Jurnal f the Krean Ceramic Sciety Vl. 5, N. 8, pp. 53~58, 2008. Synthesis f Cr-dped Y 2 O 3 -Al 2 O 3 Red Pigments and their Applicatin Kyung-Hyun Shin and Byung-Ha Lee Department f Materials Science & Engineering, Myngji University, Yngin 9-728, Krea (Received June 3, 2008; Revised July 25, 2008; Accepted August 19, 2008) Cr-dped Y 2 O 3 -Al 2 O 3 w x Á w w œw (2008 6 3 ; 2008 7 25 ; 2008 8 19 ) ABSTRACT New inrganic red pigments based n Cr-dped Y 2 O 3 and Al 2 O 3 were synthesized by slid state methd and characterizatin f their pigments were characterized by using XRD, FT-IR, SEM and UV-Vis spectrphtmeter. The single pervskite phase revealed at 150 C ~ 1550 C fr 6 h due t using mineralizers. The clr f pigment pwders resulted ut varius red-shades depending n the cmpsitins f used materials and temperatures. Glazed tiles painted with pigment pwders shwed red clr in xidatin and reductin firing. The best red clur was btained when the Cr 2 O 3 was used 0.0 mle at 150 C fr 6 h. Key wrds a Red pigments, Slid state methd, Pervskite, Reductin firing 1. t w p. t w. ù ü ƒ š, üy w.» ü cadmium red (CdS/CdSe) wš ƒ š Cd, Se e š w w š. y w p e e š ù y ww w w ù w w» w -7) w š. m Al 2 O 3 Cr 3+ (crundum), ZnAl 2 O Cr, MnAl 2 O Cr 3+ (spinel), CaSnSiO 5 Cr 3+ (sphene), ZrSiO Fe 3+ (zircn) CdSCdSe(greenckite) 1,3). ù wwš y ey xk pyrchlre, pervskite, flurite structure w w w Crrespnding authr : Kyung-Hyun Shin E-mail : shinsaem@naver.cm Tel : +82-31-330-661 Fax : +82-31-330-657 2,,8,10) š.» UV stability š» r p,, v p, enamel w t 13). w w yw 12), y j» w ƒ w û p x v wš w. ù w p ùkü redù pink w. 7)»,, wz, z w w wš, z» šy wz ƒ. 1) m š r e p šy» w. 2. x 2.1. w Y 2 O 3 (France, Industial grade), Al(OH) 3 (Junsei, Japan, chemical pure), Cr 2 O 3 (Duksan, Krea, 99%), NaF(Duksan, Krea, practical grade), MgF 2 (Junsei, Japan, chemical pure), Li 2 CO 3 (Kant, Japan, Cica- Reagent) 53
5 xá w Table 1. Prepared Cmpsitins Sample N. Cmpsitin ST YAlO 3 N. 1 YAl 0.99 Cr 0.01 O 3 N. 2 YAl 0.98 Cr 0.02 O 3 N. 3 YAl 0.97 Cr 0.03 O 3 N. YAl 0.96 Cr 0.0 O 3 N. 5 YAl 0.95 Cr 0.05 O 3 Table 1 w w. r e p w w» w w Ÿy M. Shirpur et al. 2). e p g š k z ƒ Ë z 1350 ~ 1600 C w, ƒƒ š 6 k z þƒw. 900 C¾ 5 C/min, š ¾ 3 C/min. 2.2. p p X- z (X-ray Diffratmeter, XRD-7000, Shimadzu, Japan), FT-IR(IRPrestige21 (Shimadzu, Japan), SEM(scanning eletrn micrscpy, SS- 550, Shimadzu, Japan), UV-vis spectrphtmeter(201-pc, Shimadzu, Japan) w w. 2.3. x w x w w xr z z (Seger frmular t ) w. 5cm xr ƒ 2 w. w xr» ƒ (silicnite furnace) 1260 C 30 w þ w. 900 C¾ 5 C/min, 900 ~1260 C¾ 3 C/min w. w 120 C ƒ ƒ w. Seger frmular. lime-glaze 0.326 KNaO 0.00 Al 2 O 3 3.5526 SiO 2 Fig. 1. X-ray diffractin pattern f sample ST btained n calcining in air fr 6 h at 1500 C. 3. š 3.1. XRD» w X- z ww. Ÿy w š 1500 C 6 w M. Shirpur et al. ƒ 2) Y 2 O 3 w Al 5 Y 3 O 12 Y 3 Al 5 O 12. w Ÿy 6wt% w w AlYO 3 Al 2 Y O 9 (Fig. 1). Ÿ y (NaF/MgF 2 /Li 2 CO 3 (3 wt%/2 wt%/1 wt%)) wš ù j eyw w j 0.01 mle r e p. w XRD w ùküš. Fig. 2 Ÿy ƒw 150 C w w ùkü. 150 C w w 3 w q. 1350 C w w š Al 2 Y O 9. 3.2. FT-IR w w 0.6588 CaO 0.0019 Fe 2 O 3 0.018 MgO 2.. w w w w xr UV-vis spectrmeter(201-pc, Shimadzu, Japan) d w z(cie : Cmmissin Internatinale de l'eclairage)ƒ w CIE-L * a * b * t w ùkü. Fig. 2. X-ray diffractin patterns f samples N. 1, N. 3 and N. 5 btained n calcining in air fr 6 h at 150 C. w wz
Cr-dped Y 2 O 3 -Al 2 O 3 w 55 ƒ 150 C w Á ùküš. Fig. j š w» w 150 C w w j y ùkþ. j ƒ w w j ƒw y j 0.05 mle y w j p ƒ ùkù. 00 cm 1, 52 cm 1 60 cm j p ƒ ùk 1 ù. 150 C j 0.0 mle¾ š. Fig. 3. FT-IR spectra f samples : N. 3 at different temperatures.» w FT-IR w. Reflectance mde reslutin 1 16 cm w. Fig. 3 û 1350 C w 150 C 3 w wì ùkü. 00~700 cm 1 j p 1 1) 625 cm 1, 555 cm w 1 1 35 cm 07 cm w. x w j 1300 C w j t w w š. ƒ û 1350 C j š w 15 cm š 1 60 cm 1 3.3. SEM w x» w SEM w. Fig. 5. w r e p x x w x ùkùš. 1350 C ƒ. w 6µm w. 3.. UV-Vis spectra w UV-Vis spectra UV-Vis spectra Fig. 6 ùkü. YAlO 3 j (III) w w. YAlO 3 6 q œ» 2)w. q y j (III) w ligand field thery w 3 v ƒ Ÿ ƒ 3,15,16)w. Fig.. FT-IR spectra f samples fired at 150 C. 5«8y(2008)
신경현 이병하 56 Fig. 5. SEM micrgraphs f sample N. 3(except c: N. ). 낸다. 순수한 Cr O 의 흡수밴드는 580 nm와 05 nm에서 각각 나타난다. 본 실험결과에서 이들 밴드는 15 nm와 510 nm 부근에서 넓게 나타났다. Cr O 의 흡수밴드보다 낮은 파장에서 이들 두개의 흡수밴드가 나타난 것은 결 정구조 내에서 Cr(III)에 의한 Al(III)의 치환에 의해 만들 어지는 Cr-O거리 감소(Al(III)의 이온 반경 0.51 Å, Cr(III) 의 이온 반경 0.65 Å)에 의한 ligand field의 강도가 증가 한 때문이다. Visible spectrum의 green-blue vilet 영역에 서의 강한 흡수밴드는 rthrhmbic pervskite에서 점대칭 의 낮아짐과 연관된 두개의 Cr 피크의 유착에 의한 것이 며 페로브스카이트 안료의 붉은 발색은 350~650 nm 영 역에서의 강한 흡수밴드에 의한 것 이다. 소성된 안료의 UV-vis 측정결과가 모두 같은 경향을 나타내고 있다. 3,, 5번 조합의 경우는 전체적으로 비슷한 흡수강도와 형 태를 나타내고 있다. 번 조합의 경우 흡수강도는 1500 C 소성한 안료가 제일 높게 나타나고 150 C가 두 번째로 크게 나타나는데 색상 값으로 나타낼 때 150 C 소성 안 료가 a*값이 더 크게 나오는 것은 흡수 밴드의 폭이 2 3 16) 2 3 3+ Fig. 6. UV-vis spectra f the sample N. at different temperatures. 에너지와 일치하는 A T (F)와 A T (F) 전이이 고 세 번째 스핀은 색에 영향을 미치지 않는 자외선광과 일치하는 에너지로 A T (P) 전이이다. 산화물 이온 에 의해 형성되는 ligand field에 따라 이들 밴드의 위치 는 변경될 수 있으며 관찰된 색에서 다양한 결과를 나타 Fig. 7. 한국세라믹학회지 1g 1g 1) Pigment clr crdinates in the L*a*b* space depending n different temperatures.
Cr-dped Y 2 O 3 -Al 2 O 3 w 57 Fig. 8. Clr crdinates f underglazed pigment in the L * a * b * space. 1500 C w, ƒq ùkù». w û j w 0.0 mle ƒ 0.8 e ùküš yw. 3.5. d ùkþ. ƒ û ùkü b * ùkû (Fig. 7). 150 C ùkü a w * š b * j ùk û. 150 C b û ù * a * û. wz xw» w r š» z w w. UV-vis spectrmeter(201-pc, Shimadzu, Japan) w wz w w CIE-L * a * b t * L * a * b * Fig. 7 Fig. 8 ùkü. w w ƒ y y j š 150 C w y ùkþ. y šy ü y ü w. w w š { w» ü. š ü, p y w š š, w w»..» w r e px š w. Y(AlCr)O 3 k ƒ 7) w. w y y w. x w ƒ wz wš. 1) Ÿy w 150 C r e p. 2) w wz w y y w. CIE L * a * b * ùkü w a * 22.00-33.69 ùküš. wz w z w, y a * 1.75-29.71 y 1.78-30.86 š. 3) 150 C w ƒ w w wz ùkû. ) w 150 C w j 0.0 mle ƒ ùkþ. 5«8y(2008)
58 xá w Acknwledgment 2007 ( w» ) w w w (N. R0A-2006-000-102-0) REFERENCES 1. F.G Matteucci, C. Lepri Net, M. Dndi, G. Cruciani, G. Baldi, and A. O. Bschi, Clur Develpment f Red Pervskite Pigment Y(Al,Cr)O 3 in Varius Ceramic Applicatins, Advances in Applied Ceramics, 105 [2] 99-106 (2006). 2. M. Shirpur, M. A. Faghihi Sani, and A. Mirhabibi, Synthesis and Study f a New Class f Red Pigments Based n Pervskite YAlO 3 Structure, Ceramics Internatinal, 33 [8] 127-33 (2007). 3. RU SU Pavlv, Juan B. Carda Castell, VU Blasc Marzá, and J. M. Hhemberger, New Red-shade Ceramic Pigments Based n Y 2 Sn 2 x Cr x O 7 Pyrchlre Slid Slutins, J. Am. Ceram. Sc., 85 [5] 1197-202 (2002).. Y. Marinva, J. M. Hhemberger, E. Crdncill, P. Escriban, and J. B. Carda, Study f Slid Slutins, with Pervskite Structure, fr Applivatin in the Field f the Ceramic Pigments, J. Eur. Ceram. Sc., 23 213-20 (2003). 5. M. Jansen and H. P. Letschert, Inrganic Yellw-red Pigments withut Txic Metals, Nature, 0 [] 980-82 (2000). 6. L. Sandhya Kumari, P. Prabhakar Ra, and M. Lakshmipathy Reddy, Envirnment-friendly Red Pigments frm CeO 2 -Fe 2 O 3 -Pr 6 O 11 Slid Slutins, J. Allys and Cmpunds, 61 509-15 (2008). 7. A. Garca, M. Llusar, J. Calb, M. A. Tena, and G. Mnrs, Lw-txicity Red Ceramic Pigments fr Prcelainised Stneware frm Lanthanide-cerianite Slid Slutins, Green Chemistry, 13 238-2 (2001). 8. Jitendra Kumar Kar, Rn Stevens, and Christper R. Bwen, Prcessing and Characterisatin f Varius Mixed Oxide and Pervskite-based Pigments fr High Temperature Ceramic Cluring Applicatin, J. Allys and Cmpunds, 61 77-8 (2008). 9. FU Bndili, TU Manfredini, and CU Siligardi, New Glassceramic Inclusin Pigment, J. Am. Ceram. Sc., 88 [] 1070-71 (2005). 10. Elena Lpez-Navarrete, Victr M. Orena, Francisc J. Lzar, Juan B. Carda, and Manuel Ocaa, Preparatin Thrugh Aersls f Cr-dped Y 2 Sn 2 O 7 (pyrchlre) Red-shade Pigments and Determinatin f the Cr Oxidatin State, J. Am. Ceram. Sc., 87 [11] 2108-13 (200). 11. SU Furukawa, TU Masui, and NU Imanaka, New Envirnment-friendly Yellw Pigments Based n CeO 2 -ZrO 2 Slid Slutins, J. Allys and CmpundsSG 51 60-3 (2008). 12. E. S. Cherepanv, O. S. Grum-Grzhimail, N. S. Belsttskaya, and M. S. Bibilashvili, New Grup f Ceramic Pigments, Translated frm Stekl I Keramika, N. 8, pp. 26, August, 1986. 13. R. A. Eppler and D. R. Eppler, Which Clrs Can and Cannt Be Prduced in Ceramic Glazes, Ceram. Eng. Sci. Prc., 15 [1] 281-88 (199). 1. Neil T. McDevitt and William L. Baun, Infrared Absrptin Study f Metal Oxides in the Lw Frequency Regin (700~ 200 cm 1 ), Spectrchemica, Acta, 20 799-808 (196). 15. R. Galind, M. Llusar, M. A. Tena, G. Mnrs, and J. A. Badenes, New Pink Ceramic Pigment Based n Chrmium(IV)-Dped Lutetium Gallium Garnet, J. Eur. Ceram. Sc., 27 199-205 (2007). 16. M. Marts, M. Martnez, E. Crdncill, and P. Escriban, Twards Mre Eclgical Ceramic Pigments : Study f the Influence f Glass Cmpsitin n the Clur Stability f a Pink Chrmium-dped Ceramic Pigment, J. Eur. Ceram. Sc., 27 561-67 (2007). w wz