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1 Jurnal f the Krean Ceramic Sciety Vl. 44, N. 11, pp. 639~644, Synthesis f Cbalt Oxide Free Black Clr Spinel Pigment Jun-H Kim*, Seng-H Lee, Man-Chul Suh*, and Byung-Ha Lee Department f Material Science & Engineering, Myngji University, Yng-In , Krea *Department f Chemical Engineering & Bitechnlgy, Krea Plytechnic University, Si-Heung , Krea (Received September 5, 2007; Accepted Nvember 19, 2007) COƒ ƒ v w ½ y*á yá *Á w w œw *w» w ywœw ( ; ) ABSTRACT Spinel pigments, develping black clr in high temperature glazes at xidatin r reductin atmsphere, withut CO because f its high price were synthesized by slid slutin methd. Ten mixed cmpsitins cnsisted f NiO, MnO, Fe 2, Cr 2 and Mn 2 were fired at 1250 C fr 1h. The resulting pigments were characterized by using XRD, FT-IR, SEM and UV-vis spectrmeter. Structure f the pigments are spinel and particles shape are spherical r cubic. Glazed tiles cntaining 5 wt% pigments were fired at 1260 C and 1240 C in reductin atmsphere. Clr in glazes were analyzed by UV-vis spectrmeter. Clrs f NiO MnO Fe Cr Mn mle% and NiO MnO Fe Cr Mn mle% in lime glaze shwed black in xidatin, in reductin NiO MnO Fe Cr Mn mle% and NiO MnO Fe Cr Mn mle% shwed black. In case f lime-barium glaze, NiO MnO Fe Cr Mn mle%, NiO MnO Fe Cr Mn mle% and NiO MnO Fe Cr Mn mle% shwed black clr in xidatin and NiO MnO Fe Cr Mn mle%, NiO MnO Fe Cr Mn mle% and NiO MnO Fe Cr Mn mle% shwed black ne in reductin. Key wrds : Cbalt xide, Pigment, Spinel, Black clr 1. y kw š y», Tile,», w š ƒ š x š CO-Fe 2 -Cr 2, 1) Fe 2 -Cr 2, 2,3) ZnO-Fe 2, 4) CO-Fe 2 -Cr 2 -MnO 2, 5) CO-Sb 2 O 5 6) CO w wš. w yg p l š v e e w šƒ y. w ù CO w wš w. w yg p w» w ƒ w. w Crrespnding authr : Byung-Ha Lee lbh@mju.ac.kr Tel : Fax : ,», COƒ ƒw w yg p ƒw p ƒ. 7)» p ƒ spinel ƒ w p x š ƒ y, ù m» y w t w» ƒ. CO w ƒ jš» w» wš w. 2. x 2.1. spinel yg p ƒw» w w» w» NiO, Fe 2, Cr 2, MnO, Mn 2 639

2 640 ½ yá yá Á w Table 1. Cmpsitins f Black Clr Spinel Pigment Cmpsites (mle %) Sample Material NiO MnO Fe Cr Mn w. x w NiO, Fe 2, Cr 2 (Duksan, Krea, 99%) MnO(Alfa Aesar, England, 99%), Mn 2 (Aldrich, USA, 99%) ü q š w w w w w» w» w Table 1 w. w yw spinel. 1~5 NiO, MnO š w z Fe 2, Cr 2, Mn 2 y g 6~10 Fe 2, Cr 2, Mn 2 š w z NiO, MnO y g. w w ƒƒ y e w k ƒw 30 yww z 60 C Dry Oven w. Alumina ƒ» ƒ w 1250 C¾ w. 900 C¾ 5 C/min, z š ¾ 3 C/min g, š 1 k z þw w w y w š w. w» (1) z (2) z w w ƒ 5wt% š w w xr w y» 1260 C y» 1240 C ƒƒ w KNaO Lime glaze CaO Al SiO MgO Pigment 5wt% (1) KNaO Lime CaO Al SiO 2 Barium glaze MgO BaO Pigment 5wt% (2) p w ƒƒ 1 w Rtate ring mill(rrg-120, Armstech industrial. c. Ltd, Krea) w w z ƒ p w. ƒƒ XRD(X-Ray Diffractmeter, XRD-7000, Shimadzu, Japan) FT-IR(Furier Transfrm-Infrared Spectrscpy, IR Prestige-21, Shimadzu, Japan) w w. x SEM(SEM-550, Shimadzu, Japan) w w. w UV-vis Spectrmeter(UV- 2401PC, Shimadzu, Japan) w z(cie : Cmmissim Internatinale de I'Eclairage) t (L *, a *, b ) * d w. CIE-L *, a *, b t * L *, (L * = 100) (L =0) * ùküš, a* ( a ) * (+ a ) ùkü *, b * ( b ) * y (+ b ) ùkü * w. w Applied clr system Inc. CIE Crdinates t Munsell ntatin cnversin w X, Y, Z e. 3. š 3.1. spinel w XRD w» w Table 1 yww z yw 1250 C 1 w XRD w ¾ spinel. w NiFe 2 O 4, NiCr 2 O 4 NiMn 2 O 4 spinel y ù š š q. 6~10 NiO MnO eyw Fig. 2 MnO ƒw ƒ w. w» w ƒƒ 5wt% ƒw z w wz

3 COƒ ƒ v w 641 Fig. 1. XRD patterns f prepared pigments at 1250 C. Fig. 2. d-value in cmpsitin N.6 ~ N.10 depending n MnO mle rati. <Inter-planar distance (440)> Fig. 3. XRD patterns f glaze. w XRD ww. Fig 3 ƒ w spinel ùkûš, w cristbalite w mulliteƒ FT-IR w w» w FT-IR(Furier Transfrm-Infrared Spectrscpy, IR Prestige-21, Shimadzu, Japan) ww. Table 1 w w Spinel NiFe 2 O 4, NiCr 2 O 4, NiMn 2 O 4 ƒ š w š w. w spinel ƒ w XRD w. Fig. 1 XRD 10ƒ spinel ùkû spinel 2ƒ spinel œ w ƒ» w FT-IR w. Fig. 4 w FT-IR transmit spectra w š Fig. 5 absrbance spectra ã ùkü. 1, 2, 4, 5 Ni-ferrite ferrite absrbance spectrum ùkù NiO MnOƒ, Fe 2 Cr 2 Mn 2 ƒ š spinel. spinel xk ƒ š cubic. 8) cubic xk wù e 4 xygen in š w 4 ƒ š cell 8 ƒ wš. e 8 xygen in š p 8 cell 16 ƒ wš. yw A 8 B 16 2 AB 2 O 4. 9) spinel j» w w. AB 2 O 4 yw 0.06 < r A <0.1µm š < r B <0.1µm Mn µm š, Ni µm Mn 2+ Ni 2+ inic size ƒ µm ù Mn, Ni w 2ƒ. 10) Ni 2+ Mn 2+ w. ù Cr 2 w ƒ cm 1 absrbance spectrum ùkû. Ni-Ferrite Ni-Cr ferriteƒ ƒ y f» high frequency shift ùkù. Ni-ferrite Ni-Cr ferrite absrbance spectrum w ùkû. 3 Ni-ferrite Ni-Cr ferriteƒ œ w. NiO MnO eyw 6~10 MnO ƒ w 625 cm 1 ùkù Ni-ferrite spectrum MnO š w MnO p spectrum 615 cm 1 w. 11,12) 10ƒ 3 44«11y(2007)

4 김준호 이성호 서만철 이병하 642 Fig. 4. FT-IR transmit spectra patterns f prepared pigments at 1250 C. ( : 1, : 2, : 3, : 4, : 5, : 6, : 7, : 8, : 9, : 10) Fig. 5. FT-IR absrbance spectra patterns f prepared pigments at 1250 C. ( : 10, : MnO-1250 C, : 2, : 4, : 1, : 9, : 7, : 8, : 6, : 5, : 3) 2가지 종류의 spinel상이 공존하며 나머지 9가지 안료는 서 로 고용된 단일상의 spinel으로 이루어져 있음을 알 수 있다 SEM 분석 합성된 안료입자의 입형과 크기를 알아보기 위하여 SEM (SEM-550, Shimadzu, Japan)분석을 하였다. Fig. 6에서와 같이 SEM 관찰 결과 10가지 조성의 모든 안료의 입형은 전형적인 spinel 구조를 나타내는 cubic 형태를 이루고 있다. Fig. 6에서 관찰한 결과 대부분의 spinel 결정들은 0.8~ 한국세라믹학회지 Fig. 6. SEM images f prepared pigments at 1250 C. 1.3 µm의 크기를 보이고 있다. 이들 중 MnO의 양이 점점 증가하는 6번 조성에서 10번 조성으로 갈수록 spinel 결 정의 크기가 점점 커짐을 알 수 있다. 분석 합성된 안료의 색상, 채도, 명도값을 알아보기 위하여 UV 분석을 하였으며 그 결과를 Fig. 7에 나타내었다. UV 분석 결과 조합비 변화에 따라서 안료 색상에도 영 향을 미치는 것으로 볼 수 있다*. 합성된 안료 1번 조성에 서 10번 조성까지는 명도값 L 이 30.07~32.00 범위에 있 었으며 a* : 1.30~ 0.28, b* : 0.09~2.05로 나타났다. 그 중 6~10번 안료는 NiO의 양은 감소하고, MnO 양은 증 UV

5 COƒ ƒ v w 643 Fig. 7. UV Analyzing f prepared pigments. ( ø:1, ù:2, ÿ:3, :4, ý:5, þ:6, :7, :8, û:9, ü : 10) Table 2. UV Analyzing f Lime Glaze < Oxidatin > Sample N. Clr N 1.6 Black YR 1.8/0.2 Black P 2.0/0.1 Black RP 2.2/0.1 Black N 2.3 Black R 2.3/0.1 Black R 1.7/0.1 Black YR 2.3/0.1 Black YR 1.8/0.3 Black YR 1.8/0.3 Black < Reductin > Sample Clr N N 2.4 Black Y 1.9/0.5 Black N 2.7 Black Y 2.0/0.2 Black YR 2.6/0.1 Dark gray R 2.3/0.1 Black Y 2.5/0.2 Black Y 2.1/0.4 Black Y 2.5/0.3 Dark gray Y 2.9/0.3 Dark gray ƒ. MnO w ƒw w w Munsell-HV/C N 2.9 ~ N 3.0, X, Y, Z e Dark gray ùkû.» w (1) z (2) z w ƒƒ 5wt% ƒw xr w y» 1260 C y» 1240 C 1 w. w xr w UV Table 2 Table 3 ùkü. Table 2 z y» w L * ~ a * : 0.1 ~ 0.82, b * : 0.42 ~ 1.51 ùkû. ù y» w L * ~ a * : 0.13 ~ 0.68, b * : 0.04 ~ 1.67 ùkû. w w z w 10 ƒ m ùkü w wš w y» 1 5 ƒ y Table 3. UV Analyzing f Lime-barium Glaze < Oxidatin > Clr P 2.2/0.1 Black P 2.3/0.1 Black P 2.4/0.1 Black YR 2.2/0.1 Black N 2.3 Black N 2.3 Black N 2.5 Black R 2.3/0.1 Black R 2.4/0.1 Black G 2.5/0.1 Black < Reductin > Sample Clr N P 2.2/0.1 Black YR 1.9/0.2 Black N 2.0 Black YR 2.2/0.1 Black Y 2.0/0.3 Black Y 2.2/0.1 Black N 2.5 Black YR 2.1/0.2 Black Y 2.5/0.1 Dark gray N 2.1 Black 44«11y(2007)

6 644 ½ yá yá Á w» 5 9, 10 ƒ ww. Table 4 z y» w L * ~ a * : 0.39 ~ 0.71, b * : 0.49 ~ 0.39 ùkû. y w L * ~ a * : 0.06 ~ 0.46, b * : 0.48 ~ 1.87 ùkû. z z ƒ 10ƒ m ùkü ù z w ùkû.» w y» w y» w ùkü. w wš w y» 5, 6, 7 ƒ y» 4, 7, 10 ƒ ww. 4. ƒ CO w š y y» w w wš NiO, Fe 2, Cr 2, MnO, Mn 2 w 1250 C w w. 1. y» z w NiO MnO Fe Cr Mn mle%, z w NiO MnO Fe Cr Mn mle% NiO MnO Fe Cr Mn mle% 1260 C w w w Munsell-HV/C z N 1.6 š z N 2.3 w w. 2. y» z w NiO MnO Fe Cr Mn mle%, z w NiO MnO Fe Cr Mn mle% 1240 C w w w Munsell-HV/C z N 2.4 š z N 2.0 w w. 3. w XRD FT-IR spinel ùkþ, SEM cubic xk ùkû. REFERENCE 1. Y.Shiraki, Glaze and Pigment, Deakwang, pp. 684 (1980). 2. E. Ozel and S. Turan, Prductin and Characterisatin f Irn-chrmium Pigments and Their Interactins with Transparent Glazes, J. Eur. Ceram. Sc., 23 [12] (2003). 3. A. Escardin, S. Mestre, A. Barba, V. Beltran, and A. Blasc, Synthesis Mechanism f an Irn-Chrmium Ceramic Pigment, J. Am. Ceram. Sc., 83 [1] (2000). 4. X. Y. Wang, G. Q. Yang, Z. S. Zhang, L. M. Yan, and J. H. Meng, Synthesis f Strng-magnetic Nansized Black Pigment Zn x Fe 3-x O 4, Dyes and Pigments, 74 [2] (2007). 5. K. H. Lee, M. S. Myung, and B. H. Lee, Develpment f Black Clr Spinel Pigment fr High Temperature(in Krean), J. Kr. Ceram. Sc., 44 [5] (2007). 6. D. S. Guveia, L. E. B. Sledade, C. A. Paskcimas, E. Lng, A. G. Suza, and I. M. G. Sants, Clr and Structural Analysis f C x Zn 7-x Sb 2 O 12 Pigments, Mater. Res. Bull., 41 [5] (2006). 7. R. A. Eppler, Cbalt-Free Black Pigment, Am. Ceram. Sc. Bull., (1981). 8. O. Muller and R. Ry, The Majr Ternary Structural Families, Springer-Verlag, New Yrk, R. A. Eppler, Nickel Spinels, Am. Ceram. Sc. Bull., (1982). 10. J. A. Duffy, Bnding Energy Levels and Bands in Inrganic Slids, pp. 3, Lngman Grup,. United Kingdm, N. T. McDevitt and W. L. Baun, Infrared Absrptin Study f Metal Oxides in the Lw Frequency Regin( cm 1 ), J. Spectrchimica Acta., (1964). 12. R. A. Nyquist and R. O. Kagel, Infrared Spectra f Inrganic Cmpunds, pp. 217, pp. 489, Academic Press, INC., New Yrk, w wz