KR101315126B1 - Cinnabar glaze composite for porcelain and manufacturing method of porcelain using the composite - Google Patents

Abstract

PURPOSE: A cinnabar glaze composition for the ceramic is provided to have a high-grade color sense, and implement in the living porcelain by excluding the use of the lead (Pb) component. CONSTITUTION: A cinnabar glaze composition for the ceramic comprises one kind which is selected from a glaze, a copper oxide (CuO), ZrO2, CeO2 and HfO2. The glaze comprises KNaO, CaO, Al2O3 and SiO2. The KNaO, the CaO, the Al2O3 and the SiO2 are comprised as the mole ratio of 0.1-0.4:0.3-1.0:0.25-0.4:2.5-4.0. 0.1-5 parts by weight of the copper oxide (CuO) is contained base on the 100.0 parts by weight of the glaze. 0.1-7 parts by weight of one kind which is selected from the ZrO2, the CeO2 and the HfO2 are contained base of 100.0 parts by weight of the glaze. The KNaO includes the K2O and the Na2O as the weight ratio of 1:1-2.5. The ZrO2, the CeO2 and the HfO2 are comprised as the weight ratio of 1:0.01-3:0.1-3.

Description

Cinnabar glaze composite for porcelain and manufacturing method of porcelain using the composite}

The present invention relates to a cinnabar glaze composition and a method of manufacturing ceramics using the same. More specifically, it can express beauty and luxurious color, does not contain lead (Pb), and is harmless to humans by using components that are harmless to the human body. The present invention relates to a fine ceramic glaze composition for ceramics and a method of manufacturing ceramics using the same, which can be applied, and have good gloss and color, and evenly appear in color.

Glaze is a thin layer that is painted on the surface of ceramics and fired when it is fused to the surface.

Glaze lowers the absorbency of porcelain, suppresses permeability, imparts strength to the porcelain, and makes the viewer feel visual aesthetics due to the luster expressed on the surface of the porcelain. As such, glazes coated on the surface of ceramics and polished by firing include white oil, blue oil, powdered blue oil, transparent oil, ash oil, celestial oil, crystalline oil, rapeseed oil and cinnabar oil.

Recently, there is a demand for various colors, and various glazes have been developed to meet these demands.

However, since the presently developed cinnabar glaze uses lead (Pb), which is harmful to the human body and is not environmentally friendly, its application to living magnetics is limited.

Therefore, there is a need for the development of cinnabar glaze that can be applied to life and use ingredients that are harmless to the human body.

Republic of Korea Patent Publication No. 10-0947810

The problem to be solved by the present invention is that it can express beauty and high-quality color, it does not contain lead (Pb) component and can be applied to life by using components that are harmless to the human body, both gloss and color are good, The color appearance appears evenly, and provides a fine ceramic glaze composition for ceramics and a method of manufacturing ceramics using the same.

The present invention comprises a glaze comprising KNaO, CaO, Al ₂ O ₃ and SiO ₂ , copper oxide (CuO), and at least one material selected from ZrO ₂ , CeO ₂ and HfO ₂ , the glaze is the KNaO And the CaO, the Al ₂ O ₃ and the SiO ₂ form a molar ratio of 0.1 to 0.4: 0.3 to 1.0: 0.25 to 0.4: 2.5 to 4.0, and the copper oxide (CuO) is 0.1 to 5 parts by weight of the glaze. It is contained in parts by weight, at least one material selected from ZrO ₂ , CeO ₂ and HfO ₂ provides a cinnabar glaze composition for ceramics containing 0.1 to 7 parts by weight based on 100 parts by weight of the glaze.

The KNaO may be a weight ratio of K ₂ O and Na ₂ O 1: 1 to 2.5.

The ZrO ₂ , the CeO ₂ and the HfO ₂ may form a weight ratio of 1: 0.01 to 3: 0.1 to 3.

The glaze may further include BaO, and CaO and BaO may form a molar ratio of 1: 0.1 to 1.0.

In addition, the present invention comprises the steps of preparing a glaze having a molar ratio of 0.1 to 0.4: 0.3 to 1.0: 0.25 to 0.4: 2.5 to 4.0 KNaO, CaO, Al ₂ O ₃ and SiO ₂ , 100 parts by weight of the glaze Preparing 0.1 to 5 parts by weight of copper oxide (CuO), preparing 0.1 to 7 parts by weight of at least one material selected from ZrO ₂ , CeO ₂ and HfO _{2 based} on 100 parts by weight of the glaze, and the glaze and the copper oxide. (CuO) and mixing at least one material selected from the ZrO ₂ , CeO ₂ and HfO ₂ to obtain a cinnabar glaze composition for ceramics, the step of pouring the cinnabar glaze composition for ceramics to the ceramics and the ceramic It provides a method of producing ceramics comprising the step of firing the substance in a reducing atmosphere.

The KNaO may be a weight ratio of K ₂ O and Na ₂ O 1: 1 to 2.5.

The ZrO ₂ , the CeO ₂ and the HfO ₂ may form a weight ratio of 1: 0.01 to 3: 0.1 to 3.

The glaze may further include BaO, and CaO and BaO may form a molar ratio of 1: 0.1 to 1.0.

The method of manufacturing the ceramics may further include heat treating the fired product at a temperature of 600 to 700 ° C. for 10 minutes to 48 hours after the firing step.

According to the cinnabar glaze composition for ceramics of the present invention, it can express beauty and high-quality color, it does not contain lead (Pb) component, and can be applied to everyday magnetism by using components that are harmless to the human body.

In the case of using the cinnabar glaze composition for ceramics of the present invention, both glossiness and color are good, color appearance is even, and reproducibility is excellent.

FIG. 1 is a photograph showing ceramic materials calcined by adding 1 part by weight of copper oxide (CuO) to a ceramics material in a lime barium-based glaze having the composition shown in Table 1 and then sintering them in a reducing atmosphere at 1250 ° C. for 1 hour.
2 is added to 1 part by weight of copper oxide (CuO) in the lime barium-based glaze having the composition shown in Table 1, and then lubricated in the ceramics, and then calcined by maintaining at 1250 ℃ for 1 hour, and then again at 630 ℃ 2 This is a picture showing the ceramics obtained by heat treatment for a time.
Figure 3 is added to 1 part by weight of copper oxide (CuO) to the lime barium-based glaze having the composition shown in Table 1, and then lubricated in the ceramics, and then calcined by holding at 1250 ℃ for 1 hour, and then again at 630 ℃ 6 This is a picture showing the ceramics obtained by heat treatment for a time.
4 is added to 1 part by weight of copper oxide (CuO) in the lime barium-based glaze having the composition shown in Table 1, and then lubricated in the ceramics, and then calcined by holding for 1 hour at 1250 ℃ in a reducing atmosphere, and then again 12 at 630 ℃ This is a picture showing the ceramics obtained by heat treatment for a time.
5 is added to 1 part by weight of copper oxide (CuO) in the lime barium-based glaze having the composition shown in Table 1 and then lubricated in the ceramics, and then calcined by holding at 1250 ℃ for 1 hour in a reducing atmosphere, and then again at 630 ℃ 24 This is a picture showing the ceramics obtained by heat treatment for a time.
6 is added to 1 part by weight of copper oxide (CuO) in the lime barium-based glaze having the composition shown in Table 1 and then lubricated in the ceramics, and then calcined by holding at 1250 ℃ for 1 hour in a reducing atmosphere, and then at 36 at 630 ℃ This is a picture showing the ceramics obtained by heat treatment for a time.
FIG. 7 illustrates the addition of 1 part by weight of copper oxide (CuO) to 100 parts by weight of glaze to a lime-barium based glaze having the composition shown in Table 1 to prepare a cinnabar glaze composition, and after the cinnabar glaze composition is oiled to the ceramics, a reducing atmosphere Photo shows ceramics obtained by firing at 1250 ° C for 1 hour at.
Figure 8 is a lime barium-based glaze having a composition of Table 1 by mixing 1 part by weight of copper oxide (CuO) and 1 part by weight of ZrO _{2 to} 100 parts by weight of glaze to prepare a cinnabar glaze composition, the cinnabar glaze composition to the ceramic After lubrication, it is a photograph showing the ceramics obtained by baking for 1 hour at 1250 ℃ in a reducing atmosphere.
Figure 9 is a lime barium glaze having a composition of Table 1 to 1 part by weight of copper oxide (CuO) and 1 part by weight of CeO ₂ with respect to 100 parts by weight of glaze to prepare a cinnabar glaze composition, the cinnabar glaze composition to the ceramic After lubrication, it is a photograph showing the ceramics obtained by baking for 1 hour at 1250 ℃ in a reducing atmosphere.
10 is a lime barium glaze having a composition shown in Table 1 to 1 part by weight of copper oxide (CuO) and 1 part by weight of HfO ₂ with respect to 100 parts by weight of glaze to prepare a cinnabar glaze composition, the cinnabar glaze composition to the ceramic After lubrication, it is a photograph showing the ceramics obtained by baking for 1 hour at 1250 ℃ in a reducing atmosphere.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and that various modifications may be made without departing from the scope of the present invention. It is not.

Hereinafter, pottery is a term containing pottery and porcelain, and pottery is used hereinafter as a term containing porcelain and porcelain. In addition, KNaO is used as a term containing K ₂ O and Na ₂ O.

In ceramics, raw materials such as clay, feldspar, limestone, and silica are mainly used, and ceramics refers to a product that is molded by mixing these raw materials in a predetermined ratio and then fired and cured. Pottery (소 地) of the body (지 地) has a high absorption rate because of the sound of the tapping sound and durability is relatively weak. The porcelain has almost no absorption of the body, so when it is knocked out, it produces a clear sound and is durable.

The present invention proposes a cinnabar glaze composition which is coated on the surface of ceramics and fused to the surface to be scarlet, reddish brown or reddish glossy. The glaze glaze composition is coated on the surface of the primary fired porcelain, and when the porcelain coated with the glaze glaze composition is fired, a glaze film is formed on the surface of the porcelain to give a color by light diffraction.

Jinsa glaze composition for ceramics according to a preferred embodiment of the present invention, glaze containing KNaO, CaO, Al ₂ O ₃ and SiO ₂ , copper oxide (CuO), ZrO ₂ , CeO ₂ and HfO ₂ selected from The glaze includes the above material, wherein the glaze comprises the molar ratio of 0.1 to 0.4: 0.3 to 1.0: 0.25 to 0.4: 2.5 to 4.0 of the KNaO, the CaO, the Al ₂ O _3, and the SiO ₂ , and the copper oxide (CuO) Is contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the glaze, and at least one material selected from ZrO ₂ , CeO ₂ and HfO ₂ is contained in an amount of 0.1 to 7 parts by weight based on 100 parts by weight of the glaze.

The KNaO may be a weight ratio of K ₂ O and Na ₂ O 1: 1 to 2.5.

The ZrO ₂ , the CeO ₂ and the HfO ₂ may form a weight ratio of 1: 0.01 to 3: 0.1 to 3.

The glaze may further include BaO, and CaO and BaO may form a molar ratio of 1: 0.1 to 1.0.

The present invention provides a step of preparing a glaze in which the ratio of KNaO, CaO, Al ₂ O ₃ and SiO ₂ in a molar ratio of 0.1 to 0.4: 0.3 to 1.0: 0.25 to 0.4: 2.5 to 4.0, and 100 parts by weight of the glaze Preparing 0.1 to 5 parts by weight of copper oxide (CuO), preparing 0.1 to 7 parts by weight of at least one material selected from ZrO ₂ , CeO ₂ and HfO _{2 based} on 100 parts by weight of the glaze, and the glaze and the copper oxide. (CuO) and mixing at least one material selected from the ZrO ₂ , CeO ₂ and HfO ₂ to obtain a cinnabar glaze composition for ceramics, the step of pouring the cinnabar glaze composition for ceramics to the ceramics and the ceramic It provides a method of producing ceramics comprising the step of firing the substance in a reducing atmosphere.

The KNaO may be a weight ratio of K ₂ O and Na ₂ O 1: 1 to 2.5.

The ZrO ₂ , the CeO ₂ and the HfO ₂ may form a weight ratio of 1: 0.01 to 3: 0.1 to 3. At least one material selected from ZrO ₂ , CeO ₂ and HfO ₂ exhibits stable color development of cinnabar glaze when 0.1 to 7 parts by weight is added to 100 parts by weight of the glaze.

The glaze may further include BaO, and CaO and BaO may form a molar ratio of 1: 0.1 to 1.0.

Hereinafter, the firing process will be described in detail.

The resultant mixed for the firing is charged to a furnace such as an electric furnace and the firing process is performed. The firing process is preferably performed for 10 minutes to 48 hours at a temperature of about 1000 ~ 1600 ℃. It is desirable to keep the pressure inside the furnace constant during firing.

The firing is preferably carried out at a temperature in the range of 1000 to 1600 ° C. If the firing temperature is less than 1000 ℃ due to incomplete firing may not be good thermal or mechanical properties of the ceramics, if the temperature is higher than 1600 ℃ not only because of the high energy consumption, but also may not be good physical properties of the ceramics.

The firing temperature is preferably raised at a heating rate of 1 to 50 ° C / min. If the heating rate is too slow, the time is long and productivity is deteriorated. If the heating rate is too high, thermal stress is applied due to a rapid temperature rise It is preferable to raise the temperature at the temperature raising rate in the above range.

The firing is preferably carried out at a firing temperature for 10 minutes to 48 hours. If the firing time is too long, it is not economical since the energy consumption is high. Further, it is difficult to expect further firing effect. If the firing time is small, the physical properties of the ceramic material may not be good due to incomplete firing.

Moreover, it is preferable to perform the said baking in a reducing atmosphere.

After carrying out the firing process, the furnace temperature is lowered to unload the fired body. The furnace cooling may be allowed to cool down in a natural state by turning off the furnace power source, or to set a temperature drop rate (eg, 10 ° C./min) arbitrarily. The pressure inside the furnace is preferably kept constant while the furnace temperature is lowered.

The method of manufacturing the ceramics may further include heat treating the fired product at a temperature of 600 to 700 ° C. for 10 minutes to 48 hours after the firing step. When the heat treatment is performed after the firing, the cinnabar glaze composition is more stably and vividly colored. In the process of cooling after firing to a temperature in the range of 1000 to 1600 ° C., when the temperature reaches 600 to 700 ° C., the heat treatment may be performed for 10 minutes to 48 hours, or after the firing step, the temperature of the furnace is again cooled. Heat treatment may be performed by heating the temperature to a temperature of 600 to 700 ° C.

Hereinafter, embodiments according to the present invention will be specifically shown, and the present invention is not limited to the following embodiments.

≪ Example 1 >

Table 1 below shows the composition of the lime barium glaze and its molar ratio as the glaze used in this example.

Furtherance KNaO CaO BaO Al ₂ O ₂ SiO ₂ Mole ratio 0.2 0.5 0.3 0.3 3.0

Table 2 below shows the composition of the lime glaze and its molar ratio as the glaze used in this example.

Furtherance KNaO CaO Al ₂ O ₃ SiO ₂ Mole ratio 0.2 0.8 0.35 3.5

In the lime-barium glaze and the lime-based glaze, alumina (Al ₂ O ₃ ) is 0.30 to 0.35 moles, and silica (1 mole is the molar ratio sum of the alkali and alkaline earth components (molar ratio sum of KNaO, CaO and BaO). SiO ₂ ) is 3.00 to 3.50 mol, which is relatively small, but this becomes a condition for making the glaze strong and succeeding the cinnabar glaze.

Reduction firing of copper oxide (CuO) to the glaze having the composition of Table 1 and Table 2 to obtain a cinnabar glaze red.

When the color of copper (Cu) is largely divided, it becomes blue to green in oxidative firing, and red in strong reducing firing. Neutral firing often leaves colorless or pale black, dirty spots. It is colored blue to green when copper (Cu) is present as a divalent ion in porcelain glaze, and is theoretically colorless when present as monovalent ion, and red when copper (Cu) is dispersed in colloidal state. It is because it develops.

Cinnabar glaze is no exaggeration to say that the firing method determines success. When 1 part by weight of copper oxide (CuO) was mixed with 100 parts by weight of the glaze in the glaze having the composition shown in Table 1 and Table 2, and experimented using a 1-lube kiln fueled with liquefied petroleum gas (LPG) gas, In the early stage of the heating, it was gradually heated and reduced to 6% of carbon monoxide gas concentration at 900 ° C., and the atmosphere was maintained until firing was completed to obtain a cinnabar glaze.

However, since the cinnabar glaze composition of the general composition is sensitively changed in the atmosphere, form, firing method, etc. of the kiln, the defect rate is high and the color change occurs severely.

Therefore, in order to obtain a stable cinnabar glaze, a method of obtaining a stable cinnabar glaze with the existing composition and a method of obtaining a stable cinnabar glaze by adding an additive to the existing composition were studied.

FIG. 1 is a photograph showing ceramic materials calcined by adding 1 part by weight of copper oxide (CuO) to a ceramics material in a lime barium-based glaze having the composition shown in Table 1 and then sintering them in a reducing atmosphere at 1250 ° C. for 1 hour.

2 to 6 is added to 1 parts by weight of copper oxide (CuO) to the lime barium-based glaze having the composition shown in Table 1 and then lubricated in the ceramics, and then calcined by holding at 1250 ℃ for 1 hour in a reducing atmosphere, and then again 630 The color change of the porcelain obtained by heat treatment for 2 hours, 6 hours, 12 hours, 24 hours, and 36 hours at ℃ is shown. Figure 2 shows the ceramic material heat-treated for 2 hours at 630 ℃, Figure 3 shows the ceramic material heat-treated for 6 hours at 630 ℃, Figure 4 shows the ceramic material heat-treated for 12 hours at 630 ℃ , FIG. 5 shows the ceramic material heat-treated at 630 ° C. for 24 hours, and FIG. 6 shows the ceramic material heat-treated at 630 ° C. for 36 hours.

1 to 6, when the heat treatment at 630 ° C. (in the case of FIG. 1), the cinnabar glaze, which hardly developed color, was gradually developed while increasing the heat treatment time as shown in FIGS. 2 to 6. .

This method shows the same result even if the cinnabar glaze composition is applied to the ceramics and kept at 630 ° C. during cooling, and the cooling is carried out, and the cinnabar glaze is maintained at 600 to 700 ° C. in all atmospheres without depending on oxidation and reducing atmosphere. Shows color development.

1 parts by weight of copper oxide (CuO) was added to lime-based glaze having the composition shown in Table 2, and then oiled to the ceramics, and then maintained at 1250 ° C. for 1 hour in a reducing atmosphere and calcined, followed by heat treatment at 630 ° C. again. The same result was found for.

<Example 2>

Table 1, 1 part by weight of copper oxide (CuO) and 1 part by weight of ZrO ₂ , CeO ₂ or HfO _{2 is} mixed with 100 parts by weight of glaze of lime barium-based glaze to prepare a cinnabar glaze composition. After lubricating the ceramics, it was calcined at 1250 ° C. for 1 hour in a reducing atmosphere.

FIG. 7 illustrates the addition of 1 part by weight of copper oxide (CuO) to 100 parts by weight of glaze to a lime-barium based glaze having the composition shown in Table 1 to prepare a cinnabar glaze composition, and after the cinnabar glaze composition is oiled to the ceramics, a reducing atmosphere Photo shows ceramics obtained by firing at 1250 ° C for 1 hour at.

Figure 8 is a lime barium-based glaze having a composition of Table 1 by mixing 1 part by weight of copper oxide (CuO) and 1 part by weight of ZrO _{2 to} 100 parts by weight of glaze to prepare a cinnabar glaze composition, the cinnabar glaze composition to the ceramic After lubrication, it is a photograph showing the ceramics obtained by baking for 1 hour at 1250 ℃ in a reducing atmosphere.

Figure 9 is a lime barium glaze having a composition of Table 1 to 1 part by weight of copper oxide (CuO) and 1 part by weight of CeO ₂ with respect to 100 parts by weight of glaze to prepare a cinnabar glaze composition, the cinnabar glaze composition to the ceramic After lubrication, it is a photograph showing the ceramics obtained by baking for 1 hour at 1250 ℃ in a reducing atmosphere.

10 is a lime barium glaze having a composition shown in Table 1 to 1 part by weight of copper oxide (CuO) and 1 part by weight of HfO ₂ with respect to 100 parts by weight of glaze to prepare a cinnabar glaze composition, the cinnabar glaze composition to the ceramic After lubrication, it is a photograph showing the ceramics obtained by baking for 1 hour at 1250 ℃ in a reducing atmosphere.

Referring to FIGS. 7 to 10, ZrO ₂ , CeO ₂ or HfO ₂ as opposed to showing unstable color development when using a composition (in the case of FIG. 7) with an anti-glaze glaze without adding ZrO ₂ , CeO ₂ or HfO _2. In case of using the cinnabar glaze composition added (in the case of FIGS. 8 to 10), all showed stable color development.

As mentioned above, although preferred embodiment of this invention was described in detail, this invention is not limited to the said embodiment, A various deformation | transformation by a person of ordinary skill in the art within the scope of the technical idea of this invention is carried out. This is possible.

Claims (9)

Glazes comprising KNaO, CaO, Al ₂ O ₃ and SiO ₂ ;
Copper oxide (CuO); And
At least one material selected from ZrO ₂ , CeO ₂ and HfO ₂ ,
The glaze has a molar ratio of 0.1 to 0.4: 0.3 to 1.0: 0.25 to 0.4: 2.5 to 4.0 of the KNaO, the CaO, the Al ₂ O _3, and the SiO ₂ ,
The copper oxide (CuO) is contained 0.1 to 5 parts by weight based on 100 parts by weight of the glaze,
The at least one material selected from ZrO ₂ , CeO ₂ and HfO ₂ contains 0.1 to 7 parts by weight based on 100 parts by weight of the glaze.
According to claim 1, wherein the KNaO Kina jinsa glaze composition for ceramics, characterized in that K ₂ O and Na ₂ O make a weight ratio of 1: 1 to 2.5.
The cinnabar glaze composition for ceramics according to claim 1, wherein the ZrO ₂ , the CeO _2, and the HfO ₂ form a weight ratio of 1: 0.01 to 3: 0.1 to 3.
According to claim 1, wherein the glaze further comprises BaO, wherein the CaO and BaO cinnabar glaze composition for ceramics, characterized in that the mole ratio of 1: 0.1 to 1.0.
Preparing a glaze having a molar ratio of 0.1 to 0.4: 0.3 to 1.0: 0.25 to 0.4: 2.5 to 4.0 of KNaO, CaO, Al ₂ O _3, and SiO ₂ ;
Preparing 0.1 to 5 parts by weight of copper oxide (CuO) based on 100 parts by weight of the glaze;
Preparing 0.1 to 7 parts by weight of at least one material selected from ZrO ₂ , CeO ₂ and HfO ₂ with respect to 100 parts by weight of the glaze;
Mixing the glaze, the copper oxide (CuO), and at least one material selected from ZrO ₂ , CeO _2, and HfO ₂ to obtain a cinnabar glaze composition for ceramics;
Pouring the cinnabar glaze composition for ceramics into a ceramic product; And
Calcining the pottery material being lubricated in a reducing atmosphere.
The method of claim 5, wherein the KNaO is characterized in that K ₂ O and Na ₂ O in a weight ratio of 1: 1 to 2.5.
The method of claim 5, wherein the ZrO ₂ , the CeO _2, and the HfO ₂ form a weight ratio of 1: 0.01 to 3: 0.1 to 3. 7.
The method of claim 5, wherein the glaze further comprises BaO, and the CaO and BaO form a molar ratio of 1: 0.1 to 1.0.
The method of claim 5, wherein after the firing step,
The method of producing ceramics, characterized in that it further comprises the step of heat-treating the fired product at a temperature of 600 ~ 700 ℃ for 10 minutes to 48 hours.

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