CN1186282C - Lead- and zinc-free transparent fritted glaze - Google Patents

Lead- and zinc-free transparent fritted glaze Download PDF

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Publication number
CN1186282C
CN1186282C CN 03131509 CN03131509A CN1186282C CN 1186282 C CN1186282 C CN 1186282C CN 03131509 CN03131509 CN 03131509 CN 03131509 A CN03131509 A CN 03131509A CN 1186282 C CN1186282 C CN 1186282C
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CN
China
Prior art keywords
glaze
unleaded
zinc
clear frit
frit glaze
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN 03131509
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Chinese (zh)
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CN1451622A (en
Inventor
徐和良
范盘华
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BAIFU COLOR GLAZE Co Ltd JIANGSU
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BAIFU COLOR GLAZE Co Ltd JIANGSU
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Priority to CN 03131509 priority Critical patent/CN1186282C/en
Publication of CN1451622A publication Critical patent/CN1451622A/en
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Publication of CN1186282C publication Critical patent/CN1186282C/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form

Abstract

The present invention relates to a fritted glaze without Pb and Zn for ceramic for daily use, which contains 45 to 65% of SiO2, 7 to 12% of Al2O3, 5 to 9% of CaO, 0.5 to 2% of MgO, 1.0 to 5.0% of K2O, 1 to 8% of Na2O, 0 to 8% of SrO, 0.5 to 2.0% of Li2O, 5 to 15% of B2O3, 0 to 0.05% of Fe2O3, 2 to 4% of Bi2O3 and 0.5 to 2.5 % of Y2O3. The fritted glaze without Pb and Zn, which is disclosed by the present invention has the advantages of good blank glaze combination, fine, smooth, bright and flattened glaze surface, brilliant color and no influence to color display.

Description

Unleaded no zinc clear frit glaze
Technical field
The present invention relates to a kind of domestic ceramics fritted glaze, refer to a kind of unleaded no zinc fritted glaze especially.
Technical background
With lead is the glaze of major ingredient, it is good to have melting behaviour, advantages such as specific refractory power is higher, and the glaze glossiness is good, and firing range is wide, but lead glaze goods in use facial pallor are easily separated out, physically and mentally healthy harmful to the user, a lot of leadless glazes have also appearred in the market, and the deficiency of existence is: 1, the under glazed color development is not bright-coloured, and the glaze transparency is relatively poor; 2, the glaze temperature flowing is not enough, easily produces various defectives in glaze firing; 3, firing range is narrow, and production technique is difficult to control.Chinese patent 99120405 disclosed " lead-free fritting enamel for high-grade porcelain " has adopted firing range wide, the zirconium that glossiness is good, the lithium fritted glaze, by quartz, feldspar, zircon, borax, clay, lime carbonate, rhombspar, boric acid, Strontium carbonate powder, Quilonum Retard, bone ash and zinc oxide are made into, glaze is moist, the luminance brightness height, good springiness, physical strength is big, good thermal shock stability, lead release is 0.000ppm, but,, improve the Gloss of Glazes degree though it can reduce the melt temperature of glaze owing to adopt zinc oxide to make flux in its prescription, but its color development influence to the more color pigment of glaze assistant is bigger, and is especially bigger to the influence of chromium tin serial pigment.
Summary of the invention
The present invention is just in order to overcome above-mentioned deficiency, a kind of clear frit glaze of unleaded no zinc is provided, its innovative point is not to be equipped with in the component zinc oxide, adopt rare earth element to make improvements agent, with the PbO in many components mineralizer replacement lead glaze, be to be the fritted glaze of main flux raw material with " boron-strontium-bismuth ", specifically implement like this: unleaded no zinc clear frit glaze, it is characterized in that containing in the component bismuth oxide, its chemical constitution weight percent is:
SiO 2 45-65％
Al 2O 3 7-12％
CaO 5-9％
MgO 0.5-2％
K 2O 1.0-5.0％
Na 2O 1-8％
SrO 0-8％
Li 2O 0.5-2.0％
B 2O 3 5-15％
Fe 2O 3 0-0.05％
Bi 2O 3 2-4％
Y 2O 3 0.5-2.5％
Unleaded no zinc clear frit glaze is characterized in that by potassium felspar sand, albite, quartz, lithium-containing compound the weight percent of selecting for use usually is or/and mineral, carbonate, boride, bismuth oxide and rare earth element calculate proportioning by above-mentioned chemical ingredients forms:
Potassium felspar sand 〉=250 order K 2O+Na 2O 〉=13% 0-30%
Albite 〉=250 order Na 2O 〉=10% 0-25%
Quartz 〉=200 order SiO 2〉=99% Fe 2O 3≤ 0.3% 5-35%
Lithium-containing compound is or/and mineral 1-15%
Carbonate 10-35%
Boride 5-30%
Bismuth oxide 1-6%
Rare earth element 0.1-2%
Best weight proportion is:
Potassium felspar sand 〉=250 order K 2O+Na 2O 〉=13% 5-25%
Albite 〉=250 order Na 2O 〉=10% 5-25%
Quartz 〉=200 order SiO 2〉=99% Fe 2O 3≤ 0.3% 15-35%
Lithium-containing compound is or/and mineral 1-10%
Carbonate 15-30%
Boride 10-25%
Bismuth oxide 2-4%
Rare earth element 0.5-1.5%
The present invention adopts rare earth element to make improvements agent, introduces on a small quantity in the glaze, can thoroughly change network composition in the glaze, changes crystalline structure, reaches the purpose that improves glaze quality, and rare earth element commonly used is a yttrium oxide.
The present invention adopts SrO, K 2O, Na 2O, Li 2O, Bi 2O 3Many components mineralizer replaces the PbO that contains in the lead glaze fully, both can guarantee the glaze glossiness, can guarantee the coupling of the coefficient of expansion again.The specific refractory power of SrO is bigger, can guarantee the high glossiness of glaze, with K 2O, Na 2O makes flux, can make glaze have better glossiness, whiteness and transparency, can significantly improve the glaze coefficient of expansion, Li again simultaneously 2O is a kind of oxide compound with strong fusion effect, can significantly reduce the coefficient of expansion of glaze and increase weather resistance, introduces Li in the strontium glaze 2O can obtain gloss under low temperature of glaze firing, elasticity is better, the glaze that the coefficient of expansion is little, Bi 2O 3Introducing in the glaze, is strong flux, can significantly reduce the melt temperature and the viscosity of glaze, improves the specific refractory power of glaze, forms the high gloss glaze, improves the elasticity of glaze resistance to chemical attack and glaze, has the firing temperature of broad, and the pigment color development is not had influence.
Lithium-containing compound in the component of the present invention also can be selected lithium-containing compounds such as Quilonum Retard for use or/and mineral can be selected mineral such as triphane, lithionite for use; Carbonate as flux in the component can be the one or more combination of rhombspar, Wingdale, Strontium carbonate powder, barium carbonate, Quilonum Retard etc., and boron compound can be the one or more combination of borax, boric acid etc.
In order to introduce potassium, sodium, can also add strong flux nitrate in the component of the present invention, as SODIUMNITRATE, saltpetre etc., add-on is generally 0-8%, can also add Suzhou soil among the present invention to adjust the aluminium content in the proportioning, and add-on is generally less than and equals 10%.
The unleaded no zinc fritted glaze that the present invention relates to, the base glaze is in conjunction with good, and glaze is moist, light is smooth, and it is bright-coloured to develop the color, and does not influence color development.
Embodiment
The raw mineral materials chemical constitution that following examples adopt is:
Material name SiO 2 Al 2O 3 Fe 2O 3 CaO MgO K 2O Na 2O IL
Potassium felspar sand 65.9 2 18.9 4 0.12 0.71 - 11.7 6 2.5 0.39
Albite 69.2 2 18.0 3 0.07 - - 10.3 0.2 0.3
Quartzy 99.4 1 0.27 0.08 - - - - 0.23
Lime carbonate 0.27 0.31 - 55.3 6 0.19 - - 43.87
Rhombspar 0.35 - - 30.0 21.0 - - 47.75
Triphane 65.5 3 24.9 7 0.38 0.21 0.10 0.86 0.91 0.54
Lithionite 51.0 8 22.5 0 0.26 - - 8.52 1.2 5.56
Suzhou soil 48.4 4 36.6 8 0.28 0.19 0.23 0.55 0.47 13.58
Embodiment 1, takes by weighing following material umber: quartz 25, borax 12, rhombspar 3 (〉=200 order Mg0 〉=20%), lime carbonate 8, Strontium carbonate powder 8, potassium felspar sand 10, triphane 8 (Li 2O 〉=5%, Fe 2O 3≤ 0.4%) lithionite 7 (Li, 2O 〉=4.5%, K 2O+Na 2O 〉=9%), albite 9, barium carbonate 4, SODIUMNITRATE 1, saltpetre 1.5, Quilonum Retard 1, bismuth oxide 2, yttrium oxide 0.5 is fired in Cinker clew furnace behind the batch mixing, and shrend gets final product.
Embodiment 2, take by weighing following material umber: quartz 15, borax 15, rhombspar 2 (〉=200 order MgO 〉=20%), lime carbonate 10, Strontium carbonate powder 8, potassium felspar sand 20, albite 14, Suzhou soil 6 (Al 2O 3〉=36%, Fe 2O 3≤ 0.3%), barium carbonate 2, Quilonum Retard 2, bismuth oxide 3, yttrium oxide 1, SODIUMNITRATE 2 is fired in Cinker clew furnace behind the batch mixing, and shrend gets final product.
Embodiment 3, take by weighing following material umber; Quartz 28, boric acid 16, rhombspar 2 (〉=200 order MgO 〉=20%), Suzhou soil 4 (Al 2O 3〉=36%, Fe 2O 3≤ 0.3%), lime carbonate 12, Strontium carbonate powder 7, potassium felspar sand 14.5, albite 10, barium carbonate 2, Quilonum Retard 1.5, bismuth oxide 2.5, yttrium oxide 0.5 is fired in Cinker clew furnace behind the batch mixing, and shrend gets final product.
Embodiment 4, take by weighing following material umber: quartz 27, borax 8, boric acid 12, rhombspar 2 (〉=200 order MgO 〉=20%), lime carbonate 7.5, potassium felspar sand 15, albite 20, barium carbonate 2, Quilonum Retard 2, bismuth oxide 3, yttrium oxide 1.5 is fired in Cinker clew furnace behind the batch mixing, and shrend gets final product.
The fritted glaze that makes after the above-mentioned four routine proportionings its chemical composition after testing is:
Embodiment SiO 2 Al 2O 3 Ca O Mg O K 2O Na 2O B 2O 3 Ba O Fe 2O 3 Li 2O Bi 2O 3 Sr O Y 2O 3
One 56.7 8.0 7. 2 1. 1 3. 2 2.6 5.2 3. 3 0.02 1.4 3.8 7.0 0.58
Two 46.5 10.8 8. 5 0. 5 2. 7 7.9 8.6 1. 9 0.02 1.0 3.6 6.8 1.2
Three 56.2 7.4 8. 9 0. 5 2. 0 1.7 11.0 1. 9 0.02 0.7 3.0 6.0 0.6
Four 60.3 7.8 5. 6 0. 5 2. 0 4.4 11.4 18 0.02 0.9 3.5 - 1.8
Annotate: the industrial chemicals in the foregoing description is a technical grade.

Claims (10)

1. unleaded no zinc clear frit glaze is characterized in that containing in the component bismuth oxide, and the weight percent of its chemical constitution is:
SiO 2 45-65％
Al 2O 3 7-12％
CaO 5-9％
MgO 0.5-2％
K 2O 1.0-5.0％
Na 2O 1-8％
SrO 0-8％
Li 2O 0.5-2.0％
B 2O 3 5-15％
Fe 2O 3 0-0.05％
Bi 2O 3 2-4％
Y 2O 3 0.5-2.5％
2. unleaded no zinc clear frit glaze according to claim 1 is characterized in that by potassium felspar sand, albite, quartz, lithium-containing compound or/and mineral, carbonate, boride, bismuth oxide and rare earth element calculate proportioning by above-mentioned chemical ingredients forms.
3. unleaded no zinc clear frit glaze according to claim 2 is characterized in that the weight percent proportioning of component is:
Potassium felspar sand 〉=250 order K 2O+Na 2O 〉=13% 0-30%
Albite 〉=250 order Na 2O 〉=10% 0-25%
Quartz 〉=200 order SiO 2〉=99% Fe 2O 3≤ 0.3% 5-35%
Lithium-containing compound is or/and mineral 1-15%
Carbonate 10-35%
Boride 5-30%
Bismuth oxide 1-6%
Rare earth element 0.1-2%
4. unleaded no zinc clear frit glaze according to claim 2 is characterized in that the weight percent proportioning of component is:
Potassium felspar sand 〉=250 order K 2O+Na 2O 〉=13% 5-25%
Albite 〉=250 order Na 2O 〉=10% 5-25%
Quartz 〉=200 order SiO 2〉=99% Fe 2O 3≤ 0.3% 15-35%
Lithium-containing compound is or/and mineral 1-10%
Carbonate 15-30%
Boride 10-25%
Bismuth oxide 2-4%
Rare earth element 0.5-1.5%.
5. according to claim 2,3, one of 4 described unleaded no zinc clear frit glaze, it is characterized in that lithium-containing compound or/and mineral are one or more combinations of triphane, lithionite, Quilonum Retard.
6. according to claim 2,3, one of 4 described unleaded no zinc clear frit glaze, it is characterized in that carbonate is the one or more combination of rhombspar, Wingdale, Strontium carbonate powder, barium carbonate, Quilonum Retard.
7. according to claim 2,3, one of 4 described unleaded no zinc clear frit glaze, it is characterized in that boron compound is the one or more combination of borax, boric acid.
8. according to claim 2,3, one of 4 described unleaded no zinc clear frit glaze, it is characterized in that rare earth element is a yttrium oxide.
9. according to claim 2,3, one of 4 described unleaded no zinc clear frit glaze, it is characterized in that adding in the component that nitrate, add-on are arranged is 0-8%.
10. according to claim 2,3, one of 4 described unleaded no zinc clear frit glaze, it is characterized in that adding Suzhou soil in the component, add-on is smaller or equal to 10%.
CN 03131509 2003-05-17 2003-05-17 Lead- and zinc-free transparent fritted glaze Expired - Fee Related CN1186282C (en)

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Application Number Priority Date Filing Date Title
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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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CN1186282C true CN1186282C (en) 2005-01-26

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