WO2008050937A1 - Seger formulas for the body and glaze composition of no-crack heat resistant porcelain - Google Patents

Seger formulas for the body and glaze composition of no-crack heat resistant porcelain Download PDF

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Publication number
WO2008050937A1
WO2008050937A1 PCT/KR2007/001072 KR2007001072W WO2008050937A1 WO 2008050937 A1 WO2008050937 A1 WO 2008050937A1 KR 2007001072 W KR2007001072 W KR 2007001072W WO 2008050937 A1 WO2008050937 A1 WO 2008050937A1
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Prior art keywords
mol
glaze
added
heat resistant
resistant porcelain
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PCT/KR2007/001072
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French (fr)
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Chang-Lim Park
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Phoenix Ceramics Co., Ltd.
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Publication of WO2008050937A1 publication Critical patent/WO2008050937A1/en

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    • C04B33/00—Clay-wares
    • C04B33/24—Manufacture of porcelain or white ware
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/04—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers
    • B28B11/044—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers with glaze or engobe or enamel or varnish
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    • 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
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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    • 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
    • C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Definitions

  • the examples are normal heated cooking utensils or ware bowls.
  • the necessary properties of these containers are those of high thermal shock resistance, which means they can resist rapid heating and cooling.
  • thermal shock resistance As the thermal conduction and the toughness of ceramic wares are low, sudden temperature changes cause the change of capacity in and out, and then internal stress, produced from it, cause so-called destructions by thermal shock.
  • These Ceramics have the property of high thermal shock resistance.
  • the materials of body should have a low coefficient of thermal expansion in order to have high thermal shock resistance.
  • Cordierite(2MgO • 2AI2O3 • 5SiU2) which has been made from early times, thanks to the property of high thermal shock resistance, is excellent material but it can x t endure sudden temperature changes above appropriate level. It is impossible to make the coefficient of thermal expansion zero with Cordierite , which is the most affectable to property of high thermal shock resistance. Thus sometimes the wares can be destroyed while being used.
  • Ceramics are glazed so as to prevent water permeability and to look beautiful.
  • no-crack heat resistant porcelain Most important thing for making no-crack heat resistant porcelain is to make the body and the glaze from the materials which have excellent heat resistance and an extremely low coefficient of thermal expansion; petalite and lithia mica ( Li2 ⁇ -Al2 ⁇ 3 ⁇ Si ⁇ 2 class)are good materials. Products are made of these materials as the main parts, and the viscous material (clay or kaolin) should be added, so that the mechanical strength, necessary while being used in everyday life, can be maintained.
  • the heat resistant porcelain without any cracks on the glazed surface is made as shown in drawing 1, if the rate of heat expansion of the body and that of the glaze are harmonious.
  • Drawing2a The rates of heat expansion of body of this invention after firing Drawing2b.
  • the main material of this invention is petalite and Lithia mica, which have excellence in property of high thermal shock resistance and a slightly low coefficient of heat expansion.
  • Petalite and Lithia mica are the resources of U2O as a flux and that of AI2O3 and S1O2 .
  • Clay ingredients are the resources of U2O as a flux and that of AI2O3 and S1O2 .
  • the Seger formula for the body of no-crack heat resistant porcelain is 0.20-0.45 mol of Li 2 O, 0.13-0.35 mol of MgO, 0.01-0.05 mol of Na 2 O, 0.01-0.12 mol of K 2 O, 0.01-0.06 mol of CaO, 0.01-0.02 mol of ZnO, 1 mol of Al 2 O 3 , 3.80-5.20 mol of SiO 2 . 0.01-0.10 mol of ZrO 2 , 0.01-0.02 mol of TiO2.
  • the raw materials are mixed to produce the body, which is formalized and heated into the porcelain
  • the main material is Petalite and Lithia mica, thanks to their excellent thermal shock resistance and low coefficient of heat expansion. A proper amount of clay ingredient is added to give plasticity to
  • the Seger formula of the glaze composition of no-crack heat resistant porcelain is 0.65-0.91 mol of Li 2 O, 0.02-0.10 mol of BaOCor 0.01-0.10 mol of PbO), 0.01-0.05 mol"of Na 2 O, 0.01-0.05 mol of K 2 O, 0.01-0.10 mol of CaO, 0.01-0.05 mol of ZnO, 0.35-1.40 mol of Al 2 O 3 , 0.01-0.10 mol of B 2 O 3 . 0.00-0.02 mol of Fe 2 O 3 , 2.95-7.50 mol of SiO 2 , 0.01-0.04 molecular equivalent of ZrO 2 , and the glaze was made properly according to this Seger formula.
  • the XRD graph of this invention after firing is shown in Drawing 3a and 3b.
  • the XRD graph of body composition of the invention shows that the crystal is Lithium Aluminum Silicate(Lio.6Alo.6Si 2 .4 ⁇ 6, LiAlSi 3 Os, and LiAlSi 2 Oe : Li 2 O-Al 2 O 3 -SiO 2 system). These crystals are considered to make the rate of heat expansion negative.
  • the XRD graph of glaze composition of the invention shows that the main are Lithium Aluminum Silicate(LiAlSi2 ⁇ 6, Lio.6Alo.6Si2.4O6, :
  • This invention can be helpful for health by preventing the porcelains from being polluted by detergents when washed, because they don't have cracks in spite of rapid heating and cooling.
  • This can extend a range of heat resistant porcelain manufacture, and the manufacture skill of the no-crack heat resistant porcelain can sustain and extend this industry.
  • manufacture of the no-crack heat resistant porcelain is able to make a white porcelain possible, and so it can satisfy the consumers' desire by providing them with excellent goods in various colors and designs.

Abstract

In this invention, the Seger formula of the body is, Li2O of 0.20∼0.45 mol, MgO of 0.13∼0.35 mol, Na2O of 0.01∼0.05 mol, K2O of 0.01∼0.12 mol, CaO of 0.01∼0.06 mol, ZnO of 0.01∼0.02 mol, Al2O3 of 1 mol, SiO2 of 3.80∼5.20 mol, ZrO2 of 0.01∼0.10 mol, TiO2 of 0.01∼0.02 mol. The body is made of the composition according to this Seger formula. The Seger formula of the glaze composition of no-crack heat resistant porcelain is, Li2O of 0.65∼0.91 mol, BaO of 0.02∼0.10 mol(or PbO of 0.01∼0.10 mol), Na2O of 0.01∼0.05 mol, K2O of 0.01∼0.05 mol, CaO of 0.01∼0.10 mol, ZnO of 0.01∼0.05 mol, Al2O3 of 0.35∼1.40 mol, B2O3 of 0.01∼0.10 mol, Fe2O3 of 0.00∼0.02 mol, SiO2 of 2.95∼7.50 mol, ZrO2 of 0.01∼0.04 mol. The glaze is made of the composition according to this Seger formula. No-crack heat resistant porcelain is made according to these two Seger formulas.

Description

Description
[Title of Invention]
Seger formulas for the body and glaze composition of no-crack heat resistant porcelain
[Specific explanation of Invention] [Purpose of Invention] [Technical Field]
Some of food vessels, used in everyday life, need to be rapidly heated or cooled. The examples are normal heated cooking utensils or ware bowls. The necessary properties of these containers are those of high thermal shock resistance, which means they can resist rapid heating and cooling. As the thermal conduction and the toughness of ceramic wares are low, sudden temperature changes cause the change of capacity in and out, and then internal stress, produced from it, cause so-called destructions by thermal shock. These Ceramics have the property of high thermal shock resistance. The materials of body should have a low coefficient of thermal expansion in order to have high thermal shock resistance. Cordierite(2MgO • 2AI2O3 • 5SiU2) which has been made from early times, thanks to the property of high thermal shock resistance, is excellent material but it canx t endure sudden temperature changes above appropriate level. It is impossible to make the coefficient of thermal expansion zero with Cordierite , which is the most affectable to property of high thermal shock resistance. Thus sometimes the wares can be destroyed while being used.
However, in 1948, an American, Hummel found that the body, made of Petalite, has excellent thermal shock resistance, thus has a very low coefficient of thermal expansion. After that times, U2θ-Al2θ3-Siθ2 class attract special interests as the material of the heat resistant porcelain and , in reality, has been made into heat resistant cooking vessels. This Li2O-Al2O3-SiO2 class include eucryptiteGiijO • Al2O3 • 2SiO2), sρodumene(Li2θ-Al2θ3-4Siθ2), petalite(Li2O-Al2θ3-8SiO2) and the mixture of herein above. However, Petalite has been the main material and has been made into porcelains because it can be mined natively. [Background Art]
Ceramics are glazed so as to prevent water permeability and to look beautiful.
It is important that the coefficient of thermal expansion of body and glaze should be low and should be adjusted appropriately, because ceramics should be able to endure rapid heating and cooling.
However, the ware products that have been produced and sold till now, tend to have minute cracks 0.1~2μm of diameter on the glazed surface, as shown in drawing 1. And while washing, these ceramic wares contain detergents or dregs in their cracks and then when boiled for cooking, the impurities come out to the food, they can be harmful for people's health unconsciously. Finally they have a bad effect on citizen's health.
[Technical assignment for invention]
Most important thing for making no-crack heat resistant porcelain is to make the body and the glaze from the materials which have excellent heat resistance and an extremely low coefficient of thermal expansion; petalite and lithia mica ( Li2θ-Al2θ3~Siθ2 class)are good materials. Products are made of these materials as the main parts, and the viscous material (clay or kaolin) should be added, so that the mechanical strength, necessary while being used in everyday life, can be maintained.
The problems that the products, sold in the market up to now, have, are minute cracks 0.1~2jτm of diameter on the glazed surface. When the raw materials are mixed, formalized, and heated, the ingredients are expanded according to their properties , and after finishing all the processes, the wares are cooled down. At this moment, on the glazed surface, cracks are made when the wares are shrunk. There are some raw materials which make conditions, opposed to the appearances of expanding or shrinking, when it is heated or cooled down.
The most important reason that the cracks are made on the glazed surface is the inappropriate balance between the rates of heat expansion of body and those of glaze. In other words, the rates of heat expansion of body and glaze are not harmonious. When Shrinking of glaze becomes large in cooling process, then the internal stress is made on the glazed surface of ceramic wares, and then finally, cracks are made if the limit of the elasticity is exceeded.
The heat resistant porcelain without any cracks on the glazed surface is made as shown in drawing 1, if the rate of heat expansion of the body and that of the glaze are harmonious.
At this moment, it is most significant to mix the raw materials in such a proportion that the difference between the rate of heat expansion of the body and that of the glaze is within an appropriate range, but if the proportion comes out of the range, cracks can come into being, and furthermore the goods can be destroyed, while being used. In order to eliminate cracks on the glazed surface, it is important to adjust the rate of heat expansion of glaze to a low level or mix the raw materials to increase the tenaciousness. In this case, more amount of silica can be added to the glaze in order to lower the rates of heat expansion of the glaze, or B2O3 can be added so as to increase the tenaciousness of the glaze.
[Brief Description of Drawings]
Dra wing 1. Fe-SEM photograph of this invention and existing products
(a 3,000 magnification)
Drawing2a. The rates of heat expansion of body of this invention after firing Drawing2b. The rates of heat expansion of glaze of this invention after firing Drawing3a. XRD graph of body of this invention after firing Drawing3b. XRD graph of glaze of this invention after firing
_ C — [Composition of invention]
The main material of this invention is petalite and Lithia mica, which have excellence in property of high thermal shock resistance and a slightly low coefficient of heat expansion. Petalite and Lithia mica are the resources of U2O as a flux and that of AI2O3 and S1O2 . Clay ingredients
(viscuos clay and kaolin) are added in order to give plasticity to the main material. Also MgO ingredient (Talc and Dolomite) is added to provide the body of no-crack heat resistant porcelain with low rate of heat expansion. A little amount of ZnO, Zrθ2, and T-O2 is also added in order to adjust the strengh and the rate of heat expansion of the body.
The Seger formula for the body of no-crack heat resistant porcelain is 0.20-0.45 mol of Li2O, 0.13-0.35 mol of MgO, 0.01-0.05 mol of Na2O, 0.01-0.12 mol of K2O, 0.01-0.06 mol of CaO, 0.01-0.02 mol of ZnO, 1 mol of Al2O3, 3.80-5.20 mol of SiO2. 0.01-0.10 mol of ZrO2, 0.01-0.02 mol of TiO2.. According to this Seger formula, the raw materials are mixed to produce the body, which is formalized and heated into the porcelain
In order to make no-crack glaze, of which the rate of heat expansion should be harmonious with that of the body, the main material is Petalite and Lithia mica, thanks to their excellent thermal shock resistance and low coefficient of heat expansion. A proper amount of clay ingredient is added to give plasticity to
— β — the glaze. BaO( or PbO) is added to lower the melting point of the glaze. Also a little amount of Silica stone(Quartz) and B2O3 is added so as to adjust the rate of heat expansion.
The Seger formula of the glaze composition of no-crack heat resistant porcelain is 0.65-0.91 mol of Li2O, 0.02-0.10 mol of BaOCor 0.01-0.10 mol of PbO), 0.01-0.05 mol"of Na2O, 0.01-0.05 mol of K2O, 0.01-0.10 mol of CaO, 0.01-0.05 mol of ZnO, 0.35-1.40 mol of Al2O3, 0.01-0.10 mol of B2O3. 0.00-0.02 mol of Fe2O3, 2.95-7.50 mol of SiO2, 0.01-0.04 molecular equivalent of ZrO2, and the glaze was made properly according to this Seger formula.
The result, evaluated by TMA, as shown in Drawing 2a and 2b, says that the rates of heat expansion of both the body and the glaze are negative ones. And the rates of heat expansion of both the body and the glaze are harmonious with each other,
The XRD graph of this invention after firing is shown in Drawing 3a and 3b. The XRD graph of body composition of the invention , shows that the crystal is Lithium Aluminum Silicate(Lio.6Alo.6Si2.4θ6, LiAlSi3Os, and LiAlSi2Oe : Li2O-Al2O3-SiO2 system). These crystals are considered to make the rate of heat expansion negative.
The XRD graph of glaze composition of the invention , shows that the main are Lithium Aluminum Silicate(LiAlSi2θ6, Lio.6Alo.6Si2.4O6, :
Li2O-Al2θ3-Siθ2 system) and petalite(LΪ2θ-Al2θ3-Siθ2 system). These crystals are considered to make the rate of heat expansion negative. Owing to these ingredients, the rates of heat expansion could have a minus value. According to the quantity of the crystals, the rates of heat expansion of both the body and the glaze become balanced. For these reasons, the porcelain could have the property of no-crack heat resistance.
[Effect of the invention]
This invention can be helpful for health by preventing the porcelains from being polluted by detergents when washed, because they don't have cracks in spite of rapid heating and cooling. This can extend a range of heat resistant porcelain manufacture, and the manufacture skill of the no-crack heat resistant porcelain can sustain and extend this industry. Besides, manufacture of the no-crack heat resistant porcelain is able to make a white porcelain possible, and so it can satisfy the consumers' desire by providing them with excellent goods in various colors and designs.

Claims

[The categories of bill] [claims 1]
In producing the body of no-crack heat resistant porcelain, its main raw materials are petalite and lithia mica , of which the rates of heat expansion is extremely low. And clay ingredient (viscous clay and kaolin) is added so as to give plasticity to the material, and MgO ingredient (Talc and Dolomite ) is also added. A little amount of ZnO, ZrO2, and TiO2. is added in order to adjust mechanical strength and the rate of heat expansion.
The Seger formula of the body composition of the no-crack heat resistant porcelain is Li2O of 0.20-0.45 mol, MgO of 0.13-0.35 mol, Na2O of 0.01-0.05 mol, K2O of 0.01-0.12 mol, CaO of 0.01-0.06 mol, ZnO of 0.01-0.02 mol, Al2O3 of 1 mol, SiO2 of 3.80-5.20 mol, ZrO2 of 0.01-0.10 mol, TiO2 of 0.01-0.02 mol.
The body, made of the composition according to this Seger formula and,
In producing the glaze of no-crack heat resistant porcelain, of which the rate of heat expansion is in harmony with that of the body, its main raw materials are petalite and lithia mica, which have excellent heat resistance and low rate of heat expansion. A proper amount of clay ingredient is added to give plasticity to the glaze, and BaO (or PbO) is added in order to lower the melting point of the glaze. And a little of Silica stone(Quartz) and B2O3 is added to adjust the rate of heat expansion.
The Seger formula of glaze composition of no-crack heat resistant porcelain is Li2O of 0.65-0.91 mol, BaO(or PbO of 0.01-0.10 mol) of 0.02-0.10 mol, Na2O of σ.01~0.05 mol, K2O of 0.01-0.05 mol, CaO of 0.01-0.10 mol, ZnO of 0.01-0.05 mol, Al2O3 of 0.35-1.40 mol, B2O3 of 0.01-0.10 mol, Fe2O3 of 0.00-0.02 mol, SiO2 of 2.95-7.50 mol, ZrO2 of 0.01-0.04 mol.
The glaze, made of the composition according to this Seger formula.
PCT/KR2007/001072 2006-10-25 2007-03-05 Seger formulas for the body and glaze composition of no-crack heat resistant porcelain WO2008050937A1 (en)

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CN104961448A (en) * 2015-05-13 2015-10-07 苏州市英富美欣科技有限公司 Buchner funnel ceramic material and preparation method thereof
CN105294086A (en) * 2015-10-13 2016-02-03 陕西科技大学 Ceramic tile blank and preparation method
CN110240464A (en) * 2019-04-18 2019-09-17 河南飞孟金刚石工业有限公司 Conducting steel ring material core formula
CN114538909A (en) * 2022-03-03 2022-05-27 胡晓荣 Wear-resistant heat-resistant porcelain and processing technology

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CN104961448A (en) * 2015-05-13 2015-10-07 苏州市英富美欣科技有限公司 Buchner funnel ceramic material and preparation method thereof
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CN114538909A (en) * 2022-03-03 2022-05-27 胡晓荣 Wear-resistant heat-resistant porcelain and processing technology

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