• Journal of the Korean Crystal Growth and Crystal Technology
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• v.33 no.6
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• pp.234-243
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• 2023

Zinc crystals of ZnO and SiO₂ in glaze raw materials, developed according to composition and firing requirements, are preferred because of their high decorative properties. However, most zinc crystal glazes have a high firing temperature and a narrow firing temperature range, making it difficult to use them as commercial glazes in ceramics. Therefore, in this study, it was expected that the firing temperature of a typical zinc crystal glaze could be lowered to below 1270℃ by using the eutectic effect through mixing frit, the main raw material used in manufacturing zinc crystal glaze. As a result, not only was the formation temperature of zinc crystals lower in the mixed frit glaze, but also the firing temperature range was widened to 1230~1270℃, making it possible to develop a glaze that produces crystals stably. The firing temperature was lowered to 1230~1250℃ and the holding temperature during cooling was lowered to about 950℃, resulting in the development of an economically effective glaze. When using a combination of frit, it has been shown that the holding temperature during cooling affects the recrystallization of zinc crystals depending on the composition of the glaze, and the crystal structure can be adjusted at this time. Additionally, the amount and shape of crystals can be controlled by using a nucleating agent.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.7 no.4
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• pp.648-657
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• 1997

In order to investigate the polymorphism of wagnerite, the single phase of$Mg_3(PO_4)_2$ was synthesized by heating the stoichiometric mixture of $Mg_3(PO_4)_2$ and $MgF_2$ in a sealed platinum tube at $1040^{\circ}C$ (or 3 hours, One reversible inversion was detected at $1255^{\circ}C$ and the thermal decomposition was not observed until it reached the melting point. As a result, wagnerite is thermally stable enough to be used as pigments for glazes and plastics if substituted with divalent metal ions. The contractions of d-values in $Zn_4P_2O_8F_2$ and $Zn_3MgP_2O_8F_2$ phases were observed by the substitution with metal ions which resulted in intense purple, gold and green colors. Among the several attempts of charge - coupled sub-stitution, only $A^{1+}A_3^{2+}X^{5+}X^{6+}O_8_F2$ compositions were successful to synthesize the wagnerite phase.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.7 no.4
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• pp.640-647
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• 1997

Wagnerite ($Mg_2PO_4F)$ was successfully synthesized in a sealed platinum tube and the complete substitutions of $Co^{++}, Ni^{++}, Cu^{++} \;and\;Zn^{++}$for Mg were made in the wagnerite structure. Wagnerite did not decompose until it reached its melting temperature. It was observed that wagnerite underwent only one inversion at $1255^{\circ}C$, prior to melting at $1340^{\circ}C$. The lattice parameters of wagnerites were linearly increased by the substitutions of $Co^{++}$ and $Zn^{++}$ and decreased by the substitutions of $Ni^{++}$ and $Cu^{++}$. The substitutions of wagnerite with $Co^{++}, Ni^{++}$ and $Cu^{++}$ resulted in purple, orange and green colors, respectively, The colors of pigments became more intense and suitable for coloring of glazes and plastics as the amount of metal ions increased.

• Journal of the Korean Ceramic Society
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• v.46 no.4
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• pp.405-412
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• 2009

In high temperature ceramic glazes, a stable range of pink-red colors that produced $Cr_2O_3-SnO_2-CaO-SiO_2$ pigments were factored by Cassiterite($SnO_2$) and Malayaite($CaSnSiO_5$) by $Cr_2O_3$. The experiment examined the influence of $CrCl_3$, a Sn-Cr substitution added with a mineralizer ($H_3BO_3$), as a chromophore in pigments. The experiment also studied the effect of $H_3BO_3$ (2 wt%) when added to malayaite($CaSnSiO_5$) to see if the crystalline reaction will increase. $Cr_2O_3$ was also substituted with $CrCl_3$ in order to prove how much influence $CrCl_3$ had on the $H_3BO_3$. Malayaite and cassiterite were the basic compound materials and the experiment was conducted both with and without mineralizers (2 wt% of $H_3BO_3$). Each compound was synthesized at 800, 1000, 1200, 1300, 1400, $1500^{\circ}C$ for 2 h. Synthesized pigments were analyzed by XRD, FT-IR and UV-Vis. The temperature variation produced two crystal phases that showed the different engaging effects of Cr oxidation. $CrCl_3$ produced a better effect on the malayaite crystal phase, resulting in a more defined pigmentation of the pink-red coloration compared to $Cr_2O_3$.

• Korean Journal of Materials Research
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• v.21 no.8
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• pp.450-455
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• 2011

[ $Al_2TiO_5$ ]has a high refractive index and good solubility of the chromophore in the $Al_2TiO_5$ lattice, which allows this structure to be a good candidate for the development of new ceramic pigments. However, pure $Al_2TiO_5$ is well known to decompose on firing at $900{\sim}1100^{\circ}C$. However, this process can be inhibited by the incorporation of certain metal cations into its crystalline lattice. In this study, the synthesis of gray ceramic pigment was performed by doping cobalt on the $Al_2TiO_5$ crystal structure. The $Al_2TiO_5$ was synthesized using $Al_2O_3$ and $TiO_2$, and doped with $Co_3O_4$ as a chromophore material. In order to prevent the thermal decomposition during the cooling procedure, MgO was added to samples by 0.05 mole, 0.1 mole, and 0.15 mole as a stabilizer. The samples were fired at $1500^{\circ}C$ for 2 hours and cooled naturally. The crystal structure, solubility limit, and color of the synthesized pigment were analyzed using XRD, Raman spectroscopy, UV, and UV-vis. $Al_2O_3$ was available for the formation of $CoAl_2O_4$, which should also be considered in order to explain the small amount of this phase detected in the sample with the higher $Co^{2+}$ content (${\geq}$ 0.03 mole). It was found that the solubility limit of $Co^{2+}$ in the $Al_2TiO_5$ crystal was 0.02 mole% through an analysis of Raman spectroscopy. Through the addition of a pigment with 0.02 mole% of $Co^{2+}$ to lime-barium glaze, stabilized gray color pigments with 66.54, -2.35, and 4.68 as CIE-$L^*a^*b^*$ were synthesized.

• Journal of the Korean Ceramic Society
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• v.26 no.2
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• pp.187-194
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• 1989

Synthesis of spinel pigment on ZnO-Fe2O3 system. The object of this research is the synthesis of new spinel pigments on the basic of ZnO-Fe2O3 system which was substituted by ZnO-Fe2O3 by MgO-Al2O3. This research was progressed by measuring the X-ray diffraction and the reflectances of the substitued ZnO-Fe2O3 group. Which was obtained by sintering at the temperature of 1,00$0^{\circ}C$, 1,10$0^{\circ}C$, 1,20$0^{\circ}C$ and 1,25$0^{\circ}C$ and them by regrinding. In order to coloring test, here basic compositions of Barium glaze, Zinc glaze, Lime glaze, Lead glaze and Talc glaze used in this experiment are obtained from the ceramic work. Adding synthetic stains in these basic glazes with 3%, mixing and glazing on the specimen. The specimens was fired at 1,28$0^{\circ}C$ in reducing and oxidizing atmosphere in the gas kiln. The results of the research as follow. 1. Many kinds of spinel pigment was produced on ZnO-Fe2O3 system that is to say, not always only spinel. 2. Spinel peak was observed strongly on the ZnO-Fe2O3 system withsubstituting by MgO-Fe2O3 and MgO-Al2O3 group(the ratio of MgO, Al2O3 being increased, observed more strongly). 3. The most effective temperature ranges was 1,20$0^{\circ}C$~1,25$0^{\circ}C$. 4. The color of spinel pigments on this system was observed by "stable YR". 5. It was yellow red in oxidizing and green in reducing atmosphere on the coloring test.ring test.

• Journal of Conservation Science
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• v.27 no.1
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• pp.75-90
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• 2011

At the beginning of the Chos$\breve{o}$n dynasty, punch'$\breve{o}$ng began as a simplified form of inlaid celadon, and in the two following centuries it developed into a popular folk craft in various styles and expressive decorations; overtime, it was increasingly made to resemble whiteware, and its production stopped after the Japanese invasion of Korea. In the present study, the body and glaze compositions of punch'$\breve{o}$ng were examined and compared with those of celadon and whiteware, whose compositions have previously been compared with those of Chinese ceramics. Here, the analyzed shards were organized into 28 groups based on their production sites and archaeological characteristics. For each group, the body and glaze compositions of several shards(usually three to five) were obtained, averaged, and compared with those of the other groups. These comparisons showed that the majority of the punch'$\breve{o}$ng bodies were formed, like those of celadon and whiteware, with mica-quartz porcelain stone, which was commonly used in Yuezhou, Jingdezhen, and other southern Chinese kilns. The glazes consisted of clay materials and flux components made from various proportions of wood ash, burnt limestone (glaze ash) and crushed limestone. Overall, the punch'$\breve{o}$ng glazes resembled the Kory$\breve{o}$ celadon and Kory$\breve{o}$ whiteware glazes more closely than the Chos$\breve{o}$n white wareglazes. However, the $TiO_2$ levels found in the tested punch'$\breve{o}$ng were low, similar to those of Chos$\breve{o}$n whiteware; this indicated that glaze stone was used as the clay component of the punch'$\breve{o}$ng glazes, as was the case for Chos$\breve{o}$n whiteware. This study of the material characteristics of punch'$\breve{o}$ng may be used as a comparative framework for analyzing ceramic shards discovered at current and future excavations within Korea.

• Journal of the Korean Ceramic Society
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• v.48 no.4
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• pp.298-302
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• 2011

This study developed a pigment by doping Cr to Pyrochlore-type stannate crystals and investigated the chromogenic relationship in a glaze. Crystal phases of the pigment according to firing temperatures were analyzed by XRD, and the doping relationship was analyzed by Raman Spectroscopy. Color and reflection rate of the pigment were measured by UV-vis Spectrophotometer. Consequently, stannate characteristic band appeared at 307, 408, 505 and $755cm^{-1}$ until 0.1 mole substitution of $Cr_2O_3$. However, as amount of $Cr_2O_3$ increased, the stannate characteristic peak was decreased and shift happened at the left hand side due to Cr-dope. In composition of 0.12~0.14 mole substituted, the unreacted $Cr_2O_3$ stannate characteristic peak, which was not engaged, was shown. This result shows the maximum limit of solid solution was 0.1 mole $Cr_2O_3$. The color of the glaze, which was produced by adding 6 wt% of $Y_2Sn_{1.94}Cr_{0.06}O_7$ pigment in a lime or a lime-magnesia glaze and fired the mixture at $1260^{\circ}C$, was grayish pink with $L^*$ 70.29, $a^*$ 5.68 and $b^*$ 6.27. It showed gray with $L^*$ 68.82, $a^*$ 3.07and $b^*$ 8.13 for $Y_2Sn_{1.9}Cr_{0.1}O_7$.

• Korean Journal of Materials Research
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• v.21 no.9
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• pp.515-519
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• 2011

The purpose of this study was to determine the optimal firing condition and composition for $Al_2TiO_5$ crystal, which is suitable for stable coloration in glazes at high temperatures, using $Cr_2O_3$ as chromophore for the synthesis of $Al_2TiO_5$ system pigments. $Al_2TiO_5$ has a high refractive index and good solubility of chromophore in the $Al_2TiO_5$ lattice, making this structure a good candidate for the development of new ceramic pigments. Pigments were synthesized by using $Al_2O_3$ and $TiO_2$ mainly. Various amounts of $Cr_2O_3$ such as 0.01, 0.02, 0.03, 0.04 and 0.05 mole were also added. Each compound was synthesized at $1300^{\circ}C$, $1400^{\circ}C$, and $1500^{\circ}C$ for 2 hours and cooled naturally. The crystal structure, solubility limit, and color of the synthesized pigments were analyzed by XRD, SEM, Raman spectroscopy, UV and UV-vis. The changes in color as the result of applying 6 wt% of the synthesized pigments to lime barium glaze were expressed as CIE-L*a*b* values. A $Cr_2O_3$ 0.03 mole doped $Al_2TiO_5$ brown pigment was successfully synthesize at $1400^{\circ}C$, and the values of CIE-L*a*b* parameters were L* = 44.62, a* = 3.10, and b* = 17.25. In the case of the pigment synthesized at $1500^{\circ}C$, the brown color was obtained at 0.01 mole and 0.02 mole $Cr_2O_3$, and the CIE-L*a*b* values were 55.34, 1.73, 28.64, and 49.39, 0.51, 21.33, respectively. At $1500^{\circ}C$, the maximum limit of solid solution was 0.03 mole $Cr_2O_3$. The glazed sample showed green color, and the values of the CIEL* a*b* parameters were L* = 45.69, a* = -0.98, and b* = 20.38.

• Journal of the Korean Ceramic Society
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• v.12 no.1
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• pp.29-36
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• 1975

This study was conducted to research the formation, color development and application for colored glazes of the spinel solid solutions of the green pigment. On specimens prepared by calcining the oxide and basic carbonate mixture at 1250℃ for 1.5 hour, the x-ray analysis, measurement of reflectance and the test of their stabiality as a glaze pigment were carried out. The results are summarized as follows 1) Each sample is composed of single spinel and not of mixture of spinel. 2) Formation of continuous soild solution, except for a few instances, pertaining to Vegard's law was confirmed by means of the x-ray analysis. 3) The more difference between absorption and reflectance lies, the lighter colors are. When the absorption occurs at the high-reflectance, the excitation purity becomes low. On the contrary when the absorption takes place at the low-reflectance, the excitation purity becomes low. On the contrary when the absorption takes place at the low-reflectance, the excitation purity is higher. 4) Colors obtained in the CdO-MgO-Cr2O3-Al2O3 system, as the amounts of Al3+ increased, change from green through brown to pink, and the absorption peak shifts towards violet region. 5) An increase in Co2+ in the CoO-MgO-Cr2O3-Al2O3 system, changes the color from blue green to dark blue. The excitation purity is higher, and the absorption peak shifts toward regions. 6) Colors are green in the NiO-MgO-Cr2O3 and CdO-MgO-Cr2O3 systems in general, but in the ZnO-MgO-Cr2O3 system brillant hue is not obtained. 70 According to the results of the colored glaze test, the spinels turn outto be stable as brilliant glaze pigment in the calcium-magnesia glaze.