CN104609901B - A kind of lead-free and cadmium-free clear frit and preparation method thereof - Google Patents
A kind of lead-free and cadmium-free clear frit and preparation method thereof Download PDFInfo
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Abstract
A kind of lead-free and cadmium-free clear frit and preparation method thereof, relate to ceramic glaze technical field, it is prepared from by the raw material of silica gel powder body 30 ~ 50%, boric acid 14 ~ 18%, Borax 10 ~ 17%, limestone 10 ~ 14%, Kaolin 10 ~ 14% and silica flour 0 ~ 15%, wherein, according to raw material: abrading-ball: the ratio of water=1:1.2:0.8, raw material, abrading-ball and water are placed in ball milling 24h in ball mill, then the material after ball milling are crossed 325 mesh sieves, prepare clear frit.The raw materials used lead-free and cadmium-free of the present invention, simple and easy to get, solvent for use is deionized water, safe and nontoxic, pollution-free, and low price is with low cost, it is simple to batch production；Glaze prepared by the present invention, can directly burn till, and melt temperature is low, and glossiness is good, wide baking temperature range, and smooth surface is bright；Melting behaviour is good, and preparation condition is easily-controllable, production cost is low, and production efficiency is high.
Description
Technical field
The present invention relates to ceramic glaze technical field, be specifically related to a kind of lead-free and cadmium-free clear frit and preparation method thereof.
Background technology
Clear frit refers to the barment tag of glaze, the indefiniteness vitreous body that glaze is generated after high-temperature fusion, and the color and luster of base substrate itself can be reflected by glaze layer.For a long time, enamel is all to use the fritted glaze containing lead, this is owing to leaded glaze has easily melting, good fluidity, the features such as thermal coefficient of expansion is little, good thermal shock stability, and mechanical strength is big, the heavy metal elements such as lead are fired through certain technique, ceramic surface bright-coloured lucid and lively, svelteness, glossiness can be made high, elastic big, and firing range width and be used widely.But owing to lead glaze is poisonous, the health of production environment, operator and end user being had certain detrimental effect, GB GB 12651-2003 specifies, the stripping quantity tolerance limit of the ceramic lead contacted with food is below 5ppm, is state compulsory standard.
Therefore, the research of leadless glaze is day by day paid attention to by people.In recent years, existing large quantities of leadless glazes are succeeded in developing, and come into operation, but the present Research with regard to current leadless glaze is seen, this research is still in the research of lead-free fritting enamel, and the melt temperature of this leadless glaze is 1435 ~ 1500 DEG C, melt temperature is higher, and baking temperature range is narrow；Simultaneously as oxide is more complicated on the impact of lead-free fritting enamel temperature, cause leadless glaze ceramic cannot be protected in outward appearance and performance, glaze poor transparency.
Summary of the invention
The technical problem to be solved is to overcome existing fritted glaze melt temperature high, it is difficult to ensure the defect of its outward appearance and performance, it is provided that a kind of lead-free and cadmium-free clear frit and preparation method thereof.
The present invention solves that the technical scheme that the problems referred to above are used is: a kind of lead-free and cadmium-free clear frit, the raw material of following percentage by weight be prepared from: silica gel powder body 30 ~ 50%, boric acid 14 ~ 18%, Borax 10 ~ 17%, limestone 10 ~ 14%, Kaolin 10 ~ 14% and silica flour 0 ~ 15%.
The main chemical compositions of the clear frit that the present invention is prepared from and the mass percent of each chemical composition be: SiO235 ~ 55%, B2O315 ~ 20%, Na2O 2 ~ 5%, CaO 5 ~ 8%, Al2O3
4 ~ 9%, surplus is inevitable impurity.
The preparation method of the lead-free and cadmium-free clear frit of the present invention, comprises the following steps: step one, weigh sodium silicate powder body, is dissolved in a certain amount of deionized water being sufficiently stirred for, and prepares saturated sodium silicate solution, standby；
Step 2, measured amounts acid or strong acid weak base salt, add deionized water, it is configured to the solution of 5mol/L, and in this solution, drip 1 ~ 2 phenolphthalein solution, then the sodium silicate solution of step one preparation it is added dropwise over, when stirring to redness occurs, stop dropping, and continuously stirred 3 ~ 5min, prepare homogeneous transparent colloid solution, continue the sodium silicate solution that dropping step one prepares, until forming clear gum gel completely, stop dropping, and this clear gum gel is carried out sucking filtration, then 3 ~ 4 times it are washed with deionized, dry at 50 ~ 70 DEG C, prepare silicic acid xerogel, standby；
Step 3, utilize ball mill by step 2 prepare silicic acid xerogel grinds, prepare silica gel powder body, standby；
Step 4, according to boric acid 14 ~ 18%, Borax 10 ~ 17%, limestone 10 ~ 14%, Kaolin 10 ~ 14%, silica flour 0 ~ 15% and the percentage ratio of silica gel powder body 30 ~ 50%, weigh the silica gel powder body that starting boronic acid, Borax, limestone, Kaolin, silica flour and step 3 prepare successively, according to raw material: abrading-ball: the ratio of water=1:1.2:0.8, raw material, abrading-ball and water are placed in ball milling 24h in ball mill, then the material after ball milling is crossed 325 mesh sieves, prepare clear frit.In actual use, obtained glaze glazing thickness is 0.8 ~ 1.0mm, and firing temperature is 800 ~ 1000 DEG C.
Wherein, the acid in step 2 is hydrochloric acid, nitric acid, sulphuric acid or acetic acid；Strong acid weak base salt is ammonium chloride, ammonium nitrate or ammonium sulfate.
Beneficial effect: (1), step 2 of the present invention use sol-gel process to prepare Silica hydrogel, and silica gel powder body is applied in glaze preparation as the main material of glaze, Silica hydrogel is made to constitute the Coagulating binding phase of ceramic glaze together with other dispensing, so that glaze has the basic feature of zeolite minerals, dehydration temperature wide ranges, dehydration not only will not destroy bond strength, and the three dimensional structure that also can make glaze is more stable, improves glaze intensity.
(2), the raw materials used lead-free and cadmium-free of the present invention, simple and easy to get, solvent for use is deionized water, safe and nontoxic, pollution-free, and low price is with low cost, it is simple to batch production；Glaze prepared by the present invention, can directly burn till, and melt temperature is low, and glossiness is good, wide baking temperature range, and smooth surface is bright；Melting behaviour is good, and preparation condition is easily-controllable, production cost is low, and production efficiency is high.
(3), in the present invention, Al2O3By Kaolin (Al2O3·2SiO2·2H2O) introduce, Al2O3Form the network body of glaze, can be with SiO2In conjunction with, also can be combined with basic anhydride；The SiO introduced by silica flour2, SiO2The viscosity of glaze, transparency and chemical stability can be improved, and the coefficient of expansion of glaze can be reduced；CaO can reduce the viscosity of high silicon glaze, containing 35 ~ 55%SiO in glaze prepared by the present invention2With 5 ~ 8%CaO, the ratio of the two can improve the mobility of glaze, strengthens the colorability of glaze.
(4), glaze prepared by the present invention contains the B of 15 ~ 20%2O3, B2O3Can form low-melting mixtures with silica white body, reduce the melt temperature of glaze, glaze melt viscosity reduces, and mobility increases, it is easy to sprawl into smooth glaze, B2O3Addition can increase the refractive index of glaze, improve glossiness.In the present invention, the consumption of silica flour should be reduced so that it is be converted into glass phase to greatest extent, thus decrease residual quartz and the amount of cristobalite in finished product, significantly reduce the thermal coefficient of expansion of base substrate as far as possible；In glaze, substantially it is melted because of quartz as glassy state, so reducing the consumption of quartz in glaze, decreasing the effect of Si-O structure bonding force, improving glaze thermal coefficient of expansion.
Detailed description of the invention
Being described further lead-free and cadmium-free clear frit of the present invention and preparation method thereof below in conjunction with specific embodiment, so that those skilled in the art may be better understood the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
A kind of lead-free and cadmium-free clear frit, is prepared from by the raw material of following percentage by weight: silica gel powder body 30 ~ 50%, boric acid 14 ~ 18%, Borax 10 ~ 17%, limestone 10 ~ 14%, Kaolin 10 ~ 14% and silica flour 0 ~ 15%.The main chemical compositions of the clear frit being prepared from and the mass percent of each chemical composition be: SiO235 ~ 55%, B2O315 ~ 20%, Na2O 2 ~ 5%, CaO 5 ~ 8%, Al2O3
4 ~ 9%, surplus is inevitable impurity.
Embodiment 1
The preparation method of a kind of lead-free and cadmium-free clear frit, comprises the following steps: step one, weigh sodium silicate powder body, is dissolved in a certain amount of deionized water being sufficiently stirred for, and prepares saturated sodium silicate solution, standby；
The acid of step 2, measured amounts or strong acid weak base salt, add deionized water, it is configured to the solution of 5mol/L, and in this solution, drip 1 ~ 2 phenolphthalein solution, then it is added dropwise over the sodium silicate solution of step one preparation, when stirring to redness occurs, stop dropping, continue stirring, prepare homogeneous transparent colloid solution, standby；
Step 3, be added dropwise in colloid solution prepared by step 2 step one prepare sodium silicate solution, until forming clear gum gel completely, stop dropping, and this clear gum gel is carried out sucking filtration, then 3 ~ 4 times it are washed with deionized, dry at 50 ~ 70 DEG C, prepare silicic acid xerogel, standby；
Step 4, utilize ball mill by step 3 prepare silicic acid xerogel grinds, prepare silica gel powder body, standby；
Step 5, successively weigh starting boronic acid 14.00g, Borax 10.00g, limestone 10.00g and Kaolin 10.00g, silica flour 6.00g and step 4 prepare silica gel powder body 50.00g, be placed in zirconia ball grinding jar；Weigh 120g zirconium oxide ball milling ball and put into during this ball milling fills, and measure 80mL deionized water and pour ball grinder into, at the uniform velocity ball milling 24h, then crosses 325 mesh sieves by the material after ball milling, prepares clear frit, retention 0.5 ~ 2.5% on sieve.Obtained glaze glazing thickness is 0.8 ~ 1.0mm, and firing temperature is 800 ~ 1000 DEG C.
Embodiment 2
Prepare silica gel powder body according to step one to step 4 in embodiment 1, and weigh this silica gel powder body 39.40g, boric acid 15.15g, Borax 15.15g, limestone 12.12g and Kaolin 18.18g, be placed in zirconia ball grinding jar；Weigh 120g zirconium oxide ball milling ball and put into during this ball milling fills, and measure 80mL deionized water and pour ball grinder into, at the uniform velocity ball milling 24h, then crosses 325 mesh sieves by the material after ball milling, prepares clear frit, retention 0.5 ~ 2.5% on sieve.Obtained glaze glazing thickness is 0.8 ~ 1.0mm, and firing temperature is 800 ~ 1000 DEG C.
Embodiment 3
Prepare silica gel powder body according to step one to step 4 in embodiment 1, and weigh this silica gel powder body 40.00g, boric acid 16.00g, Borax 13.00g, limestone 12.00g, Kaolin 12.00g and silica flour 7.00g, be placed in zirconia ball grinding jar；Weigh 120g zirconium oxide ball milling ball and put into during this ball milling fills, and measure 80mL deionized water and pour ball grinder into, at the uniform velocity ball milling 24h, then crosses 325 mesh sieves by the material after ball milling, prepares clear frit, retention 0.5 ~ 2.5% on sieve.Obtained glaze glazing thickness is 0.8 ~ 1.0mm, and firing temperature is 800 ~ 1000 DEG C.The preparation of glaze of the present invention is without making melt, and the drying temperature of preparation process is relatively low, and firing temperature during use is less than 1000 DEG C, it is to avoid B2O3Volatilization.
Embodiment 4
Prepare silica gel powder body according to step one to step 4 in embodiment 1, and weigh this silica gel powder body 30.00g, boric acid 18.00g, Borax 17.00g, limestone 14.00g, Kaolin 14.00g and silica flour 7.00g, be placed in zirconia ball grinding jar；Weigh 120g zirconium oxide ball milling ball and put into during this ball milling fills, and measure 80mL deionized water and pour ball grinder into, at the uniform velocity ball milling 24h, then crosses 325 mesh sieves by the material after ball milling, prepares clear frit, retention 0.5 ~ 2.5% on sieve.Obtained glaze glazing thickness is 0.8 ~ 1.0mm, and firing temperature is 800 ~ 1000 DEG C.Obtained glaze remains with Kaolin, it is possible to increase the suspension of glaze slip and bond strength.Glazing thickness is 0.8 ~ 1.0mm, and firing temperature is 800 ~ 1000 DEG C.
By the glaze prepared of embodiment 1 ~ embodiment 4, using glaze method is 0.8 ~ 1.0mm to four parts of sample base substrate glazings, glazing thickness, naturally dry, be subsequently placed in Muffle furnace, with the heating gradient of 10 DEG C, it is warming up to 750 ~ 850 DEG C, at 900 ~ 1000 DEG C, is then incubated 30min；Open fire door, make sample be naturally cooling to 60 DEG C, take out each sample air cooling to room temperature.Observing glaze situation, be evaluated glaze: the glaze flat smooth of embodiment 1 ~ 4 sample, glaze glossiness is good, and transparency is high, and glaze-body bonding is good；Water absorption rate ＜ 0.5%, rupture strength ＞ 50MPa, product is flawless by 20 ~ 150 DEG C of temperature.
Claims (4)
1. a lead-free and cadmium-free clear frit, it is characterised in that: it is prepared from by the raw material of following percentage by weight: silica gel powder body 30 ~ 50%, boric acid 14 ~ 18%, Borax 10 ~ 17%, limestone 10 ~ 14%, Kaolin 10 ~ 14% and silica flour 0 ~ 15%.
A kind of lead-free and cadmium-free clear frit the most according to claim 1, it is characterised in that: the main chemical compositions of the clear frit being prepared from and the mass percent of each chemical composition be: SiO235 ~ 55%, B2O3
15 ~ 20%, Na2O 2 ~ 5%, CaO 5 ~ 8%, Al2O3
4~9%。
The preparation method of a kind of lead-free and cadmium-free clear frit the most according to claim 1, it is characterised in that comprise the following steps:
Step one, weigh sodium silicate powder body, be dissolved in a certain amount of deionized water being sufficiently stirred for, prepare saturated sodium silicate solution, standby；
Step 2, measured amounts acid or strong acid weak base salt, add deionized water, it is configured to the solution of 5mol/L, and in this solution, drip 1 ~ 2 phenolphthalein solution, then the sodium silicate solution of step one preparation it is added dropwise over, when stirring to redness occurs, stop dropping, and continuously stirred 3 ~ 5min, prepare homogeneous transparent colloid solution, continue the sodium silicate solution that dropping step one prepares, until forming clear gum gel completely, stop dropping, and this clear gum gel is carried out sucking filtration, then 3 ~ 4 times it are washed with deionized, dry at 50 ~ 70 DEG C, prepare silicic acid xerogel, standby；
Step 3, utilize ball mill by step 2 prepare silicic acid xerogel grinds, prepare silica gel powder body, standby；
Step 4, according to boric acid 14 ~ 18%, Borax 10 ~ 17%, limestone 10 ~ 14%, Kaolin 10 ~ 14%, silica flour 0 ~ 15% and the percentage ratio of silica gel powder body 30 ~ 50%, weigh the silica gel powder body that starting boronic acid, Borax, limestone, Kaolin, silica flour and step 3 prepare successively, according to raw material: abrading-ball: the ratio of water=1:1.2:0.8, raw material, abrading-ball and water are placed in ball milling 24h in ball mill, then the material after ball milling is crossed 325 mesh sieves, prepare clear frit.
The preparation method of a kind of lead-free and cadmium-free clear frit the most according to claim 3, it is characterised in that: the acid in step 2 is hydrochloric acid, nitric acid, sulphuric acid or acetic acid；Strong acid weak base salt is ammonium chloride, ammonium nitrate or ammonium sulfate.
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| CN104961336B (en) * | 2015-06-24 | 2018-01-26 | 洛阳师范学院 | A kind of low temperature large red ceramic glaze and preparation method thereof |
| CN105131716A (en) * | 2015-10-16 | 2015-12-09 | 佛山市明朝科技开发有限公司 | Ceramic glossy glaze ink and preparation method thereof |
| CN106316129B (en) * | 2016-08-18 | 2019-02-22 | 云南坤尚科技有限公司 | A kind of manufacture craft of the basic glaze of ceramics |
| CN108250804B (en) * | 2018-01-31 | 2020-05-05 | 洛阳师范学院 | Nano vanadium-zirconium blue ceramic pigment and preparation method thereof |
| CN108751711A (en) * | 2018-07-09 | 2018-11-06 | 界首市伟盛古窑彩陶制作发展有限公司 | A kind of leadless glaze of Anti-bubble defect |
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| CN101182238A (en) * | 2006-11-14 | 2008-05-21 | 霍炳祥 | Clear glaze and method for manufacturing same |
| CN102515533A (en) * | 2011-12-10 | 2012-06-27 | 济南大学 | Alkali silicate glass frit, zirconium frit opaque glaze, zirconium raw material opaque glaze and preparation methods of the zirconium frit opaque glaze and the zirconium raw material opaque glaze |
| CN103044083A (en) * | 2012-12-28 | 2013-04-17 | 福建省佳圣轩工艺品有限公司 | Transparent glaze and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182238A (en) * | 2006-11-14 | 2008-05-21 | 霍炳祥 | Clear glaze and method for manufacturing same |
| CN102515533A (en) * | 2011-12-10 | 2012-06-27 | 济南大学 | Alkali silicate glass frit, zirconium frit opaque glaze, zirconium raw material opaque glaze and preparation methods of the zirconium frit opaque glaze and the zirconium raw material opaque glaze |
| CN103044083A (en) * | 2012-12-28 | 2013-04-17 | 福建省佳圣轩工艺品有限公司 | Transparent glaze and manufacturing method thereof |
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