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1 Jurnal f the Krean Ceramic Sciety Vl. 45, N. 5, pp. 268~275, Influence f CrCl 3 in Sphene-Pink Pigments Hyun-S Lee and Byung-Ha Lee Department f Materials Science & Engineering, Myngji University, Yngin , Krea (Received April 7, 2008; Accepted May 9, 2008) Sphene-Pink e CrCl 3 w x Á w w œw ( ; ) ABSTRACT In high temperature ceramic glazes, a stable range f pink-red clrs prducing -SnO 2 -CaO-SiO 2 pigments are factred by Cassiterite and Malayaite relatinship with. The experiment described the effect f CrCl 3 by adding H 3 B as a mineralizer t increase the frmatin f Malayaite crystal, substituting CrCl 3 instead f in pigment as a chrmphre. Synthesized pigments were analyzed by XRD, FT-IR, Raman Spectrscp, UV and UV-vis. The result shws the differences in amunt f crystal phases and xidatin state f Cr in, which causes the clr change. The melting pint f CrCl 3 is lwer than which act as a mineralizer and makes the pigment synthesized in lwer temperature at 1200 C. Hlding 3 h firing at 900 C where the synthesize frms shws better effect f Malayaite crystal phases and increasing engaged effect f CrCl 3 where the clr pigmentatin is mre defined then in. Key Wrds : Malayaite, Sphene, CrCl 3, Pigment 1. -SnO 2 -CaO-SiO 2 Sphene pink š w pink-red ùkü x š. SnO 2 -CaO-SiO 2 š g w w ƒw purple l pink-red¾ w ùkù w š ƒ Cassiterite(SnO 2 ) Malayaite(CaSnSiO 5 ) š. p 1) Malayaite ƒ š pink-red w öe. š Cr(III) Cr(IV)ƒ y x. Cr y k ƒ y w w. 2) w Cr CrCl 3 w, CrCl C û 1150 C, CrCl 3 w û w, š Cr y kƒ. CaCr Sn SiO 5-2 (wt%)h 3 B» Crrespnding authr : Hyun-S Lee Tel : Fax : CrCl 3 w w š w. p Malayaite CrCl 3 š z wš Ÿy y e ùkü. 2. x 2.1. ƒ CrCl 3 z Malayaite Cr š z» w CrCl 3 w. CrCl 3 ey Malayaite CaSnSiO 5 w š ùkù 0.02 mle 3) CrCl 3 eyw w. ƒ Table 1 ùkü Ÿy ƒ y z ƒ e Ÿy w» w Table 1 L2 O2 ƒ H 3 B y w w. y Table 2 ùkü. Table 1 2 w 900 C¾ 5 C/ min, š ¾ 3 C/min g ƒ ƒ 1200 C, 1300 C 2 w. w 268

2 Sphene-Pink e CrCl 3 w 269 Table 1. Cmpsitin f Samples with and CrCl 3 Sample Cmpsitin L2 L4 O2 O4 CaCr 0.02 Cl 3 Sn SiO 5-2 (wt%)h 3 B CaCr 0.04 Cl 3 Sn 0.97 SiO 5-2 (wt%)h 3 B CaCr 0.02 Sn SiO 5-2 (wt%)h 3 B CaCr 0.04 Sn 0.97 SiO 5-2 (wt%)h 3 B Table 2. Samples Adding Different Amunt f H 3 B Sample Cmpsitin LH2 CaCr 0.02 Cl 3 Sn SiO 5-2 (wt%)h 3 B LH4 CaCr 0.02 Cl 3 Sn SiO 5-4 (wt%)h 3 B LH6 CaCr 0.02 Cl 3 Sn SiO 5-6 (wt%)h 3 B OH2 CaCr 0.02 Sn SiO 5-2 (wt%)h 3 B OH4 CaCr 0.02 Sn SiO 5-4 (wt%)h 3 B OH6 CaCr 0.02 Sn SiO 5-6 (wt%)h 3 B w (Duksan, 99%), CrCl 3 (Junsei, Extra pure), SnO 2 (Junsei, Chemial pure), H 3 B (Duksan, 99.5%) w. w XRD, FT- IR w z z 6wt% ƒw y» 1260 C 1 w. w UV UV-vis w y ùkü y z Malayaite 800 C w» w, DTA d ùkù CrCl 3 ey 720 C, ey 740 C. š ƒƒ 800 C, 870 C w w ùkû. CrCl 3 eyw û ù ƒ Malayaite ƒ Cr š j» w y. y Table 3 ùkü w z 6wt% ƒw y» 1260 C 1 w z UV UV-vis w Fig. 1. XRD Patterns f samples L2 and O2 as Table 1, fired at 1200 C/ 2 h, 1300 C/ 2 h. y ùkü. z seger ùkü KNaO CaO Al SiO 2 (1) MgO 3. š 3.1. ƒ CrCl 3 z Malayaite w Chrmium š z» w Table 1 L2, O2 ey CrCl 3 w. w ƒƒ 1200 C 1300 C 2 w. w XRD Fig. 1 Fig. 2 ùkü Fig. 3 FT-IR ùkü. Fig. 1 XRD ùkù Cassiterite Malayaite Cristbaliteƒ œ w. w z Malayaite 1200 C w ƒ ey O2 ù 1300 C w j. 2θ w Malayaite Cassiterite Table 3. Cmpsitin f Samples with Varius Firing Schedule N0. Cmpsitin Firing Schedule LM-0 CaCr 0.02 Cl 3 Sn SiO 5-2 (wt%)h 3 B 900 C/0 h-1200 C/2 h LM-3 CaCr 0.02 Cl 3 Sn SiO 5-2 (wt%)h 3 B 900 C/3 h-1200 C/2 h LM-6 CaCr 0.02 Cl 3 Sn SiO 5-2 (wt%)h 3 B 900 C/6 h-1200 C/2 h OM-0 CaCr 0.02 Sn SiO 5-2 (wt%)h 3 B 900 C/0 h-1200 C/2 h OM-3 CaCr 0.02 Sn SiO 5-2 (wt%)h 3 B 900 C/3 h-1200 C/2 h OM-6 CaCr 0.02 Sn SiO 5-2 (wt%)h 3 B 900 C/6 h-1200 C/2 h 45«5y(2008)

3 270 x Á w Fig. 2. d value changes f Malayaite and Cassiterite phases by temperature (fired at 1200 C/ 2 h, 1300 C/2 h) based n XRD fr samples L2 and O2. š k 2θ ë d y. Cr(III) 0.69(Å), Cr(IV) 0.55(Å) Sn(IV) 0.83(Å) ü Sn 8 Cr ey ù4) 2θ f š d. d y Malayaite 2θ=28.11 ~ (2 0 0) Cassiterite 2θ=26.28 ~ (1 0 0) d w t CaF 2 (1 1 1) ùkù d» w. (d= Å) Table 1 ùkü L2 O C 1300 C z ƒ d y Cr š k ùkü. Fig. 2 ù kü. w w w O2 ƒ 1300 C Cassiterite d Cr š š Malayaite š. CrCl 3 w w w L2 ƒ 1300 C Cassiterite d yƒ š y š, Malayaite d f Cr š w ùe Fig. 3. FT-IR analysis f samples L2 and O2 as Table 1, fired at 1200 C/ 2 h, 1300 C/ 2 h. ùkû., eyw 1300 C š, ƒ Cr Cassiterite š ùkû. CrCl 3 eyw ƒ 1300 C ü š w w w 1200 C ùkû. Fig. 1 XRD Malayaite š w ù Fig. 2 ùkü d Malayaite Cr š k û w CrCl 3 w z ùkû. Fig. 3 FT-IR 1 spectra 523, 575, 696, 804, 875, 927 cm ùkù Malayaite 5,6) 1300 C w O C w L2 ƒ j peak w ƒ. L C w Malayaite ƒ û Fig. 2 d y ew Ÿy ƒ yz Sphene pink w e Malayaite w CrCl 3 w û w ù. w j» w Ÿy H 3 B ƒ y w w. w z Malayaite Cassiterite y d wš š Cr w ùkù w. Table C 2 w w w z XRD d w Fig. 4 ùkü. Fig. 4 XRD Ÿy ƒ ƒ j w w, ƒ 6wt% Malayaite w. w» w z 6wt% ƒw y» 1260 C w wz

4 Sphene-Pink e CrCl 3 w 271 Fig. 4. XRD patterns f samples LH2, LH4, LH6 and OH2, OH4, OH6 as Table 2 at 1200 C/2 h. Fig. 5. CIE L*a*b* clurimetrics parameters f pigment and glazed samples at 1200 C/2 h as Table 2 (LH2, LH4, LH6 and OH2, OH4, OH6). 1 w. UV UV-vis d w Fig. 5 CIE L*a*b* Fig. 6 UV-vis Spectra ùkü. UV d (Fig. 5) CrCl 3 w y w w ùkû. w b* ƒ û ùk ù LH2ƒ ƒ ùkü. ƒ w a* f ƒ b* kw, H 3 B w z L* f. Fig. 6 ùkù UV-vis d w CrCl 3 eyw eyw. Malayaite 7) 520 nm ùkù Tanabe-Sugan diagram, 3 A 2g (F) 3T 1g (F) w 2,8) eyw OH j ù z LH2 ƒ j ùkû. H 3 B w 2wt% ƒ LH, OH ƒ û w Ÿy ƒ ƒ w ƒ y CrCl 3 w w» w Cr w ƒ k Table 1 L4, O C¾ DTA d w. Fig. 7 DTA w CrCl 3 ƒ ey L4ƒ û w ù» w. Malayaiteƒ» w 45«5y(2008)

5 272 x Á w Fig. 6. UV-vis spectra f pigment and glazed samples at 1200 C/2 h as Table 2 (LH2, LH4, LH6 and OH2, OH4, OH6). Fig. 7. DTA spectra f pigment L4, O4 as Table 1. Fig. 8. XRD patterns f Table 2 with different maintaining time as Table 3 at 1200 C/2 h. w wz

6 Sphene-Pink e CrCl 3 w 273 Fig. 9. FT-IR analysis f samples LM-0, LM-3, LM-6 and OM- 0, OM-3, OM-6 as Table 3 at 1200 C/2 h. Fig. 10. Raman spectrscpy analysis f samples LM-0, LM-3 and OM-0, OM-3 as Table 3 at 1200 C/2 h. 800 C 3) w L4 O4 û ùkù j ù.» w Cr š jš w ù» w z, 900 C ƒƒ 0, 3, 6 j w y. y Table 3 ùkü. Table 3 y w w XRD d Fig. 8 ùkü. ƒ ey OM-0ƒ ƒ Malayaite wš, CrCl 3 ƒ ey 900 C 3 k LM-3ƒ ƒ. w Ÿy ƒ y ƒ CrCl 3 ƒ ey w w s ùkû. FT-IR d (Fig. 9) Malayaite Cr š ùkù LM-3ƒ 400, 550, 638, 852 cm 1 ƒ j. p 477, 800 cm 1 Cr(III) w 5) Om-0, LM-0 š Cr Cr(III)ƒ w ùkû. 705 cm 1 Cr(IV) w 5) w ¼ j peak Cr y w ùkû. Raman spectrscpy d (Fig. 10) x w w ùkù peak w 3 k LM-3 x Ÿ(flurescence) w k ƒ j ùkþ. w LM-3 ƒ Fig. 9 FT-IR Fig. 11 ùkü UV-vis ew. Fig. 11 z ùkù UV-vis spectra w w ùk Fig. 11. UV-vis spectra f samples LM-0, LM-3, LM-6 and OM-0, OM-3, OM-6 as Table 3 at 1200 C/2 h. 45«5y(2008)

7 274 x Á w Fig. 12. CIE L*a*b* clurimetrics parameters f pigment and glazed samples as Table 3. ü. Cr Cr(III) Cr(IV)ƒ wì w. 2) UV-vis d 520 nm ùkù Malayaite š Cr(IV) w w 2,8). w w, p LM-0 Malayaite Tanabe-Sugan diagram 3 A 2g (F) Cr(IV) w ùkù 520 nm 3 T (F) 2,8) 1g 4 A 2g 4 T 1g (F), 4 4 A 2g (F) T 2g, 4 A 2g 4T 7,9) 1g (F) w 380, 420, 600 nm ùkù Cr(III) w 2,8) w ü š Cr(III). y k LM nm ƒ w ùkù š Cr(IV). OM 740 nm Cassiterite š Cr(III) w 2,8) eyw Cassiterite š Cr(III). LM nm Cr(IV) w 2,8)ƒ w 380 nm Cr(III) 7,9)ƒ ƒ ùkù š Cr(IV) ùkþ. UV d (Fig. 12) eyw OM Fig. 10 Fig. 11 y yƒ j j y. z ùkù ¼ L* f w b* û š Cr(IV) w ùkû. Fig. 11 UV-vis ƒ CrCl 3ƒ ey w w ƒ f. LM-3 Malayaite Cr(IV) w ƒ j w ùkû. 4. -CaO-SnO 2 -SiO 2» w pink-red CrCl 3 w w ùkù. 1. CaCr 0.02 Sn SiO 5 CrCl 3 w Malayaite š z ƒ w 1200 C û. 2. Ÿy H 3 B ƒ 2wt%. ƒ ƒ Malayaite ƒwù 6wt% Malayaite wš w. 3. Sphene-pink w CrCl 3 w w y» 900 C C 2 ùkû. Malayaite ƒ š ƒ Malayaite û (1200 C) Cr(IV) w š w z j w. 4. w CrCl 3 eyw w ƒ ûš wù j w w s. Acknwledgment 2007 ( w» ) w w w. (N. R0A ) REFERENCE 1. E. Lpez-Navarretea, A. Caballera, V. M. Orerab, F. J. Lzarb, and M. Ocaa, Oxidatin State and Lcalizatin f Chrmium Ins in Cr-dped Cassiterite and Cr-dped Malayaite, J. Acta Mat., 51 [8] (2003). w wz

8 Sphene-Pink e CrCl 3 w G. Mnr s, H. Pint, J. Badenes, M. Llusar, and M. A. Tena, Chrmium(IV) Stabilizatin in New Ceramic Matrices by Cprecipitatin Methd: Applicatin as Ceramic Pigments, Z. Anrg. Allg. Chem., 631 [11] (2005). 3. H.-S. Lee, and B.-H. Lee, Cluring Effect f Malayaite Frmatin and Synthesis Sphene-Pink Pigment, J. Kr. Ceram. Sc., 45 [3] (2008). 4. EUG Crdncill, FUG del Ri,G JUG Carda, MUG Llusar, and PU Escriban,G Influence f Sme Mineralizers in the Synthesis f Sphene-Pink Pigments, J. Eur. Ceram. Sc., 18 [8] (1998). 5. FUGJUGBerry, NU Cstanatini, and LUGEU Smart Synthesis f Chrmium-cntaining frm Pigment Chrmium Recvered frm Leather Waste, J. Waste Management, 22 [7] (2002). 6. NU TU McDevitt and WU LU Baun, Infrared Absrptin Study f Metal Oxides in the Lw Frequency Regin ( cm l ), J. Spectrchimica Acta., 20 [5] (1964). 7. BUG Julián, HUG Beltrán, EUG Crdncill, PUG Escriban, JUG VU Flgad, MUGVallet-Reg, and RUGPUGdel Real, A Study f the Methd f Synthesis and Chrmatic Prperties f the Cr- SnO 2 Pigment, Eur. J. Inrg. Chem., [10] (2002). 8. A. Dmnech, F. J. Trres, E. R de Sla, and J Alarcn, Electrchemical Detectin f High Oxidatin States f Chrmium(IV and V) in Chrmium-Dped Cassiterite and Tin- Sphene Ceramic Pigmenting Systems, Eur. J. Inrg. Chem., (2006). 9. PUG LU Escriban,G CUG MU Guillem, and JUG NUG Alarcn,G Cr- SnO 2 -CaO-SiO 2 - Based Ceramic Pigments, Am. Ceram. Sc. Bull., 63 [12] (1984). 10. G. Csta, M. J. Ribeir, J. A. Labrincha, M. Dndi, F. Matteucci, and G. Cruciani, Malayaite ceramic pigments prepared with galvanic sludge, Dyes and Pigments, 78 [2] (2008). 11. XUGFaure, AUGVanderperre, and PUGClmban, Pink Pigment Optimizatin by Resnance Raman Spectrscpy, J. Raman spectrsc., 34 [4] (2003). 12. F. M. Filh, A. Z. Simes, A. Ries, L. Perazlli, E. Lng, and J. A. Varela, Dependence f the Nnlinear Electrical Behavir f SnO 2 -based Varistrs n Additin, Ceram. Int., 33 [2] (2007). 13. E. Lpez-Navarrete and M. Ocaa, A Simple Prcedure fr the Preparatin f Cr-dped tin Sphene Pigments in the Absence f Fluxes, J. Eur. Ceram. Sc., 22 [3] (2002). 14. E. Lpez-Navarrete, A. R. Gnzlez-Elipe, and M. Ocaa, Nn-cnventinal Synthesis f Cr-dped SnO 2 Pigments, Ceram. Int., 29 [4] (2003). 15. IUG Ayub, FUG JUG Berry, CUG Jhnsn, DUG A. Jhnsn, EUG A. Mre, XUGRen, and HUGMUGWidatallah, Tin-, titanium-, and magnesium-dped a- : characterizatin and ratinalizatin f the structures, Slid State Cmmunicatins, 123 [3-4] (2002). 16. M. A. Tena, S. Meseguer, C. Gargri, A. Frs, J. A. Badenes, and G. Mnrs, Study f Cr-SnO 2 Ceramic Pigment and f Ti/Sn Rati n Frmatin and Clratin f these Materials, J. Eur. Ceram. Sc., 27 [1] (2007). 45«5y(2008)