CN104609901A - Leadless and cadmiumless transparent glaze and preparation method thereof - Google Patents
Leadless and cadmiumless transparent glaze and preparation method thereof Download PDFInfo
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- CN104609901A CN104609901A CN201510060014.7A CN201510060014A CN104609901A CN 104609901 A CN104609901 A CN 104609901A CN 201510060014 A CN201510060014 A CN 201510060014A CN 104609901 A CN104609901 A CN 104609901A
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Abstract
The invention discloses a leadless and cadmiumless transparent glaze and a preparation method thereof, and relates to the technical field of ceramic glazes. The leadless and cadmiumless transparent glaze is prepared from raw materials consisting of 30-50% of silica gel powder, 14-18% of boric acid, 10-17% of borax, 10-14% of limestone, 10-14% of kaolin and 0-15% of quartz powder, wherein the transparent glaze is prepared by the steps of putting the raw materials, the grinding ball and the water at a ratio of 1:1.2:0.8 in a ball miller, ball milling for 24 hours, sieving the ball-milled materials through mesh size of 80. The raw materials provided by the invention are leadless and cadmiumless and easy to prepare, and the solvent is deionized water which is safe, nontoxic, pollution-free, cheap, and low in cost and convenient for mass production; the glaze prepared by the invention can be directly sintered, which has a low melting temperature, good gloss, wide firing temperature range and smooth and transparent surface; the leadless and cadmiumless transparent glaze has the advantages of good melting performance, easily controlled preparation condition, low production cost and high production efficiency.
Description
Technical field
The present invention relates to ceramic glaze technical field, be specifically related to a kind of lead-free and cadmium-free transparent and preparation method thereof.
Background technology
Transparent refers to the barment tag of glaze, the indefiniteness vitreum that glaze generates 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 use the fritted glaze containing plumbous, this is because leaded glaze has easy melting, good fluidity, the features such as thermal expansivity is little, good thermal shock stability, and physical strength is large, the plumbous heavy metal element that waits is fired through certain technique, can make ceramic surface bright-coloured lucid and lively, svelteness, glossiness are high, elasticity is large, and firing range is wide and be used widely.But because lead glaze is poisonous, to the health of production environment, operator and end user, there is 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 people to leadless glaze is day by day paid attention to.In recent years, existing large quantities of leadless glaze is succeeded in developing, and comes into operation, but just the present Research of 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; Meanwhile, because oxide compound affects more complicated to lead-free fritting enamel temperature, leadless glaze ceramic is caused cannot to be protected in outward appearance and performance, glaze poor transparency.
Summary of the invention
Technical problem to be solved by this invention is that to overcome existing fritted glaze melt temperature high, is difficult to the defect ensureing its outward appearance and performance, provides a kind of lead-free and cadmium-free transparent and preparation method thereof.
The present invention for the adopted technical scheme that solves the problem is: a kind of lead-free and cadmium-free transparent, is prepared from by the raw material of following weight percent: silica gel powder 30 ~ 50%, boric acid 14 ~ 18%, borax 10 ~ 17%, Wingdale 10 ~ 14%, kaolin 10 ~ 14% and silica powder 0 ~ 15%.
The main chemical compositions of the transparent that the present invention is prepared from and the mass percent of each chemical composition are: SiO
235 ~ 55%, B
2o
315 ~ 20%, Na
2o 2 ~ 5%, CaO 5 ~ 8%, Al
2o
34 ~ 9%, surplus is inevitable impurity.
The preparation method of lead-free and cadmium-free transparent of the present invention, comprises the following steps: step one, take water glass powder, is dissolved in a certain amount of deionized water and fully stirs, obtained saturated sodium silicate solution, which, for subsequent use;
Step 2, measured amounts acid or strong acid weak base salt, add deionized water, be configured to the solution of 5mol/L, and 1 ~ 2 phenolphthalein solution is dripped in this solution, then sodium silicate solution prepared by step one is dropwise added, be stirred to redness when occurring, stop dripping, and Keep agitation 3 ~ 5min, obtained homogeneous transparent colloidal solution, continue to drip the obtained sodium silicate solution of step one, until be fully formed clear gum gel, stop dripping, and this clear gum gel is carried out suction filtration, then deionized water wash is used 3 ~ 4 times, dry at 50 ~ 70 DEG C, obtained silicic acid xerogel, for subsequent use,
Step 3, the silicic acid xerogel grinds utilizing ball mill step 2 to be obtained, obtained silica gel powder, for subsequent use;
Step 4, according to the per-cent of boric acid 14 ~ 18%, borax 10 ~ 17%, Wingdale 10 ~ 14%, kaolin 10 ~ 14%, silica powder 0 ~ 15% and silica gel powder 30 ~ 50%, take the silica gel powder that starting boronic acid, borax, Wingdale, kaolin, silica powder and step 4 are obtained 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 mill ball milling 24h, then the material after ball milling is crossed 325 mesh sieves, obtained transparent.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, sulfuric 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 adopt sol-gel method to prepare Silica hydrogel, and silica gel powder is applied in glaze preparation as the main raw material of glaze, Silica hydrogel is made to form the Coagulating binding phase of ceramic glaze together with other batching, thus make glaze have the essential characteristic of zeolite minerals, dehydration temperature wide ranges, dehydration not only can not destroy bonding strength, the three-dimensional structure of glaze paint also can be made more stable, improve glaze paint 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, nontoxic, pollution-free, and low price is with low cost, be convenient 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 controlled, production cost is low, and production efficiency is high.
(3), in the present invention, Al
2o
3by kaolin (Al
2o
32SiO
22H
2o) introduce, Al
2o
3form the network body of glaze, can with SiO
2in conjunction with, also can be combined with basic oxide; The SiO introduced by silica powder
2, SiO
2the 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 invention
2with 5 ~ 8%CaO, the ratio of the two can improve the mobility of glaze, strengthens the tinting strength of glaze.
(4) B of 15 ~ 20% is contained in the glaze that, prepared by the present invention
2o
3, B
2o
3can form low-melting mixtures with silica-gel powder body, reduce the melt temperature of glaze, glaze melt viscosity reduces, and mobility increases, and is easy to sprawl into smooth glaze paint, B
2o
3add the specific refractory power that can increase glaze, improve glossiness.In the present invention, the consumption of silica powder should be reduced as far as possible, make it be converted into glassy phase to greatest extent, thus decrease the amount of residual quartz and cristobalite in finished product, significantly reduce the thermal expansivity of base substrate; In glaze, because quartz is melted substantially as vitreous state, so reduce the consumption of quartz in glaze, decrease the effect of Si-O structure bonding force, improve glaze thermal expansivity.
Embodiment
Be described further lead-free and cadmium-free transparent of the present invention and preparation method thereof below in conjunction with specific embodiment, to make those skilled in the art the present invention may be better understood and can be implemented, but illustrated embodiment is not as a limitation of the invention.
A kind of lead-free and cadmium-free transparent, is prepared from by the raw material of following weight percent: silica gel powder 30 ~ 50%, boric acid 14 ~ 18%, borax 10 ~ 17%, Wingdale 10 ~ 14%, kaolin 10 ~ 14% and silica powder 0 ~ 15%.The main chemical compositions of the transparent be prepared from and the mass percent of each chemical composition are: SiO
235 ~ 55%, B
2o
315 ~ 20%, Na
2o 2 ~ 5%, CaO 5 ~ 8%, Al
2o
34 ~ 9%, surplus is inevitable impurity.
Embodiment 1
A preparation method for lead-free and cadmium-free transparent, comprises the following steps: step one, take water glass powder, is dissolved in a certain amount of deionized water and fully stirs, obtained saturated sodium silicate solution, which, for subsequent use;
The acid of step 2, measured amounts or strong acid weak base salt, add deionized water, be configured to the solution of 5mol/L, and 1 ~ 2 phenolphthalein solution is dripped in this solution, then dropwise add sodium silicate solution prepared by step one, be stirred to redness when occurring, stop dripping, continue to stir, obtained homogeneous transparent colloidal solution, for subsequent use;
The obtained sodium silicate solution of step one is dropwise added in step 3, the colloidal solution prepared in step 2, until be fully formed clear gum gel, stop dripping, and this clear gum gel is carried out suction filtration, then deionized water wash is used 3 ~ 4 times, dry at 50 ~ 70 DEG C, obtained silicic acid xerogel, for subsequent use;
Step 4, the silicic acid xerogel grinds utilizing ball mill step 3 to be obtained, obtained silica gel powder, for subsequent use;
Step 5, take the obtained silica gel powder 50.00g of starting boronic acid 14.00g, borax 10.00g, Wingdale 10.00g and kaolin 10.00g, silica powder 6.00g and step 4 successively, be placed in zirconia ball grinding jar; Take 120g zirconium white ball milling ball to put into this ball milling and fill with, 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, obtained transparent, 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 according to step one to step 4 in embodiment 1, and take this silica gel powder 39.40g, boric acid 15.15g, borax 15.15g, Wingdale 12.12g and kaolin 18.18g, be placed in zirconia ball grinding jar; Take 120g zirconium white ball milling ball to put into this ball milling and fill with, 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, obtained transparent, 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 according to step one to step 4 in embodiment 1, and take this silica gel powder 40.00g, boric acid 16.00g, borax 13.00g, Wingdale 12.00g, kaolin 12.00g and silica powder 7.00g, be placed in zirconia ball grinding jar; Take 120g zirconium white ball milling ball to put into this ball milling and fill with, 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, obtained transparent, 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 the need to making melt, and the bake out temperature of preparation process is lower, and firing temperature during use, lower than 1000 DEG C, avoids B
2o
3volatilization.
Embodiment 4
Prepare silica gel powder according to step one to step 4 in embodiment 1, and take this silica gel powder 30.00g, boric acid 18.00g, borax 17.00g, Wingdale 14.00g, kaolin 14.00g and silica powder 7.00g, be placed in zirconia ball grinding jar; Take 120g zirconium white ball milling ball to put into this ball milling and fill with, 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, obtained transparent, retention 0.5 ~ 2.5% on sieve.Obtained glaze glazing thickness is 0.8 ~ 1.0mm, and firing temperature is 800 ~ 1000 DEG C.Remain with kaolin in obtained glaze, suspension and the bonding strength of glaze slip can be improved.Glazing thickness is 0.8 ~ 1.0mm, and firing temperature is 800 ~ 1000 DEG C.
By the obtained glaze of embodiment 1 ~ embodiment 4, adopt glaze method to the glazing of four parts of sample base substrates, glazing thickness is 0.8 ~ 1.0mm, naturally dry, be then placed in retort furnace, with the heating gradient of 10 DEG C, be warming up to 750 ~ 850 DEG C, then at 900 ~ 1000 DEG C, be incubated 30min; Open fire door, make sample Temperature fall to 60 DEG C, take out each sample air cooling to room temperature.Observe glaze paint situation, evaluate glaze paint: the glaze paint flat smooth of embodiment 1 ~ 4 sample, glaze paint glossiness is good, and transparency is high, and glaze-body bonding is good; Water-intake rate < 0.5%, folding strength > 50MPa, product is flawless by 20 ~ 150 DEG C of temperature.
Claims (4)
1. a lead-free and cadmium-free transparent, is characterized in that: be prepared from by the raw material of following weight percent: silica gel powder 30 ~ 50%, boric acid 14 ~ 18%, borax 10 ~ 17%, Wingdale 10 ~ 14%, kaolin 10 ~ 14% and silica powder 0 ~ 15%.
2. a kind of lead-free and cadmium-free transparent according to claim 1, is characterized in that: the main chemical compositions of the transparent be prepared from and the mass percent of each chemical composition are: SiO
235 ~ 55%, B
2o
315 ~ 20%, Na
2o 2 ~ 5%, CaO 5 ~ 8%, Al
2o
34 ~ 9%.
3. the preparation method of a kind of lead-free and cadmium-free transparent according to claim 1, is characterized in that, comprise the following steps:
Step one, take water glass powder, be dissolved in a certain amount of deionized water and fully stir, obtained saturated sodium silicate solution, which, for subsequent use;
Step 2, measured amounts acid or strong acid weak base salt, add deionized water, be configured to the solution of 5mol/L, and 1 ~ 2 phenolphthalein solution is dripped in this solution, then sodium silicate solution prepared by step one is dropwise added, be stirred to redness when occurring, stop dripping, and Keep agitation 3 ~ 5min, obtained homogeneous transparent colloidal solution, continue to drip the obtained sodium silicate solution of step one, until be fully formed clear gum gel, stop dripping, and this clear gum gel is carried out suction filtration, then deionized water wash is used 3 ~ 4 times, dry at 50 ~ 70 DEG C, obtained silicic acid xerogel, for subsequent use,
Step 3, the silicic acid xerogel grinds utilizing ball mill step 2 to be obtained, obtained silica gel powder, for subsequent use;
Step 4, per-cent according to boric acid 14 ~ 18%, borax 10 ~ 17%, Wingdale 10 ~ 14%, kaolin 10 ~ 14%, silica powder 0 ~ 15% and silica gel powder 30 ~ 50%, take the silica gel powder that starting boronic acid, borax, Wingdale, kaolin, silica powder and step 4 are obtained 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 mill ball milling 24h, then the material after ball milling is crossed 325 mesh sieves, obtained transparent.
4. the preparation method of a kind of lead-free and cadmium-free transparent according to claim 3, is characterized in that: the acid in step 2 is hydrochloric acid, nitric acid, sulfuric acid or acetic acid; Strong acid weak base salt is ammonium chloride, ammonium nitrate or ammonium sulfate.
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Cited By (7)
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| CN104961336A (en) * | 2015-06-24 | 2015-10-07 | 洛阳师范学院 | Low-temperature bright 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 |
| CN106316129A (en) * | 2016-08-18 | 2017-01-11 | 云南坤尚科技有限公司 | Manufacturing process of ceramic base glaze |
| CN108250804A (en) * | 2018-01-31 | 2018-07-06 | 洛阳师范学院 | A kind of nano V zirconium indigo plant 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961336A (en) * | 2015-06-24 | 2015-10-07 | 洛阳师范学院 | Low-temperature bright 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 |
| CN106316129A (en) * | 2016-08-18 | 2017-01-11 | 云南坤尚科技有限公司 | Manufacturing process of ceramic base glaze |
| 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 |
| CN108250804A (en) * | 2018-01-31 | 2018-07-06 | 洛阳师范学院 | A kind of nano V zirconium indigo plant ceramic pigment and preparation method thereof |
| 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 |
| CN112279687A (en) * | 2020-11-20 | 2021-01-29 | 广东欧文莱陶瓷有限公司 | Ceramic tile with gold texture and preparation method thereof |
| CN112979164A (en) * | 2021-03-24 | 2021-06-18 | 亚细亚建筑材料股份有限公司 | Volcanic flow rock effect digital glaze ink and preparation method and application thereof |
| CN112979164B (en) * | 2021-03-24 | 2022-08-19 | 亚细亚建筑材料股份有限公司 | Volcanic flow rock effect digital glaze ink and preparation method and application thereof |
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| CN104609901B (en) | 2016-08-24 |
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