CN106977097B - Raw glaze for transparent high-gloss medium-temperature hard porcelain and preparation method thereof - Google Patents

Raw glaze for transparent high-gloss medium-temperature hard porcelain and preparation method thereof Download PDF

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Publication number
CN106977097B
CN106977097B CN201610037202.2A CN201610037202A CN106977097B CN 106977097 B CN106977097 B CN 106977097B CN 201610037202 A CN201610037202 A CN 201610037202A CN 106977097 B CN106977097 B CN 106977097B
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Prior art keywords
parts
glaze
porcelain
glaze slip
transparent high
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CN106977097A (en
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张垠
张子祺
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Nanjing Haoqi New Material Co ltd
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Nanjing Haoqi New Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions

Abstract

The invention relates to a raw glaze for transparent high-gloss medium-temperature hard porcelain and a preparation method thereof. A transparent high-gloss medium-temperature hard raw glaze for porcelain comprises 22-32 parts of quartz sand, 1-5 parts of alumina, 10-25 parts of potash feldspar, 22-39 parts of lithium porcelain stone, 5-12 parts of carbide slag, 2-6 parts of dolomite, 4-8 parts of zinc oxide, 0.5-1.5 parts of zirconium silicate, 0-1 part of titanium dioxide and 3-7 parts of Suzhou soil. A preparation method of a raw glaze for transparent high-gloss medium-temperature hard porcelain comprises the following steps: (1) preparing materials; (2) ball milling; (3) detecting the fineness of the glaze slip; (4) sieving the glaze slip qualified by inspection to remove iron; (5) and (5) ageing.

Description

Raw glaze for transparent high-gloss medium-temperature hard porcelain and preparation method thereof
Technical Field
The invention belongs to the field of material science and engineering, relates to a ceramic glaze, and particularly relates to a raw glaze for transparent high-gloss medium-temperature hard ceramics and a preparation method thereof.
Background
The glaze is a silicate mixture, and the glaze applied on the ceramic ware is prepared by grinding quartz, feldspar and clay as raw materials, adding water, mixing, coating on the surface of a blank, roasting at a certain temperature to melt, and forming a vitreous thin layer on the surface of the ceramic ware when the temperature is reduced.
The glaze material adopted by high-grade daily porcelain, especially hard white porcelain, is mainly expressed in the aspects that a blank body has good translucency, high whiteness, high mechanical strength and the like, namely the product meets the aesthetic feeling of modern people, and simultaneously can adapt to mechanical washing, high-temperature quick disinfection and household microwave oven use of hotels and guest houses, and the glaze surface needs to be smooth, moist, soft, good in thermal stability, and capable of withstanding the use of metal knives and forks. Therefore, the glaze quality is an important mark of the grade level of the ceramic product.
At present, the firing temperature of the hard porcelain produced in large scale is about 1350 ℃, the hard porcelain can obtain the daily fine porcelain with high whiteness and high transparency through one-time firing process by selecting high-quality raw materials and fine work, but the hard porcelain has high firing temperature, large energy consumption and environmental load, high production cost and low profit, and the development of the daily porcelain is seriously restricted. Therefore, the research and development of the technology of once firing hard porcelain at medium temperature (the firing temperature of the blank and the glaze is about 1250 ℃, and is basically the same as the bisque firing temperature of the bone china) and the matched glaze thereof becomes the key for promoting the development of advanced daily fine porcelain.
With the improvement of living standard, people have higher and higher requirements on the quality of daily ceramics, and in order to improve the glaze quality of the daily ceramics, fritted glazes are mostly adopted in the ceramic manufacturing industry in recent years to produce the daily white ceramics. The fritted glaze is prepared by melting the used raw materials at high temperature to prepare glass liquid, removing gas generated by decomposing the raw materials in the process so as to reduce the occurrence of glaze defects, quenching the glass liquid with water to prepare the fritted, and grinding the prepared fritted, clay and water according to a certain proportion to prepare glaze slurry, but the fritted glaze has high production cost and large environmental load and cannot represent the future development direction of daily ceramics.
Meanwhile, a large amount of carbide slag (waste slag which is obtained by hydrolyzing carbide to obtain acetylene gas and contains calcium hydroxide as a main component) is accumulated, and research and development of the carbide slag as a resource are urgently needed. The waste material of the carbide slag is developed and used as the raw material for producing the ceramic glaze, so that a new raw material is explored for producing the glaze, and the production cost is reduced.
Disclosure of Invention
The purpose of the invention is as follows: the invention is improved aiming at the problems of the prior art, namely the first object of the invention is to disclose a raw glaze for transparent high-gloss medium-temperature hard porcelain. The second purpose of the invention is to disclose a preparation method of the raw glaze for the transparent high-gloss medium-temperature hard porcelain.
The technical scheme is as follows: a raw glaze for transparent high-gloss medium-temperature hard porcelain comprises:
22-32 parts of quartz sand, 1-5 parts of alumina, 10-25 parts of potassium feldspar, 22-39 parts of lithium porcelain stone, 5-12 parts of carbide slag, 2-6 parts of dolomite, 4-8 parts of zinc oxide, 0.5-1.5 parts of zirconium silicate, 0-1 part of titanium dioxide and 3-7 parts of Suzhou soil.
A preparation method of a raw glaze for transparent high-gloss medium-temperature hard porcelain comprises the following steps:
(1) ingredients
Preparing the following materials in parts by weight: 22-32 parts of quartz sand, 1-5 parts of alumina, 10-25 parts of potassium feldspar, 22-39 parts of lithium porcelain stone, 5-12 parts of carbide slag, 2-6 parts of dolomite, 4-8 parts of zinc oxide, 0.5-1.5 parts of zirconium silicate, 0-1 part of titanium dioxide and 3-7 parts of Suzhou soil;
(2) ball mill
Ball-milling for 14-24 hours according to the mass ratio of 1: 2-3: 0.6-1.2 to obtain glaze slip;
(3) detecting the fineness of the glaze slip
78-84 wt% of particles with the fineness of the glaze slip controlled below 10 mu m (in the glaze, the weight of the particles with the particle size below 10 mu m accounts for 78-84% of the total mass of the glaze),
(4) passing the glaze slip with qualified fineness inspection through a 200-mesh screen and then removing iron;
(5) stale flavor
And ageing the sieved and deironized glaze slip, adjusting the performance of the glaze slip, controlling the specific gravity of the glaze slip to be 1.4-1.6 g/ml and the viscosity to be 400-800 centipoises, and obtaining the transparent high-gloss medium-temperature hard raw glaze for porcelain after adjustment.
Has the advantages that: the invention discloses a transparent high-gloss medium-temperature hard porcelain raw glaze which does not contain any heavy metal components such as lead, cadmium, barium, bismuth and the like in raw material composition, and a certain amount of alkali metal, alkaline earth metal oxide, ZnO and TiO are added2And ZrO2. The fired finished porcelain glaze surface is fine, smooth and flat, and has good glossiness and high hardness; the glaze surface is not easy to fall off due to gloss, no stain is left, the cleaning is easy, and the acid and alkali resistance is good; the invention discloses a transparent high-gloss medium-temperature hard porcelain raw glaze which is prepared by grinding raw materials required by composition design, water and pebbles according to a certain proportion into glaze slip, removing iron, sieving, adjusting the performance of the glaze slip and aging without melting the raw materials at high temperature into glass frit.
The invention discloses a transparent high-gloss medium-temperature hard porcelain raw glaze which is prepared by introducing potassium oxide into potash feldspar, introducing lithium oxide into lithium china stone, introducing magnesium oxide into dolomite, introducing calcium oxide into carbide slag and introducing zirconium oxide into zirconium silicate; the method for producing the transparent glossy glaze generally considers that the glass phase in the glaze is increased during the formula design, the transparency and the glossiness of the glaze can be improved by increasing the glass phase, and the method for improving the glass phase generally increases the use of silicon dioxide, which inevitably causes the firing temperature of the glaze to be increased, the firing is difficult and the flatness of the glaze surface is reduced. In order to reduce the firing temperature, carbonate such as sodium carbonate is generally added, and the use of a large amount of carbonate can generate a large amount of gas, increase the pinholes of the glaze surface, seriously affect the quality of the glaze surface, and simultaneously CO decomposed by the carbonate2Can cause air pollution. In order to solve the problem of mutual restriction, the invention carries out scientific design of formula composition and reasonable selection of raw materials:
Li2O、Na2O、K2o is an effective component for lowering the softening temperature of the glass, appropriately increasing the fluidity of the glass, and increasing the coefficient of thermal expansion of the glaze. To prevent the carbonate from generating a large amount of gas by pyrolysis, minerals are selectedPotassium oxide and sodium oxide are introduced into potassium feldspar of raw materials, and alkali metal oxides such as lithium oxide and the like are introduced into lithium china stones, so that the use of chemical raw materials such as alkali metal carbonate and the like is avoided.
MgO and CaO are effective components for properly adjusting the fluidity, the thermal expansion coefficient and the glossiness of the glass, so that dolomite is selected to introduce magnesia and carbide slag to introduce alkaline earth metal oxides such as calcium oxide, the use of raw materials such as alkaline earth metal carbonate is eliminated, meanwhile, the dolomite and the carbide slag can improve the initial melting temperature of the glaze, and the glaze defects caused by pinholes and bubbles are reduced.
ZnO is a network intermediate, which is generally described as [ ZnO ]6]Octahedron exists in the network of the glass, and when the free oxygen content in the network structure is relatively high, zinc oxide is formed [ ZnO ]4]The glass ceramic enters a glass network to participate in forming the glass network, and a proper amount of ZnO is added into the glass, so that uniform and transparent glass can be generated, the thermal expansion coefficient of the glass is reduced, and the chemical stability and the thermal stability of glaze are improved.
In addition, in order to improve the glossiness, some intermediate oxides of glass network are usually introduced into the glass network, and many high-glossiness glaze compositions contain ions with high polarizability. The invention scientifically designs the chemical composition of glaze and introduces a certain amount of transition metal oxides ZnO and TiO2And ZrO2To improve the gloss of the glaze.
Based on the theory, the raw material composition proportion of the transparent high-gloss medium-temperature hard porcelain raw glaze selects potassium feldspar and lithium porcelain stone as solvents; selecting proper amount of ZnO and TiO2And ZrO2To improve the transparency and glossiness of the glaze; in addition, the dosage of the alumina and the calcium oxide is controlled; the use of carbonate is forbidden, so that the green glaze can achieve the effects of transparency, high gloss and no defect after being fired at 1210-1280 ℃.
The specific implementation mode is as follows:
the following describes in detail specific embodiments of the present invention.
Hereinafter, parts are parts by mass.
Detailed description of the preferred embodiment 1
A raw glaze for transparent high-gloss medium-temperature hard porcelain comprises:
24 parts of quartz sand, 3.5 parts of alumina, 24 parts of potassium feldspar, 23 parts of lithium porcelain stone, 10 parts of carbide slag, 4 parts of dolomite, 6 parts of zinc oxide, 0.3 part of titanium dioxide, 0.7 part of zirconium silicate and 4.5 parts of Suzhou soil.
A preparation method of a raw glaze for transparent high-gloss medium-temperature hard porcelain comprises the following steps:
(1) ingredients
Preparing the following materials in parts by weight: 24 parts of quartz sand, 3.5 parts of alumina, 24 parts of potassium feldspar, 23 parts of lithium porcelain stone, 10 parts of carbide slag, 4 parts of dolomite, 6 parts of zinc oxide, 0.3 part of titanium dioxide, 0.7 part of zirconium silicate and 4.5 parts of Suzhou soil;
(2) ball mill
Ball milling for 16 hours according to the mass ratio of the reference materials, the ball stone and the water of 1: 2: 0.7 to obtain glaze slip;
(3) detecting the fineness of the glaze slip
79 wt% of particles with the particle size of the glaze slip fineness below 10 mu m;
(4) passing the glaze slip with qualified fineness inspection through a 200-mesh screen and then removing iron;
(5) stale flavor
Ageing the glaze slip which is sieved to remove iron, adjusting the performance of the glaze slip, wherein the specific gravity of the glaze slip is 1.58 g/ml, the viscosity of the glaze slip is 720 centipoise, and obtaining the transparent high-gloss medium-temperature hard raw glaze for porcelain after adjustment.
Specific example 2
A raw glaze for transparent high-gloss medium-temperature hard porcelain comprises:
23 parts of quartz sand, 1.5 parts of alumina, 13 parts of potassium feldspar, 38 parts of lithium porcelain stone, 11 parts of carbide slag, 2.5 parts of dolomite, 5.5 parts of zinc oxide, 0.2 part of titanium dioxide, 0.8 part of zirconium silicate and 4.5 parts of Suzhou soil;
a preparation method of a raw glaze for transparent high-gloss medium-temperature hard porcelain comprises the following steps:
(1) ingredients
23 parts of quartz sand, 1.5 parts of alumina, 13 parts of potassium feldspar, 38 parts of lithium porcelain stone, 11 parts of carbide slag, 2.5 parts of dolomite, 5.5 parts of zinc oxide, 0.2 part of titanium dioxide, 0.8 part of zirconium silicate and 4.5 parts of Suzhou soil;
(2) ball mill
Ball milling for 18 hours according to the mass ratio of 1: 2.5: 0.9 of reference materials to the ball stone and water to obtain glaze slip;
(3) detecting the fineness of the glaze slip
Particles with the fineness of the glaze slip below 10 mu m and the particle diameter account for 81 wt%;
(4) passing the glaze slip with qualified fineness inspection through a 200-mesh screen and then removing iron;
(5) stale flavor
Ageing the glaze slip which is sieved to remove iron, adjusting the performance of the glaze slip, wherein the specific gravity of the glaze slip is 1.52 g/ml, and the viscosity of the glaze slip is 590 centipoise, and obtaining the raw glaze for the transparent high-gloss medium-temperature hard porcelain after adjustment.
Specific example 3
A raw glaze for transparent high-gloss medium-temperature hard porcelain comprises:
29.5 parts of quartz sand, 2 parts of alumina, 16 parts of potassium feldspar, 31 parts of lithium porcelain stone, 6 parts of carbide slag, 5 parts of dolomite, 5 parts of zinc oxide, 0.8 part of zirconium silicate and 4.5 parts of Suzhou soil.
A preparation method of a raw glaze for transparent high-gloss medium-temperature hard porcelain comprises the following steps:
(1) ingredients
Preparing the following materials in parts by weight: 29.5 parts of quartz sand, 2 parts of alumina, 16 parts of potassium feldspar, 31 parts of lithium porcelain stone, 6 parts of carbide slag, 5 parts of dolomite, 5 parts of zinc oxide, 0.8 part of zirconium silicate and 4.5 parts of Suzhou soil;
(2) ball mill
Ball milling for 22 hours according to the mass ratio of the reference materials, the ball stone and the water of 1: 3: 1.1 to obtain glaze slip;
(3) detecting the fineness of the glaze slip
The particles with the fineness of glaze slip below 10 mu m and the particle diameter account for 83wt percent; namely, in the glaze, the weight of particles with the particle diameter of less than 10 mu m accounts for 83 percent of the total mass of the glaze;
(4) passing the glaze slip with qualified fineness inspection through a 200-mesh screen and then removing iron;
(5) stale flavor
Ageing the glaze slip which is sieved to remove iron, adjusting the performance of the glaze slip, wherein the specific gravity of the glaze slip is 1.44 g/ml, the viscosity of the glaze slip is 470 centipoise, and obtaining the transparent high-gloss medium-temperature hard raw glaze for porcelain after adjustment.
The embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.

Claims (2)

1. The raw glaze for the transparent high-gloss medium-temperature hard porcelain is characterized by comprising the following components in parts by weight:
22-32 parts of quartz sand, 1-5 parts of alumina, 10-25 parts of potassium feldspar, 22-39 parts of lithium porcelain stone, 5-12 parts of carbide slag, 2-6 parts of dolomite, 4-8 parts of zinc oxide, 0.5-1.5 parts of zirconium silicate, 1 part of titanium dioxide and 3-7 parts of Suzhou soil.
2. A method for preparing a green glaze for transparent high-gloss medium temperature hard porcelain according to claim 1, comprising the steps of:
(1) ingredients
Preparing the following materials in parts by weight: 22-32 parts of quartz sand, 1-5 parts of alumina, 10-25 parts of potassium feldspar, 22-39 parts of lithium porcelain stone, 5-12 parts of carbide slag, 2-6 parts of dolomite, 4-8 parts of zinc oxide, 0.5-1.5 parts of zirconium silicate, 1 part of titanium dioxide and 3-7 parts of Suzhou soil;
(2) ball mill
Ball-milling for 14-24 hours according to the mass ratio of 1: 2-3: 0.6-1.2 to obtain glaze slip;
(3) detecting the fineness of the glaze slip
78-84 wt% of particles with the glaze slurry fineness controlled below 10 mu m;
(4) passing the glaze slip with qualified fineness inspection through a 200-mesh screen and then removing iron;
(5) stale flavor
And ageing the sieved and deironized glaze slip, adjusting the performance of the glaze slip, controlling the specific gravity of the glaze slip to be 1.4-1.6 g/ml, controlling the viscosity of the glaze slip to be 400-800 centipoises, and obtaining the transparent high-gloss medium-temperature hard raw glaze for porcelain after adjustment.
CN201610037202.2A 2016-01-15 2016-01-15 Raw glaze for transparent high-gloss medium-temperature hard porcelain and preparation method thereof Expired - Fee Related CN106977097B (en)

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CN109279780A (en) * 2018-12-18 2019-01-29 湖南华联瓷业股份有限公司 A kind of ceramic glaze and preparation method thereof of resistance to alkali corrosion
CN111517825A (en) * 2020-04-27 2020-08-11 佛山科学技术学院 Ceramic glaze with metal texture and preparation method and application thereof
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JPH0896621A (en) * 1994-09-28 1996-04-12 Agency Of Ind Science & Technol Conductive ceramics
CN101182242A (en) * 2007-11-02 2008-05-21 阳城县侨枫瓷业有限公司 Medium-temperature high-white zirconium-lithium slurry opaque glaze and production method thereof
CN103467067A (en) * 2013-08-15 2013-12-25 淮北市惠尔普建筑陶瓷有限公司 Polished crystal tile

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
JPH0896621A (en) * 1994-09-28 1996-04-12 Agency Of Ind Science & Technol Conductive ceramics
CN101182242A (en) * 2007-11-02 2008-05-21 阳城县侨枫瓷业有限公司 Medium-temperature high-white zirconium-lithium slurry opaque glaze and production method thereof
CN103467067A (en) * 2013-08-15 2013-12-25 淮北市惠尔普建筑陶瓷有限公司 Polished crystal tile

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