KR101670686B1

KR101670686B1 - Scratch-resistant celadon composition comprising frit

Info

Publication number: KR101670686B1
Application number: KR1020150088971A
Authority: KR
Inventors: 김규설
Original assignee: 주식회사 행남자기
Priority date: 2015-06-23
Filing date: 2015-06-23
Publication date: 2016-10-31

Abstract

The present invention further relates to a production method thereof. According to the present invention, by producing celadon using the molten frit in the celadon composition, surface illuminance and surface hardness of the celadon increase compared to existing common counterpart. Owing to improved fragility, convenience also increases when used as tableware. In addition to improved heat-resistant impact and hardness, color adjustment and mass production are possible as well.

Description

Scratch-resistant celadon composition comprising frit < RTI ID = 0.0 >

The present invention relates to a scratch resistant celadon composition containing a frit, more specifically, a melted frit. The celadon composition according to the present invention improves the surface roughness of the celadon The surface hardness is increased and the brittleness is improved. Thus, it can be more conveniently used when used as a tableware, has improved thermal shock resistance and strength, has the advantage of being able to control the chromaticity and mass production.

Celadon is a pottery containing iron and glaze. If there is not sufficient air during firing, incomplete combustion occurs, and it becomes FeO in iron oxide of Fe ₂ O ₃ mainly by carbon monoxide and turns to a weak whitish color. People in the Goryeo period called it jelly. The color is appreciated even to the present, and the research to utilize the celadon as a tableware of the living continues recently. In Kangjin County, which is the representative of Celadon, it is actively supporting the private sector in order to revitalize the celadon industry. According to a survey by Gangjin County, celadon utensils used in general shops are currently in use at a rate of 20 ~ 30%. As a result of the survey on restaurants using celadon utensils, the celadon color was dark and was not harmonious with the food, and it was thicker than the white porcelain dish, which was heavy and inconvenient to use.

The thicker the celadon utensils are, the lower the plasticity and the strength compared with the white porcelain. It is therefore necessary to improve the plasticity and strength of the substrate. In addition, celadon glaze has many pores on the surface and has a large crack resistance, resulting in a lot of scratches. This is a part that must be improved because it is related to hygiene and cleaning. Also, due to the nature of the base, the celadon tableware has a limit of form. For example, since the formability of the substrate is poor, the defective rate is high and the defective rate is high when the resin is thinly formed, resulting in a decrease in the production yield. This will be a dish that is not preferred by companies producing celadon utensils. Therefore, it is necessary to improve the formability of the celadon base. In terms of design, celadon utensils are often considered thick, dull, heavy, and dark. This is shaped thickly to maintain its shape in the traditional celadon production process. It is a reality that the celadon utensils of the sleek and sophisticated design that consumers desire are hard to come out. Therefore, if you can make a celadon tableware of various and thin design like the white porcelain dish which is widely used, it will be a requirement that can appeal to the consumers. The color also reduces the color of the food than the usual tableware if it contains the food. This means that the purpose of food, which is the basic requirement of living tableware, is lost, and it is necessary to adjust brightness and color saturation in celadon tableware and various colors other than the fixed color of the traditional celadon jade color. It is not the celadon that breaks the tradition but the celadon dishware which is a fusion of tradition and modern sophistication is needed.

Korean Laid-Open Patent Application No. 2015-0061130 (disclosed on June 4, 2015) Korean Registered Patent No. 1,343,808 (Registered on December 16, 2013) Korean Registered Patent No. 1,343,806 (Registered on December 16, 2013)

Cho, HJ et al., A Study on the Thermal Stability of Heat Resistant Fluororesin Coatings, Polymer (Korea), Vol.29, No.1, pp96-101, 2005 Kim, Dong-Hyun et al., Olefinic Thermoplastic Elastomer and Styrenic Thermoplastic Elastomer, Elastomers and Composites, Volume 45, Issue 3, 2010, pp.152-155

The present invention aims at solving the hygienic problem caused by pores and cracks on the surface of celadon glaze. That is, it increases the scratch resistance according to the increase of the hardness, toughness and roughness of the oil surface, and provides the living table according to the reduction of the oil surface crack due to the adjustment of the thermal expansion coefficient, thereby increasing the hygiene in use, We want to provide tableware.

In addition, the present invention provides a celadon tableware which is thinly formed and is light and sturdy, and also provides a celadon improved in thermal shock resistance.

The present invention also aims to provide a celadon which is out of the conventional dark and hard celadon dish design and which combines the charm of the traditional celadon with the modern sense.

The present invention relates to a substrate; The present invention solves the above problems by providing an scratch resistant celadon composition comprising frit and celadon glaze.

In one embodiment of the present invention, the substrate is a mixture of 10 parts by weight of celadon soil and 80 to 100 parts by weight of white porcelain.

In one embodiment of the present invention, the frit comprises 50 to 75 wt% of SiO ₂ , 5 to 20 wt% of Al ₂ O ₃ , 0.1 to 3 wt% of Fe ₂ O ₃ , 5 to 20 wt% of CaO, 0.1 to 3 wt% 1 to 5% by weight of K ₂ O, 0.1 to 3% by weight of Na ₂ O and 0.1 to 10% by weight of ZnO, and a content of B ₂ O ₃ of 4.9% by weight or less.

In an embodiment of the present invention, the celadon composition is characterized by having a water content of 40 to 45%.

In one embodiment of the present invention, the frit is contained in an amount of up to 50% by weight of the total weight of the glaze composition.

The present invention also provides a method of making a celadon material comprising the steps of: (a) preparing a celadon material comprising a substrate, a frit, and a celadon glaze; (b) adding water to the celadon material to form a celadon composition having a moisture content of 40 to 45%; (c) molding the celadon composition; And (d) firing the molded product at 1200 to 1400 占 폚.

The celadon composition according to the present invention improves the surface roughness of celadon celadon, increases the oil level hardness, and improves the embrittlement by using the melted frit to make the celadon more convenient than the conventional commercial celadon, Impact strength and strength are improved, chromaticity control is possible, and mass production is possible.

Fig. 1 shows a typical commercial product for living table used for scratch resistance evaluation.
2 is an XRD graph of an amorphous form.
Fig. 3 is a photograph of the surface of a commercial tableware.
4A shows the hardness analysis results of the lead products.
4B shows the result of toughness analysis of the leading products.
4C shows the results of illuminance analysis of the leading products.
4D shows the result of strength analysis of the leading products.
Figure 4E shows the results of brittleness analysis of the leading products.
5 shows the particle size of the raw materials used ((a) celadon soil, (b) white porcelain soil).
6 shows the microstructure ((a) celadon soil and (b) white porcelain soil) of the raw materials for use.
Fig. 7 shows the crystalline phases ((a) celadon soil and (b) white porcelain soil) of the raw materials for use.
8 is a view showing a process of mixing the substrate.
9 is a graph showing the plasticity of 100% celadon soil and mixed soil.
10 shows a moldability test process.
Fig. 11 shows the moldability test result (mixed substrate).
Fig. 12 is a graph showing the results of the strength measurement of the substrate.
13 is a graph showing the results of thermal expansion coefficient analysis (600 DEG C) of the substrate.
Fig. 14 shows a lease reducing furnace (2.5 rubes).
Fig. 15 shows the particle sizes ((a) to (e) frit, (i) celadon glaze) of frit and celadon glaze.
Fig. 16 shows the crystallographic image of celadon glaze and frit ((i) celadon glaze (a) to (d) frit).
17 shows the thermal expansion coefficient (600 DEG C) of celadon glaze and frit.
18 shows the appearance (1250 DEG C) of a sample subjected to reduction firing by mixing frit with celadon glaze.
19 is a graph showing the illuminance of the glaze to which the frit is added.
20 is a graph showing the hardness of the glaze to which the frit is added.
21 is a graph showing toughness of the frit added with frit.
22 is a graph showing the brittleness of frit added with frit.
23 shows the color (1250 DEG C) of the celadon oil surface reduced and fired with 2.0 L of LPG.
24 shows the color (1250 DEG C) of the celadon oil surface reduced to 2.3L by LPG.
25 shows the color (1250 DEG C) of the celadon oil surface reduced and fired with 2.6 L of LPG.
26 shows the color (1250 DEG C) of the celadon oil surface reduced to 2.9 liters by LPG.
Fig. 27 shows the change in chromaticity.
Fig. 28 shows the results of the coloring oxide addition test of celadon.
Fig. 29 shows secondary results of a coloring oxide addition test of celadon.
30 shows the results of the thermal shock test of commercial celadon and celadon prototype products.
Fig. 31 shows the wainscot after the measurement of the wear resistance.
Fig. 32 shows an optical microscope image (x300) after wear resistance measurement.
33 is a graph showing the results of measurement of wear resistance.
Fig. 34 shows the test results and test results of endurance test of celadon samples.
Fig. 35 is a diagram showing a prototype production process.

The present invention relates to a substrate; Frit, and celadon glaze.

Generally, it is reported that the strength increases as the content of alumina increases. In the present invention, the celadon soil was mixed with white alumina having a high alumina content ratio, and the plasticity before sintering was evaluated and the strength after sintering was evaluated. In the celadon soil 10%, 90% And was found to meet the quantitative target value of 100 MPa, so that a mixture of 10 parts by weight of celadon soil and 80 to 100 parts by weight of white porcelain was used. The higher the content of the celadon soil, the lower the formability. The base mixture is prepared by mixing the celadon soil dried powder and the white powdery dried powder into a pot and mixing with a ball mill in a water content slurry type.

In the present invention, frit is a glassy powder which is easy to melt and is excellent in hardness and toughness. When the frit is added to the glaze, the smoothness of the surface can be influenced and the roughness of the surface can be reduced. It is preferable to use a fleece-free frit, and it is preferable to use a fusing agent capable of firing at 1000 ° C, specifically 1200 ° C, more specifically 1250 ° C, and it is preferable to use a frit which does not affect the color during firing desirable.

The value of the thermal expansion coefficient of the substrate should be higher than the thermal expansion coefficient of the glaze and the difference should be less than 10%. When the thermal expansion coefficient of the celadon glaze is higher than that of the celadon glaze, the difference in thermal expansion coefficient becomes larger as the amount of the frit added increases.

In order to check the color of the glaze mixed with celadon glaze and frit in the present invention, the glaze is baked and fired in a mixture of 10% of celadonite and 90% of white celadon as optimum ratios. %, 30%, 50%, 70%, and 90% of the frit in the glaze. As a result, when the frit ratio in the glaze exceeds 50% desirable.

In the present invention, the celadon product can be mass-produced by molding, drying, first sintering, mass sourcing, second sintering, chemical transfer and third sintering, more specifically, , And then dried at 800 ° C for a first time, followed by massive sintering, followed by a secondary calcination at 1250 ° C in a reducing atmosphere, followed by a third calcination at 830 ° C with a chemical transfer paper attached to the calcined product .

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, This is possible.

1. Evaluation Method

1) Evaluation of scratch resistance

Hardness and toughness were measured by Vickers hardness measurement to measure Brittleness.

Vickers Hardness measurement method KSL0811 )

Is the value calculated from the surface area of the concave portion obtained from the test load when the concave portion is made on the test surface and the diagonal length of the concave portion by using a diamond quadrangular pyramid having a face angle of 136 degrees.

HV: Vickers hardness (units are not attached to HV values)

F: Test load (N) (¹)

S: surface area of concave (mm 2)

d: average length of the diagonal line of the concave portion (mm)

θ: Facing angle of the diamond press (136 °)

When the unit of test load F is Kgf, the Vickers hardness is calculated by the following formula.

2) Evaluation of thermal expansion coefficient of glaze and substrate

Measurement method of thermal expansion coefficient

The measurement of thermal expansion is a method which is useful for predicting the stress applied to the material when the material is applied in combination with other materials or in case of single-phase material, and the temperature is not constant. The sample was processed into a cylindrical shape having a length of 5 to 6 mm and a length of 25 mm and then heated at a rate of 10 ° C / min to measure the thermal expansion coefficient.

3) Evaluation of color (L *, a *, b *)

The degree of color was measured using a colorimeter to quantitatively evaluate. A colorimeter is a device designed to measure color by optical system, sensor, and program. The optical system is an illumination device usually made of an integrating sphere. Diffusion lights made in the integrating sphere are irradiated on the surface of the sample, Reading light with a sensor of a spectrophotometer.

The chromaticity measurement is a standard of measurement such as diffuse illumination or unidirectional illumination, not a single beam or double beam of a general spectrophotometer. In order to display the accepted information in the chromaticity unit, the spectral information is integrally operated to integrate a formula that can be represented by color coordinates such as L *, a *, b *, L *, C *, h * The result is calculated by the program.

4) Strength evaluation

100MPa or more (KSL1591)

The sintered body was processed into a rectangular column of 4 * 3 * 40 mm, and the parallelism of the upper and lower surfaces was chamfered to 0.02 mm or less as defined in KS B0425, and then the surface was polished to measure the three point bending strength at a crosshead speed of 0.5 mm / min .

P: Cutting value (kgfm / sec ² )

L: Distance between supports (10cm)

b: Width of specimen (cm)

d: thickness of specimen (cm)

9.8: Gravitational acceleration (m / sec ² )

5) Evaluation of thermal shock resistance

The specimens were heated to 100 ° C or higher and then quenched at room temperature. The ink was dropped on the oil surface to confirm whether cracks, peeling occurred, or cracks, cracks, or flaws in the substrate. The remaining specimens except the defective specimens were reheated and re-tested (3 repetitions). The remainder of the specimens without any defects were heated to a maximum temperature of 180 ° C.

Heat shock resistance measurement condition Measuring conditions Water temperature Below 10 ℃ Tank size Distance from surface to surface of specimen 15 mm or more,
The size that does not overlap even when several test specimens are put in. Notice Adjust the amount of water so that the water temperature is 29 ℃ or less even if the heated specimen is cooled.

6) Evaluation of plasticity

Sampling is carried out according to MHS-H-101 (Sampling method of porcelain raw material). After shrinking to 300 g, the pot mill is used to reduce the water content of the fine pulverization (325Mesh residual rate 0.2-0.3% After preparing the substrate in a kneaded state, about 200 g of the substrate was filled so that air could not flow into the molding die. The specimen was placed on the measuring instrument and the initial height (H ₀ ) was measured to the first decimal point. The stopper was dropped on the specimen and the stopper was instantaneously removed. Measure the height (H ₁ ) of the specimen deformed by the falling pressure plate to the first decimal point. About 20 g of the sample to be measured was taken and the moisture content (W ₁ ) was measured according to MSH-H-102 (glass moisture measurement method).

In the second measurement, the moisture content of the sample was adjusted to be equal to one time, and then the deformed sample height and water content were measured (repeatedly 3 to 5 times per sample).

The XY graph is expressed by the pfeffer 'korn method with the inverse value of the deformation value, that is, 1 / E _i = 1 / (H _i / H _o ) as the X value and the corresponding moisture content measurement value as the Y value. After plotting according to the measurement curve, the moisture content at 3.30, which is the inverse value of the optimum plastic deformation value, was interpolated and found to the first digit below the decimal point.

E _i = H _i / H _o

H _o : initial height of the test specimen, initial height of the test specimen shall be 40 mm.

H _i : Height of the deformed specimen in the second time (mm)

E _i : the deformation value of the i-th time

6) Surface roughness evaluation

Ra value is 0.1 탆 or less (KSB 10110-8)

(Roughness) of the oil surface was quantitatively evaluated. When the specimen was placed on the equipment and the measurement was started, the stylus moved to contact the surface of the specimen and then converted to the arithmetic average roughness (Ra) value.

7) Abrasion resistance measurement evaluation

It is an equipment for evaluating the abrasion resistance of the material during the development of the industrial system or material in general, which is subject to wear friction. Through this equipment, it is possible to check the friction coefficient, friction force and wear amount of the material. After fixing the test specimen to the jig, use a stainless steel ball to rotate the specimen for a certain distance and time with a fixed load. The friction coefficients were compared for various specimens under the same conditions.

First of all, among the lead-free frit without lead, a frit of 1000 ℃ or more was selected and Matt frit was excluded for gloss of the tableware. In this study, four kinds of Frit samples were sampled in OCI and one sample was sampled in Tomatec. It is confirmed that the use of the frit improves the crack resistance and the surface roughness of the oil surface is improved. However, since the cost of the frit is high, the use of the frit causes a cost reduction problem. .

2. Selection of glaze

Celadon glaze composition, which is the basic base, was selected by considering non - cracking glaze and two materials which are easy to supply and receive. We have started to study two types of glaze celadon glaze produced in Gangjin area in Korea and celadon glaze in Icheon area, which has many celadon production yards. Considering the thermal expansion coefficient, the cracking property, the hardness of the oil surface, and the ease of supply and demand using the two glazes having a low thermal expansion coefficient which have been recently used, the present invention can be applied to the Icheon glaze which has a relatively low thermal expansion coefficient The glaze was chosen as the base glaze.

3. Selection of possession

The selection of celadon base is easy to receive and supply as well as the glaze, and it has a higher thermal expansion coefficient than the thermal expansion coefficient of the glaze, so that it is stable in heat cracking resistance with glaze. For the first time, I tried reduction furnace first by receiving various materials such as white porcelain, celadon, and chungcheong which can be easily purchased from the surrounding area. Because of the characteristics of the celadon, the color of the base was also important because it later influenced the color in the final product. The most important one is the plasticity and strength of the substrate. If the plasticity of the substrate is not excellent, the planned mass production becomes difficult, and it can not produce a living dishware thinly and durable like ordinary porcelain. Considering this point, the possession was selected.

4. Molding method

At present, domestic celadon production is mostly produced by hands. In such a case, there is a limit of the production amount, and a lot of manpower causes a rise in the unit price of the celadon utensils. Therefore, if automatic molding is possible in the present porcelain production line by using improved substrate, it is possible to produce celadon with various designs in a certain form like the process of producing commercial white porcelain dishes. Thus, in the process of cost reduction and sales, it will be an opportunity to supply celadon dishes to overseas markets rather than small domestic celadon markets. Therefore, in this study, it is possible to produce in the automatic line if the plasticity of the substrate can be improved and a certain substrate can be produced.

5. Firing conditions

In the process of celadon production, there is a process of reduction and firing which has a great influence on color. The firing and the basic tests were carried out in a laboratory electric furnace while maintaining the best reduction conditions. In the final prototype stage, the reduction condition of the small electric furnace was applied to the leasing kiln of 2.5 rubes to produce prototypes to some extent. In this process, the important degree of reduction was kept constant.

Firing conditions (test pieces) step Temperature section (℃) speed( min ) time( min ) LPG (L) Air (L) Primary heating 0 to 900 ° C 3 ° C / min 300 0 0 Secondary heating 900 ~ 1250 ℃ 2 ° C / min 175 2.6 7 maintain 1250 ℃ maintain 30 2.6 7 Cooling 1250 ~ 30 ℃ Natural cooling - 0 0

Sintering conditions (lease return furnace) step Temperature section (℃) speed( min ) time( min ) Primary heating 0 to 900 ° C 3.08 ° C / min 300 Secondary heating 900 ~ 1250 ℃ 1.06 ° C / min 175 maintain 1250 ℃ maintain 110 Cooling 1250 ~ 50 ℃ Natural cooling -

6. Molded product type

With the developed base and glaze, they were molded and sown to form a set of coffee cups and a half-turn machine.

7. Chemical transfer paper

Improved development in traditional celadon colors In the celadon, a transfer paper designed in various shapes of colors was selected, and the transfer paper was attached directly to the material to be subjected to a chemical firing process. The transfer paper was selected through the questionnaire for the anti - foaming test and the preference for the design color.

8. Property evaluation

In addition to evaluating the quality of the developed product, we have selected a certified testing and analysis organization in order to confirm that it has been developed in accordance with the quantitative development goals of this study, and received the results of the analysis and analysis in writing. In the present invention, the Korean Polymer Testing Institute and the Daegu Machinery & Components Research Institute both received analytical samples and received official test results.

The results of research and development are as follows:

1) Leading product analysis

In order to evaluate the scratch resistance, the crystal phases of representative living beads on the market and surface roughness and oil photos were analyzed. The physical properties of the products were measured by using high-grade frit glaze, medium glaze frit glaze, commercial celadon, and foreign products which are commonly used as a Western tableware. The representative commercial product for living table used in the experiment is as shown in Fig.

As a result of XRD analysis of the product, most of the amorphous and quartz phases were found in the Elix and Gangjin celadon glazes, and in the rest of ZEN Korea, Hangmanam and Royal Copenhagen, amorphous XRD peaks were observed rather than specific peak values .

As a result of measuring the surface roughness of the above products, we could confirm the characteristics of ordinary white porcelain and blue porcelain tableware. It has been confirmed that the surface roughness (Ra) value is lowered to 0.1 or less because of the high degree of glazing which uses frit and the smoothness of the oil surface in the case of Bonghua tableware. On the other hand, in case of celadon tableware, the surface roughness was large and the surface roughness was high. In Fig. 3, it can be seen that there are many large and small bubbles on the surface of the Gangjin celadon when compared with Hornnam's Bonin China which uses most of Frit. The presence of many bubbles in the glaze layer affects the hardness and toughness of the oil surface, which greatly affects the occurrence of scratches.

We analyzed the physical properties of leading products. The analytical items were evaluated for the finished products with the five items of hardness, toughness, roughness, strength, and surface roughness which were set as quantitative targets. As a result of the analysis, the surface hardness of the lead products was more than 6.0Gpa, and the surface roughness of the mode tableware except for the celadon tableware maintained the smoothness which was difficult to confirm visually because the surface roughness Ra value was 0.1 or less. The intensity value, which is the weak point of the celadon, was measured as low as the celadon tableware as expected. As a result of calculating the embrittlement value by measuring the length of cracks (according to load) by the IF method, all living tableware was measured to be 10 or less.

2) Development of substrate composition

Generally, it is reported that the strength increases as the content of alumina (Al ₂ O ₃ ) increases. Therefore, the mixture of celadon soot with high alumina content ratio was evaluated by plasticity evaluation before firing and strength evaluation after firing. Evaluation of thermal expansion coefficient (less than 10% of coefficient of difference with glaze)

White soot was used to improve not only the strength of the celadon soil but also the plasticity. As a result of analysis of the components of white sand and celadon soils used before the experiment, the SiO ₂ content of white sand and celadon sand was 64 ~ 68% Al ₂ O ₃ The composition was more than 26.3%. The content of MgO is 0.9% higher than that of white sand, and the content of P ₂ O ₅ in white sand is 0.45% higher than that of Celadon.

Chemical composition of Celadon soil and White sand soil SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ CaO MgO K ₂ O Na ₂ O TiO ₂ P ₂ O ₅ White potato 68.38 26.53 0.15 0.85 0.33 2.52 0.73 0.05 0.48 Celadon Sat 64.25 26.29 3.67 1.50 1.22 1.56 1.09 0.39 0.03

The average particle size of celadonite was 8.20 ㎛, which was more than 3 ㎛ larger than 5.15 ㎛ of white sand, and it was confirmed that there were fine particles of less than 1 ㎛ in white sand. The fine particles are excellent in cohesive strength and good plasticity, making it suitable for molding plates or thin articles in a fully automatic molding machine. It also promotes the sintering force during firing, which also affects the strength improvement.

As a result of observation of microstructures, the shape of the particles was observed as a plate in both the Celadon soil and the White sandy soil. The plate - type microparticles of 2 ㎛ or less contained about 16% in white sand so that the improvement of plasticity was considered to be affected.

Crystalline phase analysis revealed quartz and albite crystals in common. In celadonite, muscovite and halloysite crystalline phases, and white porphyrodite microcline and kaolinite, respectively.

The base mixture was prepared by mixing the celadon soil dried powder and the white powdery dry powder into a pot and mixing with a ball mill in a moisture content slurry type (dry weight: 32 kg, moisture content: 53%, mixed for 40 minutes)

Blending ratio (%) NO . Celadon Sat White potato One 10 90 2 30 70 3 50 50

White soot was mixed with 50%, 70%, and 90% of celadon soils and the plasticity was measured. The results are shown in graphs by evaluating the plasticity in terms of the plastic deformation value (exponent) and the water content in the Peferffer's Korn method. Based on the ratio of celadon soils, it was shown that when the content of celadon soil was increased from 50%, 70% and 90% in 100% of celadon soil, the water content increased and the strain decreased. The mixture of celadon soil 10% and 90% The substrate showed the best plasticity.

As a result of the plasticity test with plasticity test, it was possible to mold all three mixed materials with automatic molding machine, but the moldability decreased with the content of celadon.

Samples were prepared by mixing 50%, 70%, and 90% of white porcelain with Celadon, Celadon, and Celadon soils at 1250 ℃ and processed into 4 * 3 * 40mm rectangular columns. The strength of the processed specimens was measured as 67.51 MPa and 132.1 MPa, respectively. The measured values were 115.63MPa, 86.93MPa and 81.71MPa, respectively. . Therefore, it was confirmed that the intensity increased with the increase of white sand content in the celadon soil. The ratio of 100MPa, which is a quantitative target, was confirmed by the composition of celadon soil 1: white sand soil 9.

As a result of measuring the thermal expansion coefficient from room temperature to 600 ℃, it was found that the white sand was highest at 7.26 * 10 ^-6 / K at 600 ℃, Was the lowest at 5.20 * 10 ^-6 / K. The mixed substrate was found to be between the values of thermal expansion coefficients of white sand and celadon soils. 6.75 * 10 ^-6 / K, 6.40 * 10 ^-6 / K, and 5.81 * 10 ^-6 / K in order.

3) Development of celadon glaze composition

Frit is a vitreous powder which is easy to melt and has excellent hardness and toughness. When added to the glaze, it affects the smoothness of the oil surface and reduces the roughness of the surface. (Hardness, toughness, brittleness, surface roughness, thermal expansion coefficient (less than 10% difference in thermal expansion coefficient with base), thermal shock resistance) after quantitatively measuring the properties after reducing and firing at 1250 ° C by mixing various types of frit in a celadon glaze The optimum composition ratio was selected. The mixture of celadon glaze and frit was prepared by adding celadon glaze solid and 325 Mesh frit into a 500 ml pot, adding water with a moisture content of 40 to 45%, and mixing the mixture at a speed of 200 rpm for 1 hour.

* Frit selection conditions - lead-free frit, solidification which can be fired at 1250 ° C, which does not affect the color during firing.

Mixing ratio of celadon glaze and frit (%) Frit Celadon glaze 10 90 30 70 50 50

The test specimens were immersed in a glaze for 6 seconds and then reduced to 1250 ℃ at room temperature.

Firing condition (0.3 lube) step Temperature section (℃) speed( min ) time( min ) LPG (L) Air (L) Primary heating 0 to 900 ° C 3 ° C / min 300 0 0 Secondary heating 900 ~ 1250 ℃ 2 ° C / min 175 2.6 7 maintain 1250 ℃ maintain 30 2.6 7 Cooling 1250 ~ 30 ℃ Natural cooling - 0 0

Sintering conditions (2.5 barrels of lease) step Temperature section (℃) speed( min ) time( min ) Primary heating 0 to 900 ° C 3.08 ° C / min 300 Secondary heating 900 ~ 1250 ℃ 1.06 ° C / min 175 maintain 1250 ℃ maintain 110 Cooling 1250 ~ 50 ℃ Natural cooling -

To improve the scratch resistance of celadon glaze, five kinds of frit were selected and the first experiment was conducted. The chemical composition of frit was investigated in order to investigate the compositional change when celite glaze was added. Celadon glaze has an iron content of less than 2% and the highest SiO ₂ content compared to frit. The main component of the frit, SiO ₂ The content of a was the highest at 63% and the lowest frit at f was 51%. The characteristics of a frit were analyzed that the content of CaO was 4 ~ 12% higher than other frit. Britt had a high 5.3% KNaO content. The content of ZnO in c frit was 7 ~ 14% higher than that of other frit. drittite contained 4.50% of B ₂ O ₃ , which was much higher than other frit. e frit has had the highest content of KNaO to 9.49% Al ₂ O ₃ And 17.3%, respectively. The content of SrO was more than 8% higher than other frit.

Celadon glaze and chemical composition of frit (i: celadon glaze, a ~ f: frit) wt (%) SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ CaO MgO K ₂ O Na ₂ O TiO ₂ P ₂ O ₅ ZrO ₂ SrO B ₂ O ₃ ZnO BaO i 66.83 13.82 1.44 12.91 0.46 3.40 1.05 0.08 - - - - - - a 63.73 5.92 0.08 17.61 0.40 2.30 0.54 0.03 0.02 0.08 0.02 1.77 7.45 0.03 b 60.16 6.66 0.06 13.11 1.21 4.35 0.95 0.01 0.00 0.01 0.01 2.54 10.91 0.00 c 54.04 9.45 0.02 10.71 0.14 1.56 0.27 0.24 0.03 0.60 0.01 4.91 18.01 0.00 d 62.51 7.11 0.07 10.70 1.40 4.36 0.74 0.01 0.01 0.35 0.62 4.57 7.50 0.03 e 51.90 17.3 0.08 5.72 2.00 4.84 4.65 0.02 0.02 0.09 8.57 0.07 3.67 1.06

Thermogravimetric analysis was performed using a thermogravimetric analyzer (DTG-60H, Shimadzu, Japan) to select frites capable of high-temperature firing at 1250 ° C. The glaze was heated from room temperature to 1300 ℃ and the frit was elevated from room temperature to 1200 ℃ at 10 ℃ / min to confirm the melting point and small amount of weight. The celadon glaze was completely melted at 1237 ° C and the weight decreased by 14%. a frit was completely melted at 1172 ° C and 4% weight loss. The britt was completely melted at 1120 ° C and the weight decreased by about 2%. c frit was completely melted at 1000 ° C and the weight was reduced by about 1.6%. The drit was completely melted at 960 ° C and the weight decreased by about 2%. The frit was completely melted at 1175 ° C and the weight was reduced by about 3%.

Analysis of celadon glaze and frit particle size showed that the average particle size of celadon glaze was 9 ㎛. The average particle size of the a pritt was 13 탆, the average particle size of the britt was 5 탆, the average particle size of the c frit was 9.6 탆, the drit frit was 20 탆 and the average size of the frit was 13.5 탆. Frittes with celadon glaze and average particle size were c frit, britt was the smallest and dritt the largest.

Analysis of celadon glaze and frit crystallization showed that all of the frit was amorphous and that of celadon glaze was Quartz, Albite and Microcline.

Celadon glaze and frit were reduced and fired at 1250 ℃ and processed to ø6 * 25mm to measure the thermal expansion coefficient. The thermal expansion coefficient of the celadon glaze was 6.83 * 10 ^-6 / K at 600 ℃, 6.33 * 10 ^-6 / K for britt, 7.11 * 10 ^-6 / K for britt, 5.24 * 10 ^-6 / K, and the dipt rate was 9.85 * 10 ^-6 / K frit, which was 5.29 * 10 ^-6 / K. Since the thermal expansion coefficient value of the substrate is higher than the thermal expansion coefficient value of the glaze and the difference must be less than 10%, the dither with higher thermal expansion coefficient than the substrate is excluded from this experiment.

In order to check the color of celadon glaze and frit mixed glaze, the optimum ratio of celadon to 10% and 90% of white celadon were mixed and fired. The glaze was prepared by adding 10%, 30%, 50%, 70% and 90% of frit to celadon glaze. As a result of the firing, it was confirmed that when the frit ratio in the glaze was increased by 50% or more, the whitening occurred. As the thermal expansion coefficient was higher than that of celadon glaze and substrate, the difference in thermal expansion coefficient between drit and frit increased as the amount of frit added increased. In the case of e-frit, as the frit content increased, the gloss disappeared and matte tended to be removed.

The frit suitable for the present invention was selected as a, b, and c through the above experiment. In mixing the frit in the celadon glaze, only the maximum 50% was added to the frit, and the mechanical properties were evaluated.

The chemical composition of the glaze added with 10%, 30%, 50% of a, b, c frit is shown in the following table.

Chemical composition of glaze SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ CaO MgO K ₂ O Na ₂ O TiO ₂ P ₂ O ₅ ZrO ₂ SrO B ₂ O ₃ ZnO BaO a1 66.53 13.03 1.30 13.39 0.46 3.29 1.00 0.07 0.00 0.01 0.00 0.18 0.75 0.00 a2 65.93 11.45 1.03 14.33 0.45 3.07 0.90 0.06 0.01 0.02 0.01 0.53 2.24 0.01 a3 65.33 9.88 0.76 15.28 0.43 2.85 0.80 0.05 0.01 0.04 0.01 0.89 3.73 0.02 b1 66.17 13.10 1.30 12.93 0.54 3.49 1.04 0.07 0.00 0.00 0.00 0.25 1.09 0.00 b2 64.84 11.67 1.03 12.97 0.69 3.69 1.02 0.06 0.00 0.00 0.00 0.76 3.27 0.00 b3 63.51 10.24 0.75 13.02 0.84 3.88 1.00 0.04 0.00 0.01 0.01 1.27 5.46 0.00 c1 65.59 13.39 1.30 12.70 0.43 3.22 0.98 0.10 0.00 0.06 0.00 0.49 1.81 0.00 c2 63.10 12.53 1.01 12.27 0.37 2.85 0.82 0.13 0.01 0.18 0.00 1.48 5.44 0.00 c3 60.61 11.66 0.73 11.85 0.30 2.48 0.66 0.16 0.02 0.30 0.01 2.47 9.07 0.00

As a result of measuring the surface roughness of the experimental glaze, it was confirmed that as the frit was added, the surface roughness value was improved and decreased. The effect of adding frit was in the order of c> b> a. The composition of ZnO was found to be higher when ZnO content was higher.

The celadon glaze without frit was 0.39 ㎛, but it decreased by at least 40% by adding 10% of a frit. The addition of 30% decreased to 0.14 ㎛ and the addition of 50% decreased to 0.11 ㎛. When b - frit was added at 10%, it decreased 62% and decreased to 0.14 ㎛. The addition of 30% decreased to 0.10 ㎛ and the addition of 50% decreased to 0.09 ㎛. The addition of 10% c - frit decreased to 0.13 ㎛. The addition of 30% decreased to 0.07 ㎛ and the addition of 50% decreased the maximum of 80% to 0.05 ㎛. Therefore, the glaze with a quantitative target of 0.1 ㎛ or less was confirmed to be a glaze containing 50% of brittite and a glaze containing 30% and 50% of cfrit.

As a result of measuring the hardness of the glaze, it was found that the hardness of the glaze is increased finely as a whole. The hardness of celadon glaze was 5.85 GPa. When 10% of a frit was added, it increased by 0.06 GPa to 5.91 GPa. When 30% was added, it increased by 0.1 GPa to 5.95 GPa and when added 50%, it increased by 0.14 GPa to 5.99 GPa. When 10% b frit was added, the value increased by 0.08 GPa and increased by 0.13 GPa when 5.93 GPa was added and increased by 0.18 GPa when added by 50%, which was 6.03 GPa. When 10% c frit was added, 0.1 GPa increased to 5.95 GPa, and when added 30%, 0.15 GPa increased to 6.0 GPa and when added 50%, 0.2 GPa increased to 6.05 GPa. The increase in the rate of increase was less than 5%. The ratio of frit to that of quantitative target of 6.0 GPa was confirmed by the glaze containing 50% brittite and the glaze containing 30% and 50% cprite.

Toughness in that the result of measuring the toughness of the glaze frit are added the listener is more added to the frit glaze yeoteuna 0.54 MPa m ^0. ⁵ has been shown to increase the value of the toughness. In the case of a frit, it was 0.85 MPa m ^0.5 when added 10%, 1.03 MPa m ^0.5 when added 30% When 50% was added, it was 1.12 MPa m ^0.5 . In the case of brittite, it was 0.97 MPa m ^0.5 when 10% was added, 1.12 MPa m ^0.5 when 30% was added, and 1.2 5 MPa m ^0.5 when 50% was added. In the case of c-frit, it was 1.05 MPa m ^0.5 when added 10%, 1.17 MPa m ^0.5 when added 30%, and 1.25 MPa m ^0.5 when 50% was added.

The brittleness was determined by hardness value and toughness value of glaze. The brittleness is a numerical representation of the property that can not be deformed when an external force is applied, and the breaking property. The smaller the value, the smaller the phenomenon of cracking. Therefore, as brittleness decreases, it can be seen that it is improved and improved. Embrittlement of the resulting violet glaze frit is not added calculated brittleness which is calculated by dividing a hardness value in toughness is the addition of 10.76 ㎛ ^0.5 yeoteuna frit was confirmed to be lowered to below 7 ㎛ ^0. ^5. a. When 10% of frit was added, 6.93 ㎛ ^0.5 , when it was added 30%, 5.79 ㎛ ^0.5 , and when 50% was added, it was lowered to 5.34 탆 ^0.5 . b. When 10% of brittite was added, 6.14 ㎛ ^0.5 , when added 30%, 5.32 ㎛ ^0.5 , and when 50% was added, it decreased to 5 ㎛ ^0.5 . When 10% c-frit was added, it was 5.66 ㎛ ^0.5 , 5.12 ㎛ ^0.5 when added 30%, and 4.82 탆 ^0.5 when added 50%. Therefore, it was confirmed that the addition of frit improves the toughness because the toughness is greatly improved. In addition, the brittleness tended to increase as the amount of frit added increased, but the width of improvement gradually decreased, and it was found that the optimum ratio was 50% or less.

Further experiments on the change of color due to the amount of LPG during reduction and firing were carried out and the results are shown in the table. Air was fixed at 7L and the amount of LPG was changed from 2.0L to 2.9L. As a result, when the amount of LPG was 2.0L, the reducing atmosphere was not properly formed and the blue light of celadon was not visible. As the frit was added, the brightness increased and the saturation decreased.

L * a * b * (1250 ° C) of the celadon surface reduced to 2.0 L of LPG NO . L * a * b * 100% 65.22 -1.44 22.95 a 10% 70.20 -1.92 20.23 a 30% 75.99 -2.43 18.07 b 10% 67.51 -2.27 23.08 b 30% 75.38 -1.92 17.90 c 10% 69.86 -1.73 21.75 c 30% 73.30 -2.08 19.50

When the amount of LPG was 2.3L, a reducing atmosphere was formed to some extent, and blue light appeared. The a * and b * values were measured a little lower.

L * a * b * (1250 ℃) of celadon oil surface reduced to 2.3L of LPG NO . L * a * b * 100% 66.16 -7.36 6.75 a 10% 70.68 -7.26 5.57 a 30% 74.13 -8.20 3.63 b 10% 69.82 -8.61 5.13 b 30% 75.80 -6.88 4.42 c 10% 71.34 -6.73 6.00 c 30% 72.94 -8.38 4.92

When the amount of LPG was 2.6L, the reducing atmosphere was stabilized and blue bluish purple color appeared and the a * value and b * value were measured to be lower.

L * a * b * (1250 ℃) of celadon oil surface reduced to 2.6L of LPG NO . L * a * b * 100% 63.97 -10.97 4.75 a 10% 72.50 -7.57 3.87 a 30% 75.19 -9.13 2.67 b 10% 71.64 -8.64 3.75 b 30% 78.23 -7.84 2.94 c 10% 74.86 -8.42 4.67 c 30% 76.38 -9.25 3.92

When the amount of LPG was 2.9L, a reducing atmosphere was overproduced and grayish blue color appeared on the substrate and oil surface, and a * value and b * value were lowest.

L * a * b * (1250 ℃) of celadon oil surface reduced to 2.9L LPG NO . L * a * b * 100% 68.01 -9.03 3.00 a 10% 70.91 -8.61 2.43 a 30% 74.93 -7.47 1.93 b 10% 70.47 -9.28 3.30 b 30% 78.05 -7.95 2.63 c 10% 72.54 -7.27 3.42 c 30% 77.92 -9.15 2.67

The coloring agent test was carried out to finely adjust the celadon color during the reduction firing. The color change was observed by adding BaO, CaO, MnO, P ₂ O ₅ , TiO ₂ and ZnO, which can be used as coloring elements, to 0.5% ~ 2.0%. The experiment was carried out for a modern blue color with a traditional green celadon celadon. The reduction conditions were tested under conditions of 2.6L of LPG and 7.0L of air, which are stable reducing atmosphere according to the above results.

As a result of the second color development test, the CuO content changed greatly from the reducing condition to the Red content as the content of CuO increased. The color of CoO in blue color is confirmed by the data above. As a result, the color can be clearly displayed even in a very small amount. Therefore, if a blue color is added in a trace amount of less than 0.05% . It can be seen that the color development test in which an Fe component that develops the jade color of the celadon is further added, proceeds close to the jade color of the traditional celadon. As a result, CuO or CoO is a strong coloring oxide and can be used in the product for the original bright color, and the change according to the content of Fe will enable the adjustment according to the color change of the traditional celadon.

As a result of the thermal shock test, it was confirmed that the ordinary commercial celadon was cracked at the oil surface at ΔT 120 ° C. and unstable to thermal shock. On the other hand, it was confirmed that the prototype manufactured by applying the celadon glaze studied in this experiment was not cracked at 120 ° C and was improved. As a result of evaluating up to? 150 ° C, it was confirmed that the cracks did not propagate to the thermal shock and that the cracks were stable.

The abrasion resistance test was conducted as an additional test. The glaze with no frit added and the frit added to measure the degree of wear of the glaze with improved surface roughness due to the continuous friction of the metal. A 10 mm stainless steel ball was fixed on the top and the specimen was fixed at the bottom and measured at a minimum load of 20 N, set to 5 m in length. The celadon glaze, which did not contain any frit, showed good penetration of the oil surface and the most abrasion, while the c 30% specimen was almost invisible to the naked eye. It was confirmed that the surface roughness was greatly improved.

The surface was observed with an optical microscope to observe the oil surface with certainty. 100% of celadon glaze appeared to be crushed in the oil field, and the a of the celadon glaze had no metal marking but a long glaze pavement. In case of b, the length of recess of glaze was smaller than a, but the marking of metal was severe. In the case of c, the denting phenomenon appeared, but the metal marking was not more severe than a and b.

As a result of measurement, the celadon glaze showed the lowest friction coefficient of 1.75 ㎛ at 5m, a of 0.87 ㎛, b of 0.57 ㎛ and c of 0.18 ㎛.

Additional experiments were conducted with the completed prototype. The endurance test was conducted to evaluate the reaction between the detergent and the transfer paper. For the test method, an intermediate holder for placing the specimen in a 4 L stainless steel container with a cover is installed. To this vessel is added a solution of 15 g of anhydrous sodium carbonate in 3 l of distilled water, and the mixture is heated to 98 to 100 ° C. While the solution is being heated, prepare the sample according to our finished product inspection standard (MHS-F-401), and then wash the specimen with distilled water heated (over 82 ° C). And washed with acetone until the thin distilled water film is uniformly formed and dried in the air. When the prepared solution is heated to the specified temperature, the samples are not overlapped with each other and the surface is completely immersed. Cover the sample and keep at 98 ~ 100 ℃ for 2 hours. After 2 hours, remove the specimen, rub the transfer part with a cleaning cloth, rinse with distilled water (82 ℃ or more) and dry in air. The time for soaking in the solution is increased to 4 hours and 6 hours and measured by the same method. The evaluation is done visually and compared with the untreated specimens. The judging grade is shown in the table below.

Rating and content of endurance test Judgment grade Degree of erosion Visual confirmation of erosion area 0 none It does not cause any substance to be burnt by rubbing operation and does not cause gloss damage. One Has a little There is a trace of some substance on the fabric for washing, a little blurred or dulled color appears, and the color change can be distinguished. 2 Usually available There is a trace on the fabric for cleaning, and you can see blurred or uneven color of obvious color. 3 Severe The greater the traces of material on the fabric, and the greater the removal of material from the ornament. 4 Absolute severity The material of the decorative part is completely removed and the color of the original decoration can not be identified.

As a result of evaluating the antifouling performance of the celadon prototype, it was judged that it was stable in the reaction with the detergent because there was no reaction such as deterioration of gloss, discoloration, or foreign substance when the test was divided into primary, secondary and tertiary.

Results of endurance test of celadon prototype Name of sample Measure Judgment Primary (2 hours) Secondary (4 hours) Third (6 hours) Color change Gloss degradation Color change Gloss degradation Color change Gloss degradation Prototype 1 none none none none none none Good Prototype 2 none none none none none none Good

3) Prototype production

We applied prototype and glaze developed in this study to a mass production line and fabricated prototype through molding, firing and transfer process. During the prototype production process, the secondary firing was carried out by renting a reduction facility (2.5 RUBE). The product was molded with an automatic molding machine and dried. After drying, the mixture was subjected to a first firing at 800 ° C, followed by a heavy firing, and then a second firing at 1250 ° C in a reducing atmosphere. A chemical transfer paper was attached to the plastic article and subjected to a third firing at 830 ° C.

Claims

10 parts by weight of celadon soil; 80 to 100 parts by weight of white porcelain; And
Glaze compositions comprising frit and celadon glaze; / RTI >
Wherein the white porcelain includes fine particles of 1 占 퐉 or less, the white porcelain and the celadon porcelain include plate-shaped fine particles of 2 占 퐉 or less,
The frit is SiO ₂ 50 to 75 wt%, Al ₂ O ₃ 5 to 20 wt.%, Fe ₂ O ₃ 0.1 to 3% by weight, CaO 5 to 20 wt%, MgO 0.1 to 3% by weight, K ₂ O 1 to 5% by weight of Na ₂ O, 0.1 to 3% by weight of Na ₂ O and 0.1 to 10% by weight of ZnO, and a content of B ₂ O ₃ of 4.9% by weight or less,
The frit is contained in an amount of not more than 50% by weight of the total weight of the glaze composition,
Wherein the difference between the thermal expansion coefficient of the substrate and the thermal expansion coefficient of the celadon glaze is 10% or less.

The method according to claim 1,
Wherein the celadia composition is formed from a water content of the glaze composition of 40 to 45% by weight.

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