Jurnal f the Krean Ceramic Sciety Vl. 47, N. 3, pp. 249~255, 2010. DOI:10.4191/KCERS.2010.47.3.249 Optical Prperties f (V, Pr)-dped ZrSiO 4 Green Pigments Kyu-Ri PynG and Byung-Ha Lee Department f Material Science & Engineering, Myngji University, YngIn, 449-728, Krea (Received March 25, 2010; Revised April 8, April 12, 2010; Accepted April 19, 2010) ù v w g Ÿw p ³ Á w w œw (2010 3 25 ; 2010 4 8, 4 12 ; 2010 4 19 ) ABSTRACT T investigate ptical prperties f (V, Pr)-dped ZrSiO 4 green pigments, samples were prepared by the ceramic methd using NaF and NaCl as mineralizers. They were characterized by X-ray diffractin, UV-Vis spectrscpy and Raman spectrscpy. The changes f clr in the samples during heating and effect f mineralizers were studied in terms f valence f the vanadium and prasedymium in the zircn matrix. (V, Pr)-dped ZrSiO 4 pigments give rise t green clratin in 800 C. The xidatin state f V and Pr ins f pigments in the glazed samples were cnfirmed by UV-Vis absrptin spectra. This absrptin spectra shwed three typical bands f trivalent Pr at the 445, 480~490, 592 nm due t f-f transitins and tw brad bands f 302~380, 400~500 nm due t f-d transitins f tetravalent Pr. Accrding t the increasing amunts f, the tw brad bands shwed decreasing intensity at 290, 640 nm due t d-d transitins f tetravalent V. Key wrds : ZrSiO 4 green pigments, Oxidatin state, Absrptin spectra, Raman mde assignment 1. üy ƒ g, ü, e y ƒ w»» ƒwš. g 1) 1948 vanadium zircn blueƒ š 1950 prasedymium zircn yellw 1960 irn zircn pinkƒ. y Ca- Cr-Si ƒ x m C-Zn-Al-Cr v x vgj t z w. Zr-Si-Pr y Zr- Si-V yw w. g j ù g p w» x. lj l 3) z w. 2) R. A. Eppler V-ZrSiO 4 f Marker Technique w NaF w in diffusin mdel Crrespnding authr : Byung-Ha Lee E-mail : da5raa@naver.cm Tel : +82-31-330-6461 Fax : +82-31-330-6457 vapr transprt mdel w. Ÿy ƒ SiO 2 w ZrO 2 ù w š w ù w { Ÿy w w š w. z Demiray et al, M. Ocana et al, G. Mnrs et al ù š w 4-6) ƒ, e w š w. v g y Na 2 MO 4 NaCl w 1956 Kat Takashima w. M. Trjan, M. Ocana et al, J. A. Badenes et al, F. Bndili et al w w f Pr ƒ g ü e ƒ 14) ¾ y w š. 7-13) S. Parasuraman g v cdpant ù w e w w. ù g jš ƒ w ƒ w š w. ù V Pr c-dpingw w w g š w r. M-ZrO 2, SiO 2 wš Ÿy NaF, NaCl w š ù v cdping g w wš w. V 2, Ÿy w y» w. 249
ù v w g Ÿw p 250 Table 1. Crystalline Phase and L* a* b* Value f V and Pr c-dped Pigments with Cntents Change f V 2 and at 800 C P 1 P 3 P 5 P 6 V 0.1 Z(vs)m(vw) Z(vs)m(vw) Z(vs)m(w) L* a* b* 61.97-16.08-14.10 70.59-15.82 9.27 76.68-4.77 49.77 V 0.13 Z(vs)m(w) Z(vs)m(w) L* a* b* 70.03-16.21 10.35 70.46-14.07 19.02 *NaF: 0.5 ml%, Hlding time : 3 h *Peak intensity: vs(very strng), m(medium), w(weak), vw(very weak) *Crystalline phase : Z: zircn, m: mnclinic ZrO 2 * V : V 2 (ml%), P: (%) 2. x 2.1. ù v cdping g w w» w p M-ZrO 2 (Yakuri) SiO 2 (Duksan) w. p prasedymium(iii, IV) xide(alfa Aesar), vanadium pentxide(junsei), Ÿy NaX (X=F, Cl)(Duksan) w., ZrO 2 SiO 2 mle yww z V 2 0.1~0.13 ml%, 1~6%, NaF NaCl 0~0.5 ml% ü ƒw g yww. ƒƒ 600 ~ 800 C 3 C ù ƒ w w w š, ƒƒ 3 w. 2.2. p w y w» w XRD(Shimadzu, XRD 7000) w. 2θ 20~70 scanning rate 10 /m d w š step size 0.2 w. g (αzrsio 4 =I ZS(200) +I M(11 ) +I M(111) +I T(111) ) 2θ 26~32 1 ùkù 4 p peak - ZrSiO 4 (200), (Mnclinic) M-ZrO 2 (11, 111) and (Tetragnal) T-ZrO 2 1 (111) w w. 15) w p V, Pr ƒ y w» w UV-Vis spectrscpy (Shimadzu, UV-2410 PC) w. w z w 1260 C w v 200~800 nm absrptin mde d w. CIE L * a * b * t w U.V PC ptical clr analysis sftware (P/ N 206-67449) w eyw. g V-O bnding mde y wš dphantƒ g raman spectra e w» w Raman spectrscpy (Dimentin D2, Lambda Slutin, Inc, U.S.A.) w. Raman spectrum vectr raman prve(rp532-us) w semicnductr 532 nm laser d w spectral reslutin 3cm -1 w. w p mw š w w V Pr ƒƒ e w r. w g d w SK 8 šy n Ÿk z w š,. 0.297 KNaO 0.157 CaO 0.734 Al 2 O 3 4.682 SiO 2 0.018 MgO 0.528 BaO ƒƒ v z 10% ƒw 4 4cm k x r w. electric furnace 3 C/min 1260 C¾ wš 30 w z þw. 3. š 3.1 X-ray diffractin 3.1.1. V 2 w y y V 2 w g w V 2 ƒ g e w. V 2 0.1, 0.13 ml% w ƒƒ1, 2, 3, 4, 5, 6% ƒw 800 C 3 w w w. w y Table 1 ùkü. Ÿy NaF 0.5 ml% ƒw w. g XRD vj ql j. ƒ ƒw 2 M-ZrO 2 ƒ š g w. ƒ g j w ù, Table 1 L* a* b* j w. 3.1.2. Ÿy w y y V 2 w w w. V 2 0.1 ml% 6% ƒ w kw Ÿy y g e w. g w 47«3y(2010)
251 ³ Á w Fig. 1. XRD patterns f different cntents f mineralizers in (V, Pr)-dped ZrSiO 4 pigments at 800 C(V 2 0.1 ml%, 6%) Z: zircn, m: mnclinic ZrO 2, C: cristbalite. Fig. 3. XRD patterns f different temperatures and cntents f mineralizers in (V, Pr)-dped ZrSiO 4 pigments.(v 2 0.1 ml%, 6%) Z: zircn, m: mnclinic ZrO 2 C: cristblite, S: Na 2 ZrSiO 4, N: NaCl, P: Pr 8 Si 6 O 24. Fig. 2. Zircn fractins with different cntents f mineralizers(naf/nacl) in (V, Pr)-dped ZrSiO 4 pigments at 800 C(V 2 0.1 ml%, 6%). (Fe, Pr, V) Ÿy. 16) w y w NaF NaCl w g, V 2 w w NaF w g ƒ w. V 2 0.1 ml%, 6%, NaF 0.5 ml% ƒw kw NaCl ƒ y 800 C 3 w w w. w y Figs. 1 2 ùkü. NaF 0.5 ml% w w w g 86% w NaCl 0.5 ml% w w w XRD g 62% w. NaF 0.3, NaCl 0.2 ml% w w w 89% ƒw š, NaF 0.2, NaCl 0.3 ml% ƒw g 91% ƒ ùkû. m-zro 2 5.4% ƒ û. x ù v w g w w Ÿy NaF NaCl wì w z ù kû, g y j Ÿy ƒ NaF 0.2, NaCl 0.3 ml%. (V, Pr)-dped g w w NaF NaCl ƒ g e w. V 2 0.1 ml%, 6%, NaF 0.2, NaCl 0.3 ml% ƒ w NaF 0.3, NaCl 0.2 ml% ƒ w 600, 700, 800 C 3 w w w. Fig. 3 ùkü. NaF NaCl œ 680 C š g» w. 16) Fig. 3 600 C NaF NaCl œ» NaCl Na 2 ZrSiO 4, Pr 8 Si 6 O 24 m-zro 2. g 700 C y» w. NaCl 0.2 ml% ƒ g w. NaCl 0.3 ml% g x ƒw ùkü» w ù m-zro 2. 800 C NaF 0.2, NaCl 0.3 ml% ƒw w g w š w yellwish green w. Na 2 ZrSiO 4 š Pr 8 Si 6 O 24. V 2 w g w w g ƒ V 2 0.1 ml%, w wz
ù v w g Ÿw p 252 Table 2. L* a* b* Value and Munsell Clr Ntatin in Glazed Samples f Synthesized (V, Pr)-dped Pigments at 800 C fr 3 h V 2 (ml%) (%) M (ml%) L* a* b* H V/C Clr 0.1 1 NF 0.5 61.97-16.08-14.10 4.0B 6.1/5.0 Light greenish blue " 2 " 68.36-16.16-4.43 7.8BG 6.7/3.4 Light bluish green " 3 " 70.59-15.82 9.27 2.2G 7.0/2.9 Light yellwish green " 4 " 75.22-10.16 32.76 0.7GY 7.4/4.5 Light greenish yellw " 6 NF 0.5 76.68-4.77 49.77 5.5Y 7.6/7.0 Greenish yellw " " NF 0.3 NC 0.2 69.91-13.21 26.74 4.1GY 6.9/4.0 Yellwish green " " NF 0.2 NC 0.3 67.51-13.89 18.04 6.9GY 6.7/3.2 Mderate yellwish green " " NC 0.5 60.41-17.37 2.63 5.4BG 5.9/3.5 Light bluish green *M : mineralizers NF :NaF NC:NaCl 6%, NaF 0.2, NaCl 0.3 ml%. NaF NaCl ƒ g j w p 700 C NaCl g j ùkû. 3.2 Optical prperties 3.2.1. Clr Table 2 V 2,, NaF, NaCl w 800 C 3 w g w w. w Ÿy ƒ» w UV-Vis spectrscpy d w CIE L * a * b t w * eyw. Table 2 ùkü. V 2 0.1 ml%, NaF 0.5 ml% ƒw ƒ ƒƒ 1, 2, 3, 4, 6% ƒ g 2% l (b* : 4.43)» w y (b* : 9.27 / 32.76) w. g ü t ü ù ü v c-dping ùkù yw w. V 2 0.1 ml% 6% ƒw Ÿy ƒ y g w y w. NaF 0.5 ml% ƒw w w w y ùkü. NaF ƒ 0.3 ml% jš NaCl 0.2 ml% ƒw w. NaCl ƒ 0.3 ml% ƒ j a* 13.89, b* 18.04 ƒ ƒw. ù NaCl 0.5 ml% ƒw w w (a* : 17.37, b* : 2.63) w. g ù v ƒ y j. x (mderate yellwish green) Ÿy NaF NaCl ƒ y. g Ÿy ƒ w Fig. 4. Optical absrptin spectras f a glazed sample with (V, Pr)-dped ZrSiO 4 pigments(v 2 0.1, NaF 0.5 ml%) accrding t different cntents f at 800 C(3 h). j w q. 3.2.2. UV-Vis absrptin spectra V 2 w g w w Ÿy ƒ y V Pr ƒ» w UV-Vis spectrscpy w. Figs. 4~6 Table 3 ùkü. Fig. 4 V 2 0.1 ml%, NaF 0.5 ml% ƒw ƒƒ 1, 2, 3, 4% ƒw 800 C 3 w w w U.V-Vis spectra. ƒw ùkü 4+ V p 13) 290, 640 nm ƒ w š, y ùkü Pr 3+ (445, 18,19) 17) 480~490, 592 nm) Pr 4+ (302~380, 400~500 nm) p ƒ w. Pr 3+ p Pr e» y 4+ ù, 445 592 nm wì ƒ ƒwš. Fig. 5 V 2 0.1 ml%, 6% wš Ÿy ƒ y 700 C 47«3y(2010)
253 ³ Á w Fig. 5. Optical absrptin spectras f a glazed sample with (V, Pr)-dped ZrSiO 4 pigments(v 2 0.1 ml%, 6%) accrding t different cntents f NaF and NaCl at 700, 800 C fr 3 h. Fig. 6. Raman spectras f ZrSiO 4 pwder and cmmercial zircn pigments. 800 C 3 w w w U.V-Vis spectra. w 800 C 4+ V w Ì Pr 4+ 3+ Pr p ƒ ƒw š, NaF 0.2, NaCl 0.3 ml% ƒw 800 C w w ƒ ƒ yw mderate yellwish green w. ƒ ë y ywš p q ƒ ë. w w ƒ ùk ùš ë. g ü 4+ V d- d wš. Pr 3+ d p f-f w w» f 4+ ùkü. Pr f-d w. g ü w 4+ V 4+, Pr 3+, Pr y w Table 3 ùkü. (1) visible spectrum frm 400 t 700nm ƒ Ÿ vilet-blue 400~500 nm t 1g f 18)» w 4+ Pr ƒ. Blue 445 nm Blue-green 480~ 490 nm, yellw 592 nm ƒƒ 3 3 3 P 1, H 4 3 3 P 0, H 4 1D 2» w 4 ƒ. k 3 H 4 3 3 3 P 2, P 1, P 0, 1D 2» k w 3+ Pr p 17) G. D. A. Licciulli et al w y ew. Red 640nm 4+ V p 2 B 2 1 E 5)» w g t. x w w ƒ 400 ~ 500 nm 4+ Pr 445, 480 ~ 490, 592 nm Pr 4+ p wì 3+ ƒw š, 640 nm V p w. (2) Ultravilet regin frm 200 t 400 nm H 4 3 P 2, 3H 4 Ultravilet 290 nm 2 B 1 2 A 1 5)» w 4+ V ƒ, ƒ w t w. 302~380 nm Pr p 4+ 2t 2g f 18)» w V 4+ q w w yw. 3.2.3. Raman spectra w w (V, Pr)-dped g raman Table 3. Summery f the Absrptin Bands and Assignments f Sample with (V, Pr)-dped ZrSiO 4 Pigments(V 2 0.1 ml%, 6%) accrding t Different Cntents f NaF and NaCl at 800 C(3 h) Valence state Band Assignments Wavelength (nm) 445 480~490 480~490 592 Pr 3+ f-f transitin 17) 3 H 4 3 3 P 2 H 4 3 3 P 1 H 4 3 P 0 3H 4 1 D 2 w wz Pr 4+ Wavelength (nm) 302~380 400~500 V 4+ f-d transitin 18,19) 2t 2g G f t 1g G f Wavelength (nm) 290 640 d-d transitin 4) 2 B 1 G 2 A 1 2B 1 G 2 E
ù v w g Ÿw p 254 Table 4. Assignment f Raman Vibratinal Mdes in Synthesized (V, Pr)-dped Zircn Pigments and Cmmercial Zircn Pwder Cmpared with thse Observed fr tgether with Cmmercial Zircn Pigments (V, Pr) c-dped SZP (V, Pr) c-dped CZSP Pr-dped CZSP V-dped CZSP ṽ ṽ ṽ ṽ ṽ Cmmercial ZrSiO 4 Pwder /cm -1 /cm -1 /cm -1 /cm -1 /cm -1 Mde Assignment 20,21) 1005 1003 1003 1003 1005 Zircn B 1g Si-O v 3 972 980 980 970 972 Zircn A 1g Si-O v 1 950 950 950 V-O 625 623 622 622 625 Zircn B 1g 472 473 473 V-O 434 432 432 434 434 Zircn B 1g 401 401 390 407 Zircn E g Si-O v 4 386 V-O 353 352 352 352 353 Zircn E g 224 220 221 222 222 Zircn E g External mde(rt.) 198 201 200 198 198 Zircn E g External mde(trans.) *SZP : Synthesized ZrSiO 4 Pigment / CZSP : Cmmercial ZrSiO 4 Pigment mde y w» w w. g q ƒ š g w w g w Fig. 6 Table 4 ùkü. g q» w 1005(B 1g ), 972 (A 1g ), 401(E g )cm wavenumber Si-O -1 stretching mde w vj ƒ š 21) w. External mde 222 (E g ), 198 (E g ) peak 353 (E g )cm g p vjƒ -1. V-dped pigment spectra ƒƒ 950(v 1, stretching), 473(v 4, bending), 386(v 2, bending) cm -1 V-O mde ƒ 20). ù g x g raman spectra ql, v y ù v g m-zro 2 p vjƒ. v ƒ ƒw g û XRD ew. V 2 0.1 ml%, 6%, NaF 0.5 ml% ƒw NaCl ƒ y 800 C 3 w w w. Ÿy ƒ raman spectra» w w d w Fig. 7 ùkü. y NaF 0.2, NaCl 0.3% ƒw w w Si-O stretching mde 21) p vjƒ 1005 cm -1 (B 1g ) y š, 865, 801, 789, 687,437, 353, 223 cm g p vj ƒ x -1. NaCl NaF ƒƒ 0.5 ml% w w w 950(v 1, stretching) 972 cm -1 (A 1g ) vj ratiƒ. Fig. 7. Raman spectras f V 2 0.1 ml%, 6% dped zircn green pigments accrding t different cntents(ml%) f mineralizers(naf/nacl) at 800(3h). Z: Zircn, M: M-ZrO 2. 950 cm -1 V-O vibratin mde p vj ƒ ùkû. Table 4 ùkü y (V, Pr)-dped g 1005, 972, 950, 625, 472, 434, 353, 224 cm -1 raman active mde g p vjƒ y. 4. ù v cdpingw g š w w. V 2, NaF NaCl ƒ y w Ÿy ƒ g e w. w g ü V, Pr ƒƒ e w w. 47«3y(2010)
255 ³ Á w (1) (V, Pr)-dped g w, V 2 0.1 ml%, 6% NaF 0.2, NaCl 0.3 ml% ƒw 800 C 3h w w w, w e L* 67.51, a* 13.89, b* 18.04. (2) V 2 0.1 ml%, 6% ƒw NaF 0.2, NaCl 0.3 ml% ƒw w w g 91%, Ÿy NaF NaCl w g g. w NaCl ƒ w. (3) w UV-Vis V in 4 k + ƒ ƒw vj w. Pr in 3+ w + + 3 4 4+ k œ w. Pr 445, 480~490, 592 nm, Pr 302~380, 400~ 500 nm p vjƒ š ƒ ƒw ƒw. (4) w Raman -1 1005, 972, 950, 625, 472, 434, 353, 224, 198 cm zircn active mde -1 950 cm V-O bnding mde y w. Acknwledgments This wrk was supprted by Krea Science and Engineering (KOSEF) grant funded by Krean Gvernment (MOST) (N. ROA-2006-000-10442-0). REFERENCES 1. A. García, M. Llusar, J. Calb, M. A. Tena, and G. Mnrós, Lw-Txicity Red Ceramic Pigments fr Prcelainised Stneware frm Lanthanide Cerianite Slid Slutins, Green Chemistry, 3 [5] 238-42 (2001). 2. R. Munz, N. Mas, B. Julian, F. Marquez, H. Beltran, P. Escriban, and E. Crdncill, Envirnmental Study f Cr 2 O 3 Al 2 O 3 Green Ceramic Pigment Synthesis, J. Eur. Ceram. Sc., 24 [7] 2087-94 (2004). 3. R. A. Eppler, Mechanism f Frmatin f Zircn Stains, J. Am. Ceram. Sc., 53 [8] 457-62 (1970). 4. T. Demiray, D. K. Nath, and F. A. Hummel, Zircn-Vanadium Blue Pigment, J. Am. Ceram. Sc., 53 [1] 1-4 (1970). 5. M. Ocana and A. R. Gnzalez-Elipe, Spectrscpic Studies n the Lcalizatin f Vanadium(IV) in Vanadium Dped Zircn Pigments, J. Am. Ceram. Sc., 81 [2] 395-409 (1998). 6. G. Mnrs, J. Carda, M. A. Tena, and P. Escriban, Different Kinds f Slid Slutins in the V 2 -ZrSiO 4 -NaF System by Sl-Gel Prcesses and their Characterizatin, J. Eur. Ceram. Sc., 11 [1] 77-86 (1993). 7. C. A. Seabright, Yellw Pigments fr Ceramic Ware, US Patent 2,992,123 (1961). 8. E. Kat and H. Takashima, Study f Zircn Pigments- Vanadium Blue, Rep. Gv. Ind. Res. Inst, Nagya, 4 [2] 147-50 (1956). 9. M. Trjan, Synthesis f Yellw Pigments, Dyes and Pigments, 9 [4] 261-73 (1988). 10. M. Ocana, A. Caballer, A. R. Gnzalez-Elipe, and P. Tartaj, C. J. Serna, Valence and Lcalizatin in Pr-dped Zircn, J. Slid State Chem., 139 [2] 412-15 (1998). 11. M. Ocana, A. Caballer, A. R. Gnzalez-Elipe, P. Tartaj, C. J. Serna, and R. I. Merin The Effects f the NaF Flux n the Oxidatin State and Lcalisatin f Prasedymium in Pr-dped Zircn Pigments, J. Eur. Ceram. Sc., 19 [5] 641-48 (1999). 12. M. Shyama, H. Nasu, and K. Kamiya, Preparatin f Rare Earth-Zircn Pigments by the Sl-Gel Methd, J. Ceram. Sc. Jpn., 106 [3] 279-84 (1998). 13. M. Llusar, J. B. Vicent, J. Badenes, M. A. Tena, and G. Mnrs, Envirnmental Optimisatin f Blue Vanadium Zircn Ceramic Pigment, J. Eur. Ceram. Sc., 19 [15] 2647-57 (1999). 14. S. Parasuraman, Investigatin f Zircn and Cerium Sulphide Based Inrganic Pigments, pp. 17-32, Prject Reprt, Dept. Metal. Mater. Eng., India, 2003. 15. Y. Kann, Thermdynamic and Crystallgraphic Discussin f the Frmatin and Dissciatin f Zircn, J. Mater. Sci., 24 [7] 2415-20 (1989). 16. K. R. Pyn and B. H. Lee, The Influence f Firing Cnditins n the Clr Prperties f Pr-ZrSiO 4 Pigments Synthesized using Rice Husk Ash, J. Kr. Ceram. Sc., 46 [4] 397-404 (2009). 17. G. De A. Licciulli and M. Nacucchi, Unifrmly Dispersed Pr +3 Dped Silica Glass by the Sl-Gel Prcess, J. Nn- Crys. Slid., 201 [1] 153-58 (1996). 18. H. E. Hefdraad, Charge-Transfer Spectra f Tetravalent Lanthanide Ins in Oxides, J. Inr. Nucl. Chem., 37 [3] 1917-21 (1975). 19. D. Pawlak, Z. Frukacz, Z. Mierczyk, A. Suchcki, and J. Zachara, Spectrscpic and Crystalgraphic Studies f YAG:Pr 4+ Single Crystals, J. Ally. Cmp., 275 [2] 361-64 (1998). 20. D. De Waal, A. M. Heyns and G. Pretrius, Raman Spectrscpic Investigatins f ZrSiO 4 :V 4+, the Blue Zircn Vanadium Pigment, J. Ramans. Spec., 27 [4] 657-62 (1996). 21. V. Presser and C. Gltzbach, Metamictizatin in Zircn : Raman Investigatin Fllwing a Rietveld Apprach, J. Ramans. Spec., 40 [5] 499-508 (2009). w wz