KR101289759B1 - Crystalline glazes containing iron and ceramic manufactured using the composition - Google Patents

Abstract

PURPOSE: Crystalline glaze containing iron (Fe) is provided to form a unique pattern on the surface of ceramics by the iron components, using rusted tin, stones, and iron oxides in an optimum ratio. CONSTITUTION: Crystalline glaze contains 0.5-10 wt% of 1-100 um granules of rusted tin, 0.5-10 wt% of 50-200 mesh stones, 0.05-10 wt% of 1-100 um granules of iron oxides, 10-45 wt% of 50-200 mesh feldspar, 10-20 wt% of 1-100 um granules of zinc, 10-25 wt% of 50-200 mesh limestone, and 10-20 wt% of 50-200 mesh kaolin. The stones are one or more selected from hematite (Fe2O3), magnetite (Fe3O4), or Ilmenite. A plasticizing and cooling method of the crystalline glaze comprises the following steps: heating a crystalline glaze composition to 1,230-1,250°C, and maintaining the temperature for 30 minutes-1 hour; and cooling the heated crystalline glaze composition to 1,100-1,150°C and maintaining the temperature for 2-4 hours.

Description

Crystalline oil containing iron and ceramics produced using the same {CRYSTALLINE GLAZES CONTAINING IRON AND CERAMIC MANUFACTURED USING THE COMPOSITION}

The present invention relates to a crystalline oil containing iron (Fe) and ceramics that can further enhance the aesthetics by forming a unique pattern of iron components on the surface by using the crystalline oil.

Generally, transparent oil is composed of a single homogeneous phase, whereas crystalline oil is a glaze composed of two or more phases and refers to one of heterogeneous glazes. In general, a heterogeneous glaze is a phase in which another phase is dispersed or aggregated on a transparent glass, and in particular, crystals that can be identified by a microscope or the naked eye are separated and formed on the surface or inside of the glaze which is a crystalline oil transparent phase. Says glaze.

Glaze is a glass that covers the surface of clay products, increasing the strength and forming an oil film on the surface to prevent direct penetration of moisture into the body. In addition, glaze has various colors and patterns, and is used as an aesthetic means to bring a decorative effect to present the beauty of ceramic works to the user.

Among them, crystalline oil is unusual in appearance unlike other glazes. Irregular mesh glass, ie, when the glaze melts, it is saturated with a crystalline substance in the glaze, and when it is slowly cooled, it precipitates inside or outside the glaze and displays a beautiful shape on the surface to identify the crystal with a microscope or the naked eye. Says glaze.

Crystalline oil shows various crystal forms such as acicular, scalloped or circular on oil surface. One of the important factors for making such crystals is zinc crystallization and the crystallized oil obtained by containing zinc is relatively large in size. ) Has the form The main crystalline oils are zinc crystalline oil, zinc titanium crystalline oil, titanium crystalline oil, manganese crystalline oil, cobalt crystalline oil and aventurine oil.

Crystalline oils have the chemical and physical properties of glazes, which are melted to form and grow crystallization, and have basic oxides that are included in the melt and used to produce silicates, such as those that represent crystalline compounds during cooling, depending on the conditions. The relationship between the melting temperature and the holding time after melting, the temperature change after nucleation, and the crystal ripening time do not produce crystals if any of these four conditions is misaligned.

Although the present invention also relates to such crystalline oil, the constituent oil constituting the crystalline oil contains a large amount of iron spots (spots caused by the iron component) is naturally formed to a crystal oil that can further enhance the aesthetics of the ceramic surface will be.

In relation to such crystalline oil, Republic of Korea Patent 10-0908305 (Registration date July 10, 2009) 'Method for manufacturing crystalline oil ceramics', Republic of Korea Patent 10-1141262 (Registration date April 23, 2012)' Multiple Crystal oil and a method of manufacturing ceramics using the same that can exhibit color and marbling patterns have been disclosed.

However, the techniques disclosed in the above-mentioned patents do not meet the object required in the present invention because the technique for forming a unique pattern by iron to be proposed in the present invention is not disclosed.

Republic of Korea Patent Registration 10-0908305 (Registration Date July 10, 2009) Republic of Korea Patent Registration 10-1141262 (Registration date April 23, 2012)

In order to solve the above problem,

The present invention provides a crystalline oil containing iron so that iron spots (spots caused by iron components) can be naturally expressed on the surface of pottery by using it in the manufacture of porcelain, and by using the crystalline oil, the aesthetic sense is further enhanced. It is an object of the invention to provide a ceramic that can be raised.

In order to achieve the above object,

The present invention is 0.5 ~ 10wt% corroded tin of 1 ~ 100㎛ fine particles,

0.5-10wt% of 50-200mesh stone, which is at least one selected from hematite (Fe ₂ O ₃ ), magnetite (Fe ₃ O ₄ ) or titanium iron,

0.5 to 10wt% of iron oxide (Fe ₂ O ₃ ) of 1 to 100㎛ fine particles,

5 ~ 30wt% of silica of 50 ~ 200mesh,

SiO ₂ 76.76wt%, Al ₂ O ₃ 13.3wt%, Fe ₂ O ₃ 0.037wt%, CaO 0.45wt%, MgO 0.02wt%, K ₂ O 3.85wt%, Na ₂ O 5.53wt%, Ig.loss 0.053 10-45wt% of feldspar of 50-200mesh having a wt% composition,

ZnO 99.1wt%, MgO 0.26wt%, P ₂ O ₅ 0.06wt%, Fe ₂ O ₃ 0.12wt%, Al ₂ O ₃ 0.17wt%, SiO ₂ 0.24wt%, Ig.loss 0.05wt% 10-20 wt% of 1-100 µm fine zinc,

10 ~ 25wt of limestone of 50 ~ 200mesh with the composition of SiO ₂ 1.08wt%, Al ₂ O ₃ 0.25wt%, Fe ₂ O ₃ 0.28wt%, CaO 53.7wt%, MgO 1.29wt%, Ig.loss 43.4wt% %Wow,

_{SiO 2 43.38wt%, Al 2 O} 3 41.00wt%, Fe 2 O 3 1.02wt%, CaO 0.98wt%, MgO 0.78wt%, K 2 O 0.39wt%, Na 2 O 1.51wt%, Ig.loss 10.94 Technical composition of iron-containing crystalline oil prepared by calcining and cooling a mixture prepared by mixing 10-20 wt% of 50-200mesh kaolin having a wt% component composition,

As a technical configuration for ceramics produced using the crystalline oil containing the iron,

After first roasting any one or two or more selected from sancheongto, buncheongto or cheongjato, apply the glaze to the surface of the base and apply the crystalline oil of claim 1 to a thickness of 1.0-1.3mm. The main technical configuration is the technical configuration of ceramics manufactured using crystal oil obtained by firing at 1,200 ~ 1,300 ° C.

In the technical configuration of the crystalline oil, the calcination / cooling was performed at a target temperature of 1,230 ° C. to 1,250 ° C., and then maintained at the target temperature for 30 minutes to 1 hour, followed by cooling to a crystal growth temperature of 1,100 ° C. to 1,150 ° C. After holding for 2-4 hours,

More specifically, after the temperature is raised to the target temperature of 1,250 ℃, it is maintained for 30 minutes to 1 hour at the target temperature and then cooled by 100 ℃ characterized in that it is maintained for 2 hours, 3 hours and 4 hours at 1,150 ℃.

Crystalline oil containing iron (Fe) according to the present invention and porcelain produced using the same to increase the value of porcelain by improving the aesthetics of porcelain surface decoration by naturally expressing the iron point by the iron (Fe) component It has the advantage of being able to give.

1 is a photograph for replacing the figure showing an example 1 of ceramics produced according to the present invention.
Figure 2 is a replacement picture showing an example 2 of the ceramics produced according to the present invention.
Figure 3 is a replacement picture showing an example 3 of the ceramics produced according to the present invention.

Let us look at the details of the above technical configuration.

First, we will look at the technical configuration of the crystalline oil in more detail.

Among the components constituting the crystalline oil, 1 to 100 μm of finely corroded tins are pulverized by taking only corroded tins.

Representative metals that cause corrosion are iron, and the reduction potential of iron is as follows.

Fe ₂ ⁺ (aq) + 2e--> Fe (s) E ⁰ = -0.44 (V) (1)

When iron is exposed to an aqueous solution, the reaction proceeds:

Fe (s) + H ₂ O + 1 / 2O _2- > Fe (OH) ₂ (2)

When the material of Fe (OH) ₂ is pure it is white but usually green or dark green due to its initial oxidation by air. By accessing dissolved oxygen to the outside of the oxidized coating surface, Fe (OH) ₂ is oxidized as follows.

Fe (OH) ₂ + 1 / 2H ₂ O + 1 / 4O _2- > Fe (OH) ₃ (3)

Fe (OH) ₃ is orange or reddish brown and usually forms most of the rust. If oxygen is not sufficient Fe (OH) ₂ is not being oxidized to _{Fe 2 O 3 Fe 2 O 4} · Black rust is in the form of nH ₂ O.

In addition, the hematite (Fe ₂ O ₃ ), titanium iron and magnetite is a material containing a large amount of iron, the hematite (hematite, Fe ₂ O ₃ ) is MgO 0.58wt%, TiO ₂ 13.00wt%, FeO 9.89 wt%, Fe ₂ O ₃ has a composition ratio of 76.53wt%,

The titanium pyrite has a component composition ratio of MgO 3.51wt%, FeO 48.45wt%, TiO ₂ 48.04wt%,

The magnetite is Fe ₂ O ₃ 52.6wt%, MgO 24.03wt%, SiO ₂ 18.6wt%, Al ₂ O ₃ 2.54wt%, MnO 0.95wt%, K ₂ O 0.69wt%, Na ₂ O 0.13wt%, CaO 0.3 wt%, TiO ₂ 0.12 wt%, P ₂ O ₅ 0.04 wt%.

The stone is any one or more selected from hematite (hematite, Fe ₂ O ₃ ), magnetite (Fe ₃ O ₄ ) or titanium iron stone, more preferably hematite (hematite, Fe ₂ O ₃ ), magnetite ( Fe ₃ O ₄ ), a mixture of titanium iron in a weight ratio of 0.5 to 1: 0.5 to 1: 0.5 to 1 is used.

The iron oxide (Iron Oxide; Fe ₂ O ₃ ) is a red powder having a molecular weight of 157.9 is a neutral oxide, depending on the conditions it is also called a positive oxide by the role of basic or acidic. The iron oxide is a component that controls the properties of the glaze.

The Fe ₂ O ₃ is a crystal coloring agent that is generally used, the color of both the background color and the crystal color from yellow to brown, but in some cases the background color is light brown, the crystal color is colored gold.

The corroded tin, stone, and iron oxide are used to make the iron point naturally expressed in the crystalline oil of the present invention. When the amount is less than 0.5wt%, the iron point is difficult to be properly expressed on the surface of porcelain. In order to provide the crystalline oil, it is preferable to limit the amount of the tin, stone and iron oxide used in the range of 0.5 to 10 wt% based on the total crystalline oil, respectively.

The silica (SiO ₂ ) is a generic term for minerals and rocks mainly composed of SiO ₂ , and is a main oxide having a content of 59.12% in the rock sphere, and most of them form silicates. The role of silica in the glaze affects the aging temperature, viscosity, coefficient of thermal expansion, hardness and strength of the glaze. The amount of silica used to form crystalline oil is 5 to 30 wt%, the coating power may drop when less than 5 wt%, and when it exceeds 30 wt%, cracking may occur during the firing process. It is preferably used as.

The feldspar is any one or more selected from potassium feldspar (orthoclase), sodium feldspar (albite), calcium feldspar (anorthite), barium feldspar (celsian), plagioclase, lithium feldspar (petalite), nepheline 10 It is used in the case of ~ 45wt%, if less than 10wt% may reduce the coating power, if it exceeds 45wt% may cause cracks during the firing process, the feldspar is preferably used in 10 ~ 45wt%.

The zinc is zinc oxide (ZnO) and has a molecular weight of 81.4 and a specific gravity of 5.6 white powder. Zinc oxide is obtained by reacting zinc zinc in metal zinc with O2, and the zinc produced is called zinc flower because its particles are very hard. Zincation can act as a strong solvent in glazes in place of alkaline soluble oxides because of their relatively low water solubility. The zinc oxide has an effect of increasing strength and friction on the oil surface by using the crystalline oil, and serves to enhance gloss and whiteness.

When the amount of zinc used is less than 10wt%, it is difficult to expect the effect of increasing the glossiness, so the amount of zinc used is preferably limited within the range of 10 to 20wt%.

The limestone is a kind of aqueous rock containing a large amount of calcium, and the chemical formula is added to the glaze as CaCO ₃ to make the surface of the glaze smooth and even and have an emulsion function. The limestone has a specific surface area of 2.75-3.26 m 2 / g, microcrystalline calcite ore with a pH of 9.78, microcrystalline surrogate ore with a specific surface area of 3.14 m 2 / g, and a pH of 9.87, coarse surrogate with a specific surface area of 2.97 m 2 / g and a pH of 9.77. Select one or more of crystalline ore, specific calcite type ore with specific surface area of 2.96 ~ 3.30 ㎡ / g, pH 9.85, mix with water in 1: 1 weight ratio, ball mill pulverization for 11 ~ 12 hours and sift 200mesh After drying, 50mesh sieve again.

The limestone is used in 10 to 25 wt% with respect to the total weight of the crystalline oil, when less than 10wt% may not be well expressed, the limestone is preferably used in the range of 10-25wt%. Do.

The kaolin (Al ₂ O ₃ · 2SiO ₂ · 2H ₂ O) is a mineral consisting of the smallest particles of the minerals produced in nature, kaolinite (koalinite), necklite of granular plate crystal of hardness 2 ~ 2.5, specific gravity 2.6 ( Any one or more of nacrite, dickite or halloysite on a tube is selected and used.

The kaolinite (koalinite), neckite (nacrite), dickite (dickite) is represented by the formula Al ₂ O ₂ · 2 SiO ₂ · 4H ₂ O, the halloysite (halloysite) is represented by the formula Al ₂ O ₃ · 2SiO ₂ It is represented by 4H ₂ O.

The kaolin is pulverized by mixing kaolin and water in a 1: 1 weight ratio, pulverized for 23 ~ 25 hours using a ball mill, and then sifted 200mesh and dried again to 50mesh sieve.

The kaolin contains alumina (Al ₂ O ₃ ) that acts as a stabilizer to increase the viscosity and harden the crystalline oil, and when used in less than 10wt%, the stability of the crystalline oil is lowered, Kaolin is preferably used in the range of 10 to 20wt%.

Specific examples of the mixing ratio of the components constituting the crystalline oil are as follows.

0.5 wt% of corroded tin; 0.6 wt% of hematite (Fe ₂ O ₃ ): magnetite (Fe ₃ O ₄ ): titanium iron in a 1: 1: 1 weight ratio; 0.5 wt% of iron oxide (Fe ₂ O ₃ ); 30wt% of silica; With feldspar 20.4 wt%; 20 wt% zinc; 18 wt% limestone; Kaolin 10wt%; composition by mixing.

5 wt% of corroded tin; Hematite (Fe ₂ O ₃ ): magnetite (Fe ₃ O ₄ ): 6wt% of stone mixed with titanium iron in a 1: 1: 1 weight ratio; 5 wt% of iron oxide (Fe ₂ O ₃ ); 15.6 wt% of silica; With feldspar 20.4 wt%; 20 wt% zinc; 18 wt% limestone; Kaolin 10wt%; composition by mixing.

10 wt% of corroded tin; Hematite (Fe ₂ O ₃ ): magnetite (Fe ₃ O ₄ ): 9wt% of stone mixed with titanium iron in a 1: 1: 1 weight ratio; 10 wt% iron oxide (Fe ₂ O ₃ ); 5wt% of silica; With feldspar 20.4 wt%; With 17.6 wt% zinc; 18 wt% limestone; Kaolin 10wt%; composition by mixing.

Crystallized oil having the above-mentioned composition consists of crystal nuclei when it becomes a high-temperature fluidized liquid. At this time, the temperature is drastically lowered to lower the melting temperature to 100 ° C. or higher, and then the ripening temperature of the crystal nuclei is about 1,100 ° C. to 1,150 ° C. It should be kept for ~ 4 hours.

Crystalline oil precipitates crystals in the cooling process rather than the temperature raising process. Once melted and homogenized, the glaze attempts to change into a thermodynamically stable phase once the thermodynamically unsaturated crystal product has cooled to a certain temperature.

The firing method is oxidatively calcined using a kiln, and in general, crystalline oils have a complex or separated temperature difference between nucleation, growth, and glassy viscosity depending on the base oil composition. After maintaining at a low temperature of ~ 150 ℃ and slowly cooled to form a crystal, the crystal shape and size is varied according to the time, temperature control.

Therefore, in order to produce crystals according to the firing conditions with stable crystalline oil, the temperature is raised to a speed of 3 ° C./min up to 900 ° C., and a temperature of 2 ° C./min is raised to a target temperature of 1,230 ° C. to 1,250 ° C. The melt is homogenized by maintaining at a melting temperature of 1,230 ° C. to 1,250 ° C. for 30 minutes to 1 hour, and then cooled at a rate of 4 ° C./min to reach a crystal growth temperature of 1,100 ° C. to 1,150 ° C., at the crystal growth temperature. Hold for 2-4 hours.

More specifically, after heating the mixture of Example 3 to the target temperature of 1,250 ℃, and maintained at the target temperature for 30 minutes to 1 hour and then cooled by 100 ℃ for 2 hours, 3 hours and 4 hours at 1,150 ℃ Keep it.

Ceramics manufactured using the crystalline oil maintained at 1,150 ° C. for 2 hours are characterized in that the size of the crystals is fine, as shown in FIG. 1,

Ceramics manufactured using the crystalline oil maintained at 1,150 ° C. for 3 hours (FIG. 2) is characterized by a somewhat larger crystal size than the ceramics shown in FIG. 1.

Ceramics manufactured using the crystalline oil maintained at 1,150 ° C. for 4 hours (FIG. 3) can be seen to show the largest crystals among the ceramics presented above.

That is, the longer the retention time, the larger the size of the crystal, and conversely, if it is too short, the crystal will not grow sufficiently.

And, looking at the manufacturing process of the ceramics using the crystalline oil,

The porcelain is a surface of the base coated with glaze after first roasting any one or two or more selected from sancheongto, buncheongto or cheongjato. The thickness of the crystal oil according to the present invention is 1.0-1.3mm. After lubricating, it is calcined at 1,200 to 1,300 ° C., and the prepared examples are shown in FIGS. 1 to 3.

The iron-based crystalline oil prepared according to the present invention is used for a substance prepared by using any one or two or more kinds selected from sancheongto, buncheongto, or cheongjato. It is highly applicable to the industry by enhancing the aesthetics by decorating the porcelain to further enhance the value of ceramics.

Claims (5)

0.5 ~ 10wt% of corroded tin in 1 ~ 100㎛ granules,
0.5-10wt% of 50-200mesh stone, which is at least one selected from hematite (Fe ₂ O ₃ ), magnetite (Fe ₃ O ₄ ) or titanium iron,
0.5 to 10wt% of iron oxide (Fe ₂ O ₃ ) of 1 to 100㎛ fine particles,
5 ~ 30wt% of silica of 50 ~ 200mesh,
10 ~ 45wt% of feldspar of 50 ~ 200mesh,
10-20 wt% of 1-100 µm fine zinc,
10 ~ 25wt% of limestone of 50 ~ 200mesh,
Iron-containing crystalline oil, characterized in that prepared by firing and cooling the mixture of 10 to 20wt% of 50-200mesh kaolin.
The method according to claim 1,
Hematite (hematite, Fe ₂ O ₃ ) has a composition ratio of 0.58wt% MgO, 13.00wt% TiO _2, 9.89wt% FeO, 76.53wt% Fe ₂ O ₃ ,
Titanium pyrite has a component composition ratio of MgO 3.51wt%, FeO 48.45wt%, TiO ₂ 48.04wt%,
Magnetite is Fe ₂ O ₃ 52.6wt%, MgO 24.03wt%, SiO ₂ 18.6wt%, Al ₂ O ₃ 2.54wt%, MnO 0.95wt%, K ₂ O 0.69wt%, Na ₂ O 0.13wt%, CaO 0.3 An iron-containing crystalline oil, characterized by having a component composition ratio of wt%, TiO ₂ 0.12 wt%, and P ₂ O ₅ 0.04 wt%.
The method according to claim 1,
Firing and cooling are to be heated to the target temperature of 1,230 ℃ ~ 1,250 ℃, and then maintained at the target temperature for 30 minutes ~ 1 hour, then cooled to 1,100 ℃ ~ 1,150 ℃ crystal growth temperature and maintained for 2-4 hours A crystalline oil containing iron characterized by the above-mentioned.
The method according to claim 1,
Firing and cooling after heating up to the target temperature of 1,250 ℃, it is maintained for 30 minutes to 1 hour at the target temperature and then cooled by 100 ℃ to maintain at 1,150 ℃ for 2 hours, 3 hours and 4 hours Crystalline oil containing.
After first roasting any one or two or more selected from sancheongto, buncheongto or cheongjato, apply the glaze to the surface of the base and apply the crystalline oil of claim 1 to a thickness of 1.0-1.3mm. Porcelain produced using a crystalline oil, characterized in that by firing at 1,200 ~ 1,300 ℃.

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