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1 Jurnal f the Krean Ceramic Sciety Vl. 7, N. 6, pp. 608~61, 010. DOI:10.191/KCERS Synthesis and Characterizatin f Al-dped Uvarvite Green Pigments Sung-Gyu Se and Byung-Ha Lee Department f Materials Science & Engineering, Myngji University, Yngin 9-78, Krea (Received July 9, 010; Revised August 16, September 6, 010; Accepted September 15, 010) Al-dped Uvarvite w p ³Á w w œw ( ; , 9 6 ; ) ABSTRACT Uvarvite Garnet is green pigment prepared by using, CaO and which are widely used in ceramic industry. The synthesis f abve pigment was carried ut by mixing, and CaC as frmulated and then firing at 1000~100 C. T investigate the ptimum synthesis cnditin f the Uvarvite Garnet. it was prepared by using CaO t replace CaC, CaF and CaCl. T get green brighter clr, Al + was substituted fr Cr +. They were characterized by X-ray diffractin, UV-Vis spectrscpy, Raman spectrscpy and SEM analysis. When the pigments were applied t lime glazes (6 wt%), clr parameters f Uvarvite Garnet shwed the L* =0.99, a*=6. and b* =17.0. Key wrds : Uvarvite, Green, Pigments, Garnet 1. x t w w ù Ö š. t j w w.» š UV ƒ š» r p,, v p, ù w t y.» j 1) ceramic matrix insluble clred crystalline phase j.» w» ) w» (tinctrial strength) š (high temperature stability) üyw (chemical resistance) w. ) w š š w w š» v. ) y, w ùkü. CaO w CaO- - w w, Uvarvite (Ca Cr(SiO ) ) š w š. 5) Uvarvite w Ÿ w Crrespnding authr : Byung-Ha Lee lbh@mju.ac.kr Tel : Fax : ù ƒ yw A B (SiO ) tx. ƒ 8 A Site Ca + (1.1 Å), Mg + (0.78 Å), Fe + (0.87 Å) j ƒ ew, B Site ƒ 6 Cr + (0.69 Å), Al + (0.57 Å), Fe + (0.6 Å) ƒ. w 6), y,,, w ƒ w. p ƒ w š š, š w üyw š. x w w 5) v g w ƒ w š. g y ¾ ùký Uvarvite w ƒ. v Uvarvite w ƒ w Uvarvite k wš. w Uvarvite + + w ³ wš Cr Al ey w w wš w.. x Uvarvite w w» w 608

2 Al-dped Uvarvite w p 609 Table 1. Cmpsitins f the Uvarvite (mle%) CaC CaF CaCl Table. Cmpsitins f the Al-dped Sample (mle%) Al CaC CaF CaCl Uvarvit N N N (Duksan, Krea 99%), CaC (Junsei, Janpan, 99.5%), CaCl (Kkusan, Janpan, 95%), CaF (Junsei, Japan, 98%), (Junsei, Japan, Extra pure) w. Uvarvite w w w CaC CaF š CaCl w Table 1 ùkü. ƒƒ w e g w p yww. 60 C z y» 900 C¾ 5C/min 1000 C~100 C¾ C/min g 1 k z þƒw. w ùkù 7 w(table 1)» Uvarvite Cr + + Al eyw w» w Table Al eyw. z sƒ» z. Seger eq.(1) y w z w 6wt% ƒw xr w y» 160 C/0 w. w p sƒw» w X- z»(xrd-7000, Shimadzu, Japan) d w š, ƒ Al š Raman(Dimensin- P Raman). x x (SS-550, Shimadzu, Japan) w š, j»»(sald-7101, Shimadzu, Japan) d w. w z UV-vis Spectrmeter (UV-01PC, Shimadzu, Japan) d w CIE(cmmissin internatinale de l'éclairage) L* a* b* ùkü. Fig. 1. XRD patterns f sample ~8, fired at 100 C/1 h. (1) lime glaze 0.6 KNaO CaO 0.0 Al MgO add. pigments 6 wt% eq.(1). š Uvarvite w w» w Table 1 ƒ w 100 C 1 w. w XRD Fig. 1 ùkü. 7 w Uvarviteƒ w. Table 1 CaC CaF eyw ƒ œ w CaF CaCl š CaC.5 mle ƒw CaSiƒ œ w. 1 mle, CaC mle, CaF 0.5 mle, CaCl 0.75 mle, mle Uvarvite w w. w» w Fig. 1 7 w 1000 ~ 100 C 100 C w XRD w. Fig. Uvarvite 1000 C l KCl ƒ œ w. ƒ CaSi Uvarvite ƒw ƒ 100 C l Uvarvite w. Uvarvite w 100 Cƒ q» v w 100 C û w w. w w» w Cr Al e y wš Table ww 100 C 1 w. XRD 7«6y(010)

3 서성규 이병하 610 Fig. 5. Fig.. XRD patterns f cmpsitin 7 fired at 1000~100C/ 1 h. SEM micrgraphs f fired sample(100c). Fig. 에 나타내었다. 그 결과 Cr O 대신 치환된 Al O 의 영향으로 Al SiO Peak이 0. mle부터 나타나 치환한계는 0.1 mle임을 알 수 있다. 이와 같은 치환한계를 보다 명확히 하기 위하여 Raman 분석하였으며 그 결과를 Fig. 에 나타내었다. Raman spectrscpy 측정 시 나타나는 Uvarvite의 주 특성밴드 는 69 cm, 50 cm, 796 cm, 80 cm, 89 cm 로써 Uvarvite의 180 cm ~1000 cm 의 특성밴드 중 180 cm 에 서 나타나는 band는 SiO 사면체의 translatins를 나타내고 60 cm 은 Ca 이온의 translatins 그리고 60 cm 은 SiO 사면체의 internal stretching, bending, rtatinal vibratin 에 관한 특성 밴드를 보여준다. Fig. 의 분석결과에서 Cr O 의 일부를 Al O 로 치환함에 따라 0. mle부터 peak 이 오른쪽으로 shift된 것을 볼 수 있는데 이는 미 반응 Al O 에 의한 영향이다. 특히 50~600 cm 에서 Al O 가 0. mle치환된 조성부터 Al O 의 존재로 인한 Peak의 변 5 7) + 8) Fig.. Fig.. XRD Patterns f Al-dped sample N.1~N., fired at 100C/1 h. Raman spectra f Al-dped sample N.1~ N., fired at 100C/1 h. 한국세라믹학회지

4 Al-dped Uvarvite w p 611 Fig. 6. Particle size analysis f the uvarvite fired at 100 C. Table. Results f the Glazed Tiles Sample X L* a* b* (H) (V)/(C) Clr Uvarvite /.0 GY NO /.7 GY NO /.9 GY NO /.8 GY Fig. 7. UV-vis spectra f Al-dped samples fired at 100 C/1 h. y. Uvarviteü š Al š w 0.1 mle. 100 C w w x» w SEM w Fig. 5 ùkü. Uvarvite x 1, Fig. 6 10~0 µm j». z» w z w 160 C w UV-vis d w UVvis spectra Fig. 7 ùkü. w Uvarvite Cr electrnic d-d transitin w ƒ ƒ w. Space grup Iad ƒ + Cr 8 16a site w. q y Cr + A g T g U-band A g T 1g Y w Ÿ wš w ƒ w. y w x 9,10) ligand Fig. 8. CIE L*a*b* clrimetric parameters f the glazed tiles fired at 160 C/0 min. field e w ùkü. UV-vis Cr + ƒ š w 80 nm, 0 nm, 600 nm Intensity. w, Uvarvite ü + Cr w š ey + Al ƒw ƒ w. w w CIE-L*a*b* Munsell t Table 7«6y(010)

5 61 ³Á w Fig. 8 mw ùkü. CIE-L*a*b* L*»(Lightness) 100, 0 ùkü. a* (+), (-) ùkü. b* (+) y, (-) ùkü. Munsell t (H Hue), (V Value), (C Chrma) ùkü. w Uvarvite w r L* 8.15, a* 6.87, b* 18.5 š Al š w 0.1 mle ƒ 1 r L* 0.99, a* 6., b* 17.0»ƒ š. x w š ùk û. Al ƒ 0.~0. mle ey w Al ƒw L*a*b* ù w w Uvarvite ƒ š 1 ww š q.. š w ƒ w w. w Al eyw» Uvarvite w w. (1) Uvarvite w w» w 1 mle, CaC mle, CaF 0.5 mle, CaCl 0.75 mle, mle 100 C 1h w w. () Al ƒ 0.1 mle v x w š Uvarvite ùkû. () w SEM w x Uvarvite 1 š 10~0 µm. () w z 6wt% ƒw xw, L* 0.99, a* 6., b* Acknwledgment 009 ( w» ) w w w. (N. R0A ) REFERENCES 1. R. A. Eppler and D. R. Eppler, Which Clrs Can and- Cannt Be Prduced in Ceramic Glazes, Ceram. Eng. Sci. Prc., 15 [1] (199).. A. Burgyan and Richard A. Eppler, Classificatin f Mixed-Metal-Oxide Inrganic Pigments, Am. Ceram. Sc. Bull., 6 [9] (198).. E. Ozel and S. Turan, Prductin and Characterisatin f Irn-chrmium Pigments and Their Interactins with Transparent Glazes, J. Eur. Ceram. Sc., 0970 (00).. K.-H. Lee, Y.-S. Lee, J.-S. Park, and B.-H. Lee Preparatin and Characterizatin f Black Zircnia Ceramics by Black Clr Spinel Pigment, J. Kr. Ceram. Sc., 5 [] 19 (008). 5. A. S. Bystrikv and Yu. F. Petrv, Synthesis f Chrmium Pigment f the Garnet Type, Build. Ceram. Res. Inst., 8 1- (1968). 6. G.-J. Kim, J.-S. Kim, W.-S. Kim, and J.-B. Chi, Gelgical and Mineralgical Prperties f the Red Garnet Stnes, J. Miner. Sc. Kr., (00). 7. A. Chpelas, Single Crystal Raman Spectrum f Uvarvite, Ca Si O 1, Phys. Chem. Miner., 55-0 (005). 8. M. Andrut and M. Wildner, The Crystal Chemistry f Birefringent Natural Uvarvites, Phys. Chem. Miner., (00). 9. Radstin S. Pavlv, V. B. Marzand, and J. B. Carda, Electrnic Absrptin Spectrscpy and Clur f Chrmium dped Slids, J. Mater. Chem., (00). 10. R. Galind, M. Llusar, M. A. Tena, G. Mnrs, and J. A. Badenes, New Pink Ceramic Pigments Based n Chrmium(IV)-dped Lutenium Gallium Garnet, J. Eur. Ceram. Sc., (007). w wz