 250 orders or thinner mesh screen makes the enamel color ceramic glaze base-material;
(4) be to make the enamel color ceramic glaze powder mixture after 0.5~1: 1 mixed with the base-material made and coloring oxide according to weight ratio, 's 0.5~2: 1 mixed with powder mixture and water according to weight ratio, and add the additive of 0.5~3WT%, mixing and stirring.
Preferred scheme is: described coloring oxide is one or several mixtures in ferric oxide, chromic oxide, cupric oxide, weisspiessglanz, nickel oxide, cobalt oxide, stannic oxide, the manganese oxide; Described additive is polyvinyl alcohol, carboxymethyl cellulose, organic gel class.
The present invention compared with prior art has following advantage and beneficial effect:
The present invention introduces rare earth compound yttrium oxide (Y by optimizing colour enamels base glaze formulation 2O 3) alternative partial oxidation zinc and CaF 2Make it have rational chemical constitution and better physical performance index, reach the firing temperature that improves basic glaze, improve the high-temperature viscosity of basic glaze, widen the firing range of basic glaze, reduce the coefficient of expansion of basic glaze, make its color development that is more suitable for the coloring metal oxide compound, the purpose that can produce colour enamels under the high melting glaze.The present invention introduces Vanadium Pentoxide in FLAKES (P simultaneously 2O 5) as the branch phase composition of tinting material, be not subjected to the influence of cover-coat enamel when allowing the color color development, guarantee that the color development of tinting pigment is stable.
The basic glaze of enamel color ceramic glaze of the present invention belongs to high-temp leadless frit glaze, it is wide to have firing range, applied widely, can be used for china, white clouds soil porcelain, the Shi porcelain, bone china, imitative china, the soft enamel assistant that oxydizing flame such as fine pottery burn till paints the pigment fusing assistant, the colour generation that helps painted oxide compounds such as various colour enamelss, the product that adopts this kind glaze to make as the under-glaze pigment fusing assistant, bright-colored, pure, full, it is fuzzy not have diffusion, no color differnece, this base glaze also can be used for preparation and produce the shades of colour glaze, the ceramic hardness of glaze surface height that adopts this glaze to produce, glossiness is good, the transparence height has improved the quality and the class of product.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further details:
Raw materials used main chemical constitution weight percent among table 1 embodiment
The main chemical constitution weight percent of the basic glaze of enamel color ceramic glaze among table 2 embodiment
Title Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
??SiO 2 ??52.75 ??46.82 ??44.60 ??59.51
??Al 2O 3 ??5.17 ??7.28 ??8.95 ??6.41
??B 2O 3 ??7.66 ??6.26 ??7.21 ??5.33
??CaO ??5.41 ??9.54 ??9.73 ??5.04
??MgO ??2.07 ??2.45 ??/ ??1.12
Title Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
??P 2O 5 ??1.75 ??0.90 ??4.80 ??/
??SrO ??2.37 ??3.41 ??0.82 ??1.21
??Li 2O ??1.81 ??2.68 ??2.25 ??0.62
??K 2O ??2.75 ??3.11 ??2.82 ??1.99
??Na 2O ??3.63 ??3.78 ??3.06 ??2.26
??ZnO ??2.94 ??4.56 ??4.65 ??5.89
??ZrO 2 ??1.86 ??1.67 ??0.76 ??/
??Y 2O 3 ??1.90 ??2.19 ??0.39 ??0.92
Annotate: the part of less than 100% is Fe in the chemical constitution weight percentage 2O 3, TiO 2Igloss (IL) and conventional raw mineral materials impurity.
Embodiment 1: with 38 parts of silica powders (325 order), and nepheline powder (325 order): 25 parts, 12 parts of boraxs, 3 parts in zinc oxide, 2 parts of zirconium silicates, 2 parts of yttrium oxides, 6 parts in lime carbonate, 3 parts in magnesiumcarbonate, 2 parts of Vanadium Pentoxide in FLAKESs, 3 parts of Strontium carbonate powders, 4 parts of Quilonum Retards.After above-mentioned raw materials mixed,, put into the cold water shrend and make frit 1380 ℃~1450 ℃ fusings.
Frit is packed in the ball mill, add water, high alumina ballstone and kaolin (0~15%) or other glaze slip properties modifier and grind to form glaze slip, it is surplus less than 0.03% that fineness is controlled at 10000-hole sieve, then through 80~100 ℃ of oven dry, and make powder and cross 250 mesh sieves, basic glaze and the coloring oxide (ferric oxide) made are prepared burden according to 1: 2 ratio, again according to material: the ratio of water=50: 33 adds entry, and outer doping (PVA polyvinyl alcohol 0.5%) mixing and stirring promptly can be used for enamel colored drawing under the ceramic glaze.
Embodiment 2: with 26 parts of silica powders (325 order), and nepheline powder (325 order): 35 parts, 10 parts of boraxs, 5 parts in zinc oxide, 2 parts of zirconium silicates, 2.5 parts of yttrium oxides, 10 parts in lime carbonate, 3.5 parts in magnesiumcarbonate, 1 part of Vanadium Pentoxide in FLAKES, 2 parts of Strontium carbonate powders, 3 parts of Quilonum Retards.After above-mentioned raw materials mixed,, put into the cold water shrend and make frit 1380 ℃~1450 ℃ fusings.
Frit is packed in the ball mill, add water, high alumina ballstone and kaolin (0~10%) or other glaze slip properties modifier and grind to form glaze slip, it is surplus less than 0.03% that fineness is controlled at 10000-hole sieve, then through 80~100 ℃ of oven dry, and make powder and cross 250 mesh sieves, with the basic glaze made and coloring oxide or oxide mixture (cupric oxide) ratio batching according to 3: 5, again according to material: the ratio of water=5: 3 adds entry, and outer doping (PVA polyvinyl alcohol 1.0%) mixing and stirring promptly can be used for enamel colored drawing under the ceramic glaze.
Embodiment 3: with 25 parts of silica powders (325 order), and nepheline powder (325 order): 25 parts, 10 parts of kaolin, 12 parts of boraxs, 5 parts in zinc oxide, 1 part of zirconium silicate, 0.5 part of yttrium oxide, 10.5 parts in lime carbonate, 5 parts of Vanadium Pentoxide in FLAKESs, 1 part of Strontium carbonate powder, 5 parts of Quilonum Retards.After above-mentioned raw materials mixed,, put into the cold water shrend and make frit 1380 ℃~1450 ℃ fusings.
Frit is packed in the ball mill, add water, high alumina ballstone and kaolin (0~6%) or other glaze slip properties modifier and grind to form glaze slip, it is surplus less than 0.03% that fineness is controlled at 10000-hole sieve, then through 80~100 ℃ of oven dry, and make powder and cross 250 mesh sieves, with the basic glaze made and coloring oxide (ferric oxide and cupric oxide) according to 7: the ratio batching of (4: 6), again according to material: the ratio of water=10: 7 adds entry, and outer doping (PVA polyvinyl alcohol 0.5%) mixing and stirring promptly can be used for enamel colored drawing under the ceramic glaze.
Embodiment 4: with 44 parts of silica powders (325 order), and nepheline powder (325 order): 20 parts, 6 parts of kaolin, 8 parts of boraxs, 6 parts in zinc oxide, 1 part of yttrium oxide, 9 parts in lime carbonate, 2 parts in magnesiumcarbonate, 2 parts of Strontium carbonate powders, 2 parts of Quilonum Retards.After above-mentioned raw materials mixed,, put into the cold water shrend and make frit 1380 ℃~1450 ℃ fusings.
Frit is packed in the ball mill, add water, high alumina ballstone and kaolin (0%) or other glaze slip properties modifier and grind to form glaze slip, it is surplus less than 0.03% that fineness is controlled at 10000-hole sieve, then through 80~100 ℃ of oven dry, and make powder and cross 250 mesh sieves, is to prepare burden at 20: 13 the basic glaze made and coloring oxide (weisspiessglanz) according to weight ratio, again according to material: the ratio of water=50: 33 adds entry, and outer doping (carboxymethyl cellulose 0.5%) mixing and stirring promptly can be used for enamel colored drawing under the ceramic glaze.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to the protection domain of inventing type.

Claims (10)

1. the base-material of an enamel color ceramic glaze is characterized in that: comprise following component and content (WT%):
SiO 2?44~63%,Al 2O 3?5~12%,CaO?5~12%,MgO?0~5%,P 2O 5?0~5%,SrO?0.5~5%,ZnO?2~8%,K 2O?1~6.5%,Na 2O?1~5%,Li 2O?0.5~5%,B 2O 3?1~8%,ZrO 2?0~4%,Y 2O 3?0.2~4%。
2. the base-material of enamel color ceramic glaze as claimed in claim 1 is characterized in that: comprise following component and content (WT%):
SiO 2?45~55%,Al 2O 3?7~10%,CaO?5~10%,MgO?0~3%,P 2O 5?0.5~2%,SrO?0.5~3%,ZnO?3~6%,K 2O?1~4%,Na 2O?2~4%,Li 2O?0.5~3%,B 2O 3?5~8%,ZrO 2?0~2%,Y 2O 3?0.5~3%。
3. an enamel color ceramic glaze comprises base-material and coloring oxide as claim 1 or 2 described enamel color ceramic glazes; The weight ratio of described enamel color ceramic glaze base-material and coloring oxide is 0.5~1: 1.
4. enamel color ceramic glaze as claimed in claim 3 is characterized in that coloring oxide is one or several mixtures in ferric oxide, chromic oxide, cupric oxide, weisspiessglanz, nickel oxide, cobalt oxide, stannic oxide, the manganese oxide.
5. enamel color ceramic glaze as claimed in claim 4 is characterized in that: also comprise additive, described additive is that total glaze weight percent is 0.5~3WT%.
6. enamel color ceramic glaze as claimed in claim 5 is characterized in that: described additive is polyvinyl alcohol, carboxymethyl cellulose, organic gel class.
7. a technology for preparing enamel color ceramic glaze comprises the steps:
(1) gets the silica powder 25~45% that 325 orders or thinner mesh screen sieve, get the nepheline powder 20~40% that 325 orders or thinner mesh screen sieve, borax 2~20%, zinc oxide 2~7%, zirconium silicate 0~5%, yttrium oxide 0.1~3%, lime carbonate 6~16%, magnesiumcarbonate 0~8%, Vanadium Pentoxide in FLAKES 0~5%, Strontium carbonate powder 0.5~6%, Quilonum Retard 2~10%;
(2) above-mentioned raw materials is mixed after, 1360 ℃~1480 ℃ fusings, put into the cold water shrend and make frit;
(3) frit is packed in the ball mill, add the kaolin that water, high alumina ballstone and 0~15%325 order or thinner mesh screen sieve, or other glaze slip properties modifier grinds to form glaze slip, it is surplus less than 0.03% that fineness is controlled at 10000-hole sieve, then through 80~100 ℃ of oven dry, and make that powder is crossed 250 orders or thinner mesh screen makes the enamel color ceramic glaze base-material;
(4) be to make the enamel color ceramic glaze powder mixture after 0.5~1: 1 mixed with the base-material made and coloring oxide according to weight ratio, 's 0.5~2: 1 mixed with powder mixture and water according to weight ratio, and add the additive of 0.5~3WT%, mixing and stirring.
8. the technology of preparation ceramic glaze as claimed in claim 7 is characterized in that: described coloring oxide is one or several mixtures in ferric oxide, chromic oxide, cupric oxide, weisspiessglanz, nickel oxide, cobalt oxide, stannic oxide, the manganese oxide; Described additive is polyvinyl alcohol, carboxymethyl cellulose, organic gel class.
9. the application of an enamel color ceramic glaze, each described enamel color ceramic glaze of claim 4~6 are applied to the enamel colored drawing of the soft porcelain that oxydizing flame burns till.
10. the application of enamel color ceramic glaze as claimed in claim 9 is characterized in that: the soft porcelain that described oxydizing flame burns till is china or white clouds soil porcelain or Shi porcelain or bone china or imitative china or fine pottery; Described colour enamels is depicted as under glazed and paints.
CN200910189328A 2009-12-29 2009-12-29 Enamel color ceramic glaze and production process and application thereof Pending CN101768016A (en)

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Application publication date: 20100707