DOI QR코드

DOI QR Code

Synthesis and Formation Mechanism of Cobalt Doped Willemite Blue Pigments

Co-Doped Willemite 파란색 안료의 합성과 생성기구

  • Hwang, Dong-Ha (Department of Material Science & Engineering, Myongji University) ;
  • Han, Kyong-Sop (Division of Material Science, KIST) ;
  • Lee, Byung-Ha (Department of Material Science & Engineering, Myongji University)
  • 황동하 (명지대학교 공과대학 신소재공학과) ;
  • 한경섭 (한국과학기술연구원) ;
  • 이병하 (명지대학교 공과대학 신소재공학과)
  • Received : 2010.07.14
  • Accepted : 2010.09.14
  • Published : 2010.11.30

Abstract

Turquoise blue pigment of Vanadium-zircon blue (DCMA number 14-42-2), which was already commercialized, was stable to be reproduced but insufficient to give strong blue. However, it possible to obtain more intense blue by partially substituting cobalt ions into the willemite($Zn_2SiO_4$) lattice classified into DCMA number 7-10-2 for blue ceramic pigment. By the composition of willemite $Co_xZn_{2-x}SiO_4$(X=0.01, 0.03, 0.05, 0.07, 0.09 mole), this study used reagent grade zinc oxide, cobalt oxide and silicon dioxide as starting materials, carrying out the synthesis with solid reaction method by adding $H_3BO_3$ as a mineralizer. The firing temperature was between $1200^{\circ}C$ and $1400^{\circ}C$. The characteristics of synthesized pigment were analyzed by X-ray diffraction, Raman spectroscopy and SEM and the characteristics of color tones were analyzed by UV-Vis spectroscopy and CIE-$L^*a^*b^*$ measurement. As a result, the optimal composition was $Zn_{1.95}Co_{0.05}$ with 1wt% of $H_3BO_3$ as a mineralizer and firing condition was $1350^{\circ}C$/3 h. $L^*a^*b^*$ value was 29.25, 41.03, -59.93 for on glaze pigment and 37.03, 36.41, -60.03 for under glaze pigment.

Keywords

References

  1. M. S. H. Katou, “A Study on the Synthesis of Red Ceramic Pigments,” Nagoya Institute of Technology, Report No. 288, Nagoya, 2000.
  2. U. G. Ime, “A Study on the Internationalization of Traditional Techniques Korea:Pottery (in Korean),” pp. 1-322, National Research Foundation of Korea, Seoul, 1994.
  3. K. M. Lee, “Introduction of Pigment,” pp. 1-340, Korea Plastic Technical Information Centet, Seoul, 1989.
  4. R. A. Eppler, “Classification of Mised Oxide Inorganic Pigments,” J. Am. Ceram. Soc., 62 [9] 1001-3 (1983).
  5. G. T. Chandrappa, S. Ghosh, and K. C. Pattil, “Synthesis and Properites of Willemite, $Zn_{2}SiO_{4}$, and $M^{2+}:\;Zn_{2}SiO_{4}$ (M=Co and Ni),” J. Mater. Synth. Process., 7 [5] 273-79 (1999). https://doi.org/10.1023/A:1021816803246
  6. S. G. Son, J. H. Lee, J. M. Lee, and Y. D. Kim, “Low Temperature Synthesis of Willemite Powder (in Korean),” J. Kor. Ceram. Soc., 45 [7] 401-4 (2008). https://doi.org/10.4191/KCERS.2008.45.7.401
  7. G. N. Maslennikova, N. P. Fomina, and A. I. Glebycheva, “Study of the Effect of Substitution of $SiO_{2}\;by\;SnO_{2},\;TiO_{2},\;of\;ZrO_{2}$ in Pigments,” Steklo i Keramika, 7 [28] 28-30 (1976).
  8. A. Fores, M. Llusar, J. A. Badenes, J. Tena, M. A. Tena and G. Monros, “Cobalt Minimization in Willemite($Co_{x}Zn_{2-x}SiO_{4}$) Ceramic Pigments,” Green Chem., 2 93-100 (2000). https://doi.org/10.1039/b000748j
  9. J. K. Lee, J. O. Kim, Y. H. Baek, J. S. Lee, B. H. Lee, and D, W. Shin, “Ceramics Raw Materials,” pp. 3-424, Info. Tech. Cor., Seoul, 1967.
  10. S. N. Lee, S. C. Noh, and S. G. Kim, “Colorimetric Analysis and Matching the Notion of the Munsell System for Reproduced Colors with Variable Dot Area Rates (in Korean),” Pukyong National University, Pusan, 23 [2] 819-53 (1982).
  11. D. D. Waal, “Micro-Raman and Portable Raman Spectroscopic Investigation of Blue Pigments in Selected Delfts Plates (17-20th Century),” J. Raman Spectroscopy., 40 2162-70 (2009). https://doi.org/10.1002/jrs.2389
  12. C. R. Bamford, phys. “The Aplication of the Ligand Field Theory to Coloured Glasses,” Chem. Glasses., 3 [6] 189-202 (1962).
  13. M. C. Wittels, “Modern Aspects of the Vitreous State,” J. Phys. Chem. Sol., 23 [5] 195-254 (1960).
  14. F. Corma and V. Lambies, “Investigation of Some Inorganic Pigments of Co(II),” J. Rev. de Chim. Minre., 17 110-17 (1980).
  15. F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry; pp. 261-268, Inc. 3rd ed., John Wiley & Sons, New York, 1972.
  16. J. Ferguson, D. L. Wood, and L.G. Uitert, “Crystal-Field Spectra of $d^{3,7}$ Ions. V. Tetrahedral $Co^{2+}\;in\;ZnAl_{2}O_{4}$ Spinel,” J. Chem. Phy., 51 2904-10 (1969). https://doi.org/10.1063/1.1672431
  17. T. C. Brunold, H. U. Gudel, and E. Cavalli, “Absorption and Luminescence Spectroscopy of $Zn_{2}SiO_{4}$ Willemite Crystals Doped with $Co^{2+}$,” J. Chem. Phy. Lett., 252 [1] 112-20 (1996). https://doi.org/10.1016/S0009-2614(96)00141-8

Cited by

  1. Gray Pigment vol.49, pp.1, 2012, https://doi.org/10.4191/kcers.2012.49.1.084
  2. Investigation of Color Mecchanism in Co-Doped Augite Purple for Color Glaze vol.23, pp.5, 2013, https://doi.org/10.3740/MRSK.2013.23.5.271