• 한국결정성장학회지
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• 제33권6호
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• pp.234-243
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• 2023

유약원료 내의 ZnO와 SiO₂의 조성과 소성요건에 따라 생성되어 표면으로 석출된 아연결정은 매우 장식성이 높아 선호된다. 하지만 아연결정유약은 대부분 소성온도가 높고 소성온도 폭이 좁아 상용유약으로 사용하기 어렵다. 따라서 본 연구에서는 아연결정유약 제조 시 사용하는 주원료인 frit를 혼용하여 공융효과를 이용하면 일반적인 아연결정유약의 소성온도를 1270℃보다 아연결정의 유약 생성온도를 낮출 수 있을 것으로 기대하였다. 그 결과 Frit 혼용 유약에서는 아연결정의 생성온도가 낮아질 뿐 아니라 1230~1270℃로 소성온도 폭이 넓어져 안정적으로 결정이 생성되는 유약을 개발할 수 있었다. 소성 최고온도를 1230~1250℃로 낮추고 냉각 시 유지온도를 약 950℃까지 낮출 수 있었으며, 경제적으로 효과적인 유약을 개발할 수 있었다. Frit 혼용으로, 유약의 조성에 따라 냉각 시 유지온도는 아연결정의 재결정화에 영향을 주는 것으로 나타났으며 이때 결정형을 조절할 수 있다. 또한, 조핵제의 활용으로 결정 생성 량과 형태의 제어가 가능하다.

• 한국결정성장학회지
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• 제7권4호
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• pp.648-657
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• 1997

합성원료로써 $Mg_3(PO_4)_2$와 $MgF_2$분말을 혼합한 후 백금밀폐용기를 사용하여 $1040^{\circ}C$에서 단일상의 wagnerite$(Mg_2PO_4F)$를 합성하였으며 이 결정상의 동질이상에 대하여 연구한 결과, 이미 발표된 연구 결과들과는 달리 $1255^{\circ}C$에서 단 한번의 가역적인 상전이가 관찰되었고, $1340^{\circ}C$에서 용융될 때까지 열분해 현상은 나타나지 않았으며, 이로써 2가 금속이온의 치환에 의해 여러 종류의 고용체를 합성해 낼 경우, 유약 및 플라스틱의 색상발현을 위한 안료로 사용될 수 있는 것으로 밝혀졌다. $Zn_4P_2O_8F_2$와 $Zn_3MgP_2O_8F_2$ wagnerite의 Zn 대신 2가 금속을 치환한 경우, 전반적으로 d값이 줄어들었으며 Co는 자주색, Ni은 금색, Cu는 녹색을 나타내었다. 또한 charge-coupled 치환을 시도한 결과, $A^{1+}A_3^{2+}X^{5+}X^{6+}O_8_F2$의 경우만 wagnerite가 형성되었다.

• 한국결정성장학회지
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• 제7권4호
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• pp.640-647
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• 1997

백금밀폐용기를 사용하여 wagnerite($Mg_2PO_4F)$를 합성하는데 성공하였으며, 유약용안료로 사용하기에 적합한 발색을 위해 $Co^{++}, Ni^{++}, Cu^{++} $등을 첨가하여 wagnerite의 Mg와 금속이온간의 전 성분구간에 걸쳐 고용체(solid solution)을 합성하였다. wagnerite는 용융점($1340^{\circ}C$)에 도달할 때까지 안정하여서 열분해되지 않았으며, 용융전에 오직 한 번의 가역적인 상전이가 $1255^{\circ}C$에서 일어남을 관찰하였다. wagnerite의 격자상수는 금속이온의 첨가량에 비례하여 직선적으로 변화하였는데 $Co^{++}$와 $Zn^{++}$ 첨가시는 증가하였으며, $Ni^{++}$과 $Cu^{++}$를 첨가한 경우에는 감소하였다. 또한 금속이온 첨가시, $Co^{++}$는 자주색, $Ni^{++}$는 노란색, $Cu^{++}$는 녹색을 발현시켰으며 이들의 색조는 첨가량이 증가할수록 밝고 진하여져서 유약 및 플라스틱을 착색하기에 적합한 색상을 나타내었다.

• 한국세라믹학회지
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• 제46권4호
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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 $Cr_2O_3$.

• 한국재료학회지
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• 제21권8호
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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.

• 한국세라믹학회지
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• 제26권2호
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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.

• 보존과학회지
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• 제27권1호
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• pp.75-90
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• 2011

분청사기는 조선초기에 고려상감청자의 무늬가 간소화 된 상태로 시작되었다. 그 후 200여 년 동안에 다양하고 활달한 문양의 민속공예로 발달하였고, 점점 백자를 닮아가는 방향으로 변해가다가, 임진왜란이후에 생산이 중단되었다. 이 논문에서는 분청의 태토와 유약에 대한 화학조성을 분석하고, 여러 도요지들의 결과들을 서로 비교하였다. 또한 다른 논문들에서 중국의 경우와 비교 관찰된 고려청자와 조선백자들에 대한 결과들과 비교 하였다. 생산도요지와 고고학적인 특성에 의하여 28 그룹으로 나누었으며, 각 각의 그룹에서 셋에서 다섯편의 도편을 분석하고, 그들의 평균값을 비교자료로 사용하였다. 분청태토는 한국청자와 백자와 같이 중국 남쪽의 월주요, 경덕진요에서 사용된 운모-석영계의 도석으로 만들어졌다. 유약은 점토질의 원료에 나무재, 태운 석회석과 곱게 빻은 석회가루를 다양한 비율로 혼합되었다. 분청유약의 특성은 조선백자보다는 고려청자와 고려백자에 더 가깝다. 다만 티타늄산화물의 함량은 조선백자와 같이 낮은데, 그 이유는 글래이즈 스톤으로 알려진 도석계의 점토가 분청유약을 제조 하는데 혼합 되었기 때문으로 추정된다. 이 연구의 체계적인 비교방법과 물질적 특성에 대한 내용들은 현재 빠른 속도로 발굴되고 있는 도요지들에 대해서 적용될 수 있을 것이다.

• 한국세라믹학회지
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• 제48권4호
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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 $Y_2Sn_{1.9}Cr_{0.1}O_7$.

• 한국재료학회지
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• 제21권9호
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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.

• 한국세라믹학회지
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• 제12권1호
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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.