Be applicable to the lead-free fritting enamel that twice firing is used
Technical field
The present invention relates to a kind of improved lead-free fritting enamel, be applicable to the twice firing of multiple porcelain.
Background technology
Along with people to natural cognitive ability and growth in the living standard, the many source of pollution in our daily life are found.For ensureing that the mankind live more healthily, be the earth Sustainable development that ensures that the mankind depend on for existence, people have formulated various restrictions and standard, and this wherein just comprises the domestic ceramics based article closely bound up with the human lives.
Being in the high-grade daily-use fine porcelain of characteristics with twice firing (high temperature biscuiting, low temperature glaze firing) in the world, is the main flow kind with the sclerotin porcelain, the history in existing more than 200 year.To twentieth century the 1970s and 1980s, succeed in developing steatite ceramic, quartz enriched porcelain again in Shandong, to the twentieth century end, succeeded in developing the high-grade daily-use fine porcelain of twice firings such as synthetic sclerotin porcelain again, these high-grade town of porcelains must use fritted glaze.
Because excellent appearance and Practical Performance that lead compound brought, the glaze of for example bright jade-like stone profit, good glaze fit and wide firing range, this leaded glaze was used by domestic and international high-grade daily-use fine porcelain (soft porcelain) manufacturer over more than 200 year always.But there is a fatal weakness in this lead glaze that contains, and that is exactly the harm to environment and human body of the lead poisoning that causes in glaze processing and the use at pottery.
The intravital average lead tolerance of modern has been 500 times of ancients before 1000 according to authoritative report of survey! And the mankind lack initiatively, effective safeguard procedures.Lead is invaded the cerebral nerve tissue by blood after entering human body, almost all internal organs of human body is all worked the mischief! Particularly children are in growth and development stage, and the grownup is more responsive to lead ratio, thus to the absorbed dose of lead than high several times of grownup, it is particularly serious to be injured.Lead enters also seriously influences fetation in pregnant woman's body, cause deformity etc.Prevent lead poisoning effectively, become one of problem that current scientist explores, captures.
Strict restriction has been made to lead, the quantity of cadmium release of ceramics ware for daily use in countries in the world.At present, the China national compulsory standard is defined as plumbous, quantity of cadmium release, the lead release of flat articles must not surpass 5/1000000ths (≯ 5ppm), quantity of cadmium release must not surpass 5/1000000ths (≯ 0.5ppm); FDA (FDA) standard be flat class vessel lead release must not surpass 3/1000000ths (≯ 3ppm); California, USA six or five agreements stipulate flat class vessel lead release must not surpass 1,000,000/point two two or six (≯ 0.226ppm); Europe newest standards also be defined in lead release must not surpass 1,000,000/point two (≯ 0.2ppm).
In recent years, high-grade daily-use fine porcelain manufacturer is strong day by day to the demand of the unleaded molten fast glaze of high quality both at home and abroad, multiple lead-free fritting enamel occurred thereupon, forms difference, and performance is different.Have plenty of self product quality problem, the glaze plane defect is many, bubbles, no optical phenomenon is serious, become the major obstacle of the high-grade porcelain production of twice firing always; Have plenty of adaptability and be restricted, the leadless glaze that has is only limited on sclerotin porcelain, the quartz enriched porcelain and is suitable for, and can not use on steatite ceramic, or the like.
Summary of the invention
The object of the present invention is to provide a kind of lead-free fritting enamel that is applicable to that twice firing is used, brand-new composition, stable and reliable product quality, wide adaptability.
The lead-free fritting enamel that is applicable to that twice firing is used of the present invention, its product chemistry weight percent consists of:
SiO
235.0 Al~60.0%,
2O
314.0~18.0%, CaO 3.0~10.0%, MgO 0.0~5.0%, K
2O 5.0~10.0%, Na
2O 2.0~5.0%, ZnO 5.0~10.0%, B
2O
34.0~12.0%, SrO 1.0~5.0%, Li
2O 0.0~1.0%, BaO 0.0~8.0% and ZrO
25.0~9.0%.
Best group becomes:
SiO
240.0 Al~55.0%,
2O
314.0~16.0%, CaO 3.5~8.5%, MgO 0.0~3.5%, K
2O 5.0~8.0%, Na
2O 2.0~4.0%, ZnO 5.0~8.0%, B
2O
36.0~10.0%, SrO 1.0~4.0%, Li
2O 0.0~0.5%, BaO 1.0~5.0% and ZrO
25.0~7.0%.
Corresponding with it, its batching consists of with the weight percent of raw material:
Feldspar 35.0~60.0%, quartz 4.0~20.0%, aluminium hydroxide 0.0~10.0%, talcum 1.0~10.0%, light calcium carbonate 5.0~20.0%, zinc oxide 1.0~10.0%, borax 5.0~15.0%, boric acid 2.0~10.0%, Strontium carbonate powder 0.0~10.0%, Quilonum Retard 0.0~5.0%, barium carbonate 1.0~10.0%, kaolin 5.0~25.0% and zirconium white 5.0~10.0%.
Best group becomes:
Feldspar 40.0~55.0%, quartz 4.0~15.0%, aluminium hydroxide 0.0~7.0%, talcum 1.0~6.0%, light calcium carbonate 5.0~15.0%, zinc oxide 2.0~8.0%, borax 5.0~10.0%, boric acid 3.0~8.0%, Strontium carbonate powder 1.0~8.0%, Quilonum Retard 0.0~4.0%, barium carbonate 1.0~8.0%, kaolin 7.0~20.0% and zirconium white 5.0~8.0%.
Among the present invention:
(1) Al
2O
3Content is higher, obtains suitable high temperature viscosity and surface tension, and glass structure is stable, avoids producing the glaze bubble.
(2) ZrO
2Content is higher, improves the high temperature viscosity and the surface tension of glaze, reduces the rising power of glaze bubble; Slight opaque effect can improve the glaze whiteness, improves hardness of glaze surface and erosion resistance.Simultaneously, increase ZrO
2The contact surface of molecule and other compositions is brought into play its effectiveness more fully.
Lead-free fritting enamel preparation method of the present invention is basic identical with common fritted glaze preparation method, and the raw material beyond the kaolin is mixed, and carries out high temperature melting and becomes frit, and then pulverize with the kaolin mixed grinding that to make glaze standby.According to enameling method glazing on biscuit of conventional twice firing, carry out twice firing again and get final product, the firing range of adaptation is 1130 ℃~1170 ℃.The technology identical with existing routine techniques repeats no more.
Prove through test of many times, lead-free fritting enamel of the present invention is because the innovation (high alumina, high zirconium) on forming, make it be applicable to the multiple biscuiting base substrate of magnesia porcelain, sclerotin porcelain, quartz enriched porcelain, fine pottery etc., equal matched well with it, reach high intensity and thermostability, the magnesia porcelain that especially can adapt to unique properties has preferably solved the optical issue of covering of magnesia ceramic glaze surface.Use fritted glaze of the present invention, can obtain good glaze quality, finished product rate height, the ratio of first-grade products can reach 92%, and the present invention is unleaded, the cadmium composition, and plumbous, quantity of cadmium release is zero naturally, has fundamentally stopped plumbous, plumbous, the cadmium stripping of cadmium, health environment-friendly.
Description of drawings
Fig. 1, lead-free fritting enamel preparation technology FB(flow block) of the present invention.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
The embodiment 1-4 of lead-free fritting enamel of the present invention sees Table 1.
(continued on next page)
The proportion material of table 1, lead-free fritting enamel and corresponding chemical weight percentage composition table
Annotate: the part of less than 100% is Fe in the chemical weight percentage composition
2O
3, TiO
2Etc. conventional raw mineral materials impurity.
Lead-free fritting enamel preparation method of the present invention is basic identical with common fritted glaze preparation method, and the raw material beyond the kaolin is mixed, and carries out high temperature melting and becomes frit, and then pulverize with the kaolin mixed grinding that to make glaze standby.According to enameling method glazing on biscuit of conventional twice firing, carry out twice firing again and get final product.
The main performance index of each embodiment of lead-free fritting enamel of the present invention sees Table 2.
Table 2, each embodiment main performance index table
Lead-free fritting enamel of the present invention is tested on multiple porcelain base substrate, and wherein typical porcelain sees Table 3 for example.
The base substrate chemistry weight percentage composition table of table 3, test porcelain kind
The performance index of lead-free fritting enamel of the present invention on the above-mentioned porcelain kind base substrate of enumerating see Table 4.
Test sees Table 5 with the chemical weight percentage composition of raw material.
(continued on next page)
Table 4, the performance index table of lead-free fritting enamel of the present invention on various porcelain kinds
Table 5, the test chemical weight percentage composition table of raw material
Embodiment 5
The present invention is applicable to the lead-free fritting enamel that twice firing is used, and its batching consists of with the weight percent of raw material:
Feldspar 35.5%, quartz 15.0%, talcum 3.5%, light calcium carbonate 6.0%, zinc oxide 3.0%, borax 8.0%, boric acid 2.0%, Quilonum Retard 2.0%, barium carbonate 8.0%, kaolin 10.0% and zirconium white 7.0%.
Embodiment 6
The present invention is applicable to the lead-free fritting enamel that twice firing is used, and its batching consists of with the weight percent of raw material:
Feldspar 38.0%, quartz 12.0%, aluminium hydroxide 5.0%, talcum 5.0%, light calcium carbonate 5.0%, zinc oxide 2.0%, borax 10.0%, boric acid 4.0%, Strontium carbonate powder 2.0%, barium carbonate 3.0%, kaolin 6.0% and zirconium white 8.0%.
Embodiment 7
The present invention is applicable to the lead-free fritting enamel that twice firing is used, and its batching consists of with the weight percent of raw material:
Feldspar 52.0%, quartz 7.0%, talcum 1.0%, light calcium carbonate 5.5%, zinc oxide 1.0%, borax 6.0%, boric acid 2.0%, Strontium carbonate powder 0.5%, barium carbonate 5.0%, kaolin 15.0% and zirconium white 5.0%.
Embodiment 8
The present invention is applicable to the lead-free fritting enamel that twice firing is used, and its batching consists of with the weight percent of raw material:
Feldspar 45.0%, quartz 8.0%, aluminium hydroxide 1.0%, talcum 3.0%, light calcium carbonate 7.0%, zinc oxide 2.5%, borax 10.0%, boric acid 4.0%, Strontium carbonate powder 0.5%, Quilonum Retard 1.0%, barium carbonate 4.0%, kaolin 6.0% and zirconium white 8.0%.