Jurnal f the Krean Ceramic Sciety Vl. 44, N. 11, pp. 639~644, 2007. 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 449-728, Krea *Department f Chemical Engineering & Bitechnlgy, Krea Plytechnic University, Si-Heung 429-793, Krea (Received September 5, 2007; Accepted Nvember 19, 2007) COƒ ƒ v w ½ y*á yá *Á w w œw *w» w ywœw (2007 9 5 ; 2007 11 19 ) 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 0.875 MnO 0.125 Fe 2 0.4875 Cr 2 0.50 Mn 2 0.0125 mle% and NiO 0.875 MnO 0.125 Fe 2 0.3875 Cr 2 0.50 Mn 2 0.1125 mle% in lime glaze shwed black in xidatin, in reductin NiO 0.875 MnO 0.125 Fe 2 0.4875 Cr 2 0.50 Mn 2 0.0125 mle% and NiO 0.875 MnO 0.125 Fe 2 0.4375 Cr 2 0.55 Mn 2 0.0125 mle% shwed black. In case f lime-barium glaze, NiO 0.875 MnO 0.125 Fe 2 0.3875 Cr 2 0.50 Mn 2 0.1125 mle%, NiO 0.975 MnO 0.075 Fe 2 0.4375 Cr 2 0.50 Mn 2 0.0625 mle% and NiO 0.925 MnO 0.075 Fe 2 0.4375 Cr 2 0.50 Mn 2 0.0625 mle% shwed black clr in xidatin and NiO 0.875 MnO 0.125 Fe 2 0.3875 Cr 2 0.50 Mn 2 0.1125 mle%, NiO 0.925 MnO 0.075 Fe 2 0.4375 Cr 2 0.50 Mn 2 0.0625 mle% and NiO 0.725 MnO 0.275 Fe 2 0.4375 Cr 2 0.50 Mn 2 0.0625 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 E-mail : lbh@mju.ac.kr Tel : +82-31-330-6461 Fax : +82-31-330-6457,», 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 2.1.1. yg p ƒw» w w» w» NiO, Fe 2, Cr 2, MnO, Mn 2 639
640 ½ yá yá Á w Table 1. Cmpsitins f Black Clr Spinel Pigment Cmpsites (mle %) Sample Material 1 2 3 4 5 6 7 8 9 10 NiO 0.875 0.875 0.875 0.875 0.875 0.975 0.925 0.825 0.775 0.725 MnO 0.125 0.125 0.125 0.125 0.125 0.025 0.075 0.175 0.225 0.275 Fe 2 0.4875 0.4875 0.4375 0.4375 0.3875 0.4375 0.4375 0.4375 0.4375 0.4375 Cr 2 0.50 0.45 0.55 0.45 0.50 0.50 0.50 0.50 0.50 0.50 Mn 2 0.0125 0.0625 0.0125 0.1125 0.1125 0.0625 0.0625 0.0625 0.0625 0.0625 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. 2.1.2. 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. 2.1.3. 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. 0.3264 KNaO Lime glaze 0.6583 CaO 0.4040 Al 2 3.5526 SiO 2 0.0148 MgO Pigment 5wt% (1) 0.2969 KNaO Lime 0.1567 CaO 0.4040 Al2 3.5526 SiO 2 Barium glaze 0.0185 MgO 0.5279 BaO Pigment 5wt% (2) 2.1.4. 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 3.1.1. XRD w» w Table 1 yww z yw 1250 C 1 w XRD w. 1 10 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
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. 3.1.2. 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 0.055 < r B <0.1µm Mn 2+ 0.08 µm š, Ni 2+ 0.069 µm Mn 2+ Ni 2+ inic size ƒ 0.011 µm ù Mn, Ni w 2ƒ. 10) Ni 2+ Mn 2+ w. ù Cr 2 w ƒ 3 890 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)
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. 3.1.3. 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 3.1.4. UV
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 1 16.15 0.10 0.42 N 1.6 Black 2 18.51 0.62 0.65 4.5YR 1.8/0.2 Black 3 20.29 0.46 0.54 3.9P 2.0/0.1 Black 4 22.71 0.70 0.15 4.7RP 2.2/0.1 Black 5 23.63 0.52 0.04 N 2.3 Black 6 23.34 0.57 0.05 0.3R 2.3/0.1 Black 7 17.62 0.72 0.15 4.5R 1.7/0.1 Black 8 23.32 0.58 0.51 2.3YR 2.3/0.1 Black 9 18.04 0.82 1.38 7.8YR 1.8/0.3 Black 10 18.42 0.72 1.51 8.8YR 1.8/0.3 Black < Reductin > Sample Clr N. 1 24.14 0.51 0.04 N 2.4 Black 2 19.24 0.34 2.81 2.9Y 1.9/0.5 Black 3 27.28 0.34 0.15 N 2.7 Black 4 20.89 0.46 1.37 0.1Y 2.0/0.2 Black 5 26.39 0.29 0.71 8.6YR 2.6/0.1 Dark gray 6 23.35 0.68 1.29 6.5R 2.3/0.1 Black 7 25.51 0.20 1.24 1.9Y 2.5/0.2 Black 8 21.53 0.13 2.55 5.1Y 2.1/0.4 Black 9 25.80 0.18 1.83 2.8Y 2.5/0.3 Dark gray 10 30.11 0.06 1.67 3.4Y 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 * 16.15 ~ 26.31 a * : 0.1 ~ 0.82, b * : 0.42 ~ 1.51 ùkû. ù y» w L * 19.24 ~ 30.11 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 1 22.77 0.43 0.37 6.6P 2.2/0.1 Black 2 23.35 0.39 0.49 3.2P 2.3/0.1 Black 3 24.27 0.53 0.36 8.7P 2.4/0.1 Black 4 22.20 0.56 0.39 0.7YR 2.2/0.1 Black 5 23.56 0.47 0.29 N 2.3 Black 6 23.56 0.47 0.29 N 2.3 Black 7 25.35 0.40 0.28 N 2.5 Black 8 23.52 0.55 0.29 8.0R 2.3/0.1 Black 9 24.94 0.55 0.15 2.9R 2.4/0.1 Black 10 25.13 0.71 0.12 6.3G 2.5/0.1 Black < Reductin > Sample Clr N. 1 22.72 0.46 0.48 4.7P 2.2/0.1 Black 2 19.87 0.46 0.89 8.1YR 1.9/0.2 Black 3 20.01 0.18 0.52 N 2.0 Black 4 22.10 0.34 0.76 8.5YR 2.2/0.1 Black 5 20.48 0.06 1.87 4.0Y 2.0/0.3 Black 6 22.87 0.10 0.62 1.9Y 2.2/0.1 Black 7 25.49 0.25 0.29 N 2.5 Black 8 21.32 0.38 0.90 8.9YR 2.1/0.2 Black 9 26.02 0.14 0.79 1.6Y 2.5/0.1 Dark gray 10 21.48 0.34 0.39 N 2.1 Black 44«11y(2007)
644 ½ yá yá Á w» 5 9, 10 ƒ ww. Table 4 z y» w L * 22.77 ~ 25.35 a * : 0.39 ~ 0.71, b * : 0.49 ~ 0.39 ùkû. y w L * 19.87 ~ 26.02 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 0.875 MnO 0.125 Fe 2 0.4875 Cr 2 0.50 Mn 2 0.0125 mle%, z w NiO 0.875 MnO 0.125 Fe 2 0.3875 Cr 2 0.50 Mn 2 0.1125 mle% NiO 0.975 MnO 0.075 Fe 2 0.4375 Cr 2 0.50 Mn 2 0.0625 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 0.875 MnO 0.125 Fe 2 0.4875 Cr 2 0.50 Mn 2 0.0125 mle%, z w NiO 0.875 MnO 0.125 Fe 2 0.4375 Cr 2 0.55 Mn 2 0.0125 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] 2097-104 (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] 29-32 (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] 269-72 (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] 160-65 (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] 2049-56 (2006). 7. R. A. Eppler, Cbalt-Free Black Pigment, Am. Ceram. Sc. Bull., 60 562-65 (1981). 8. O. Muller and R. Ry, The Majr Ternary Structural Families, Springer-Verlag, New Yrk, 1974. 9. R. A. Eppler, Nickel Spinels, Am. Ceram. Sc. Bull., 61 847-50 (1982). 10. J. A. Duffy, Bnding Energy Levels and Bands in Inrganic Slids, pp. 3, Lngman Grup,. United Kingdm, 1990. 11. N. T. McDevitt and W. L. Baun, Infrared Absrptin Study f Metal Oxides in the Lw Frequency Regin(700-240 cm 1 ), J. Spectrchimica Acta., 20 799-805 (1964). 12. R. A. Nyquist and R. O. Kagel, Infrared Spectra f Inrganic Cmpunds, pp. 217, pp. 489, Academic Press, INC., New Yrk, 1971. w wz