Jurnal f the Krean Ceramic Sciety Vl. 7, N. 6, pp. 603~607, 00. DOI:0.9/KCERS.00.7.6.603 Synthesis and Frmatin Mechanism f Cbalt Dped Willemite Blue Pigments Dng-Ha Hwang, Han Kyng-Sp, and Byung-Ha Lee Department f Material Science & Engineering, Myngji University, Yngin 9-78, Krea Divisin f Material Science, KIST, Seul 30-650, Krea (Received July, 00; Revised August, 00; Accepted September, 00) C-Dped Willemite q w» y wáw Á w w œ w œw w w» (00 7 ; 00 8 ; 00 9 ) ABSTRACT Turquise blue pigment f Vanadium-zircn blue (DCMA number --), which was already cmmercialized, was stable t be reprduced but insufficient t give strng blue. Hwever, it pssible t btain mre intense blue by partially substituting cbalt ins int the willemite(zn ) lattice classified int DCMA number 7-0- fr blue ceramic pigment. By the cmpsitin f willemite C x Zn -x (X=0.0, 0.03, 0.05, 0.07, 0.09 mle), this study used reagent grade zinc xide, cbalt xide and silicn dixide as starting materials, carrying ut the synthesis with slid reactin methd by adding H 3 as a mineralizer. The firing temperature was between 00 C and 00 C. The characteristics f synthesized pigment were analyzed by X-ray diffractin, Raman spectrscpy and SEM and the characteristics f clr tnes were analyzed by UV-Vis spectrscpy and CIE-Lab measurement. As a result, the ptimal cmpsitin was Zn.95 C 0.05 with wt% f H 3 as a mineralizer and firing cnditin was 350 C/3 h. Lab value was 9.5,.03, -59.93 fr n glaze pigment and 37.03, 36., -60.03 fr under glaze pigment. Key wrds : Willemite, C x Zn pigment, Clr prperties, Blue ceramic pigment. x š yw q q(856 ) w z 9» z w ú. j y ) š, w w w z w w. 9» ) w q» Prussian blue( y77), Cbalt vilet( 800), Cbalt blue(w 80), Cbalt vilet( y859).» 3) ( ),» ( ), wz ( w ), z ( ) š. ) DCMA(Dry Clr Manufacturers Assciatin)System w y w x» blue C-Al, C-Zn-Al, Spinel C-Zn- Crrespnding authr : Byung-Ha Lee E-mail : sdyh85@hanmail.net Tel : +8-3-330-66 Fax : +8-3-330-657 Si Willemitex š ƒ. 5) Willemite(Zn ) xÿ ù glass ceramic,»,, ƒ 5,6) š w ³ Zn in + tetrahedral e 3/8 w phenacite grup rthsilicate w. C ƒw 7) willemite š Zn in + tetrahedral e C in w + w, ww. 8) willemite ZnO CO e yw z wz w Willemite (Zn ) q w wš w.. x.. Zn w w» w C x Zn -x ww. w C 3 O (Cbalt(II,III) Oxide, Duksan), ZnO(Zinc Oxide, Duksan), 603
60 y wáw Á w Table. Cmpsitins f Samples with CO (mle) Sample Cmpsitin W HW HWC HWC HWC3 HWC HWC5 Zn Zn Zn.99 C 0.0 Zn.97 C 0.03 Zn.95 C 0.05 Zn.93 C 0.07 Zn 0.99 C 0.0 SiO (Silicn Dixide, Junsei) w. Table W ww p g š k z, ƒ 00, 50, 300, 350, 00 C w. w w» w Ÿy 9) Bric Acid,, 3, wt% ƒw 350 C 3, 6, 9,, 5, 8 yw. q» w Table CO 0.0, 0.03, 0.05, 0.07, 0.0 mle y. Table ùkü. 900 C¾ 5 C/min, š 350 C¾ 3C/min 3 w z þƒw... p» w X z (X-ray Diffratmeter, XRD-7000, shimadzu, Japan) w w š, w ü š» w Raman spectrscpy(lanbda slutins, Inc., U.S.A)RP 53-US w w. w x j»» w SEM(scanning electrn micrscpy, ss-550, shinadzu, Japan) w w. d UV-vis Spectrphtmeter (0-pc, shimadzu, Japan) w d w, (Muncell) t 0) (H:hue), (V:value), (C:chrma) CIE-L a b ùkü. x r d ww..3.» w z () z wz () z w. Lime barium Glaze 0.3 KNaO 0.5 CaO 0.873 Al O 3.6579 SiO () 0. BaO 0. MgO Fig.. XRD patterns f samples synthesized at 00, 50, 300, 350, and 00 C/3h. Lime zinc Glaze 0.09 K O 0.0 Na O 0.390 CaO 0.873 Al O 3.6579 SiO () 0.0089 MgO 0.539 ZnO z (ver glaze stain) z w xr z 70 C w 3 w z þƒw. wz (under glaze stain) xr, w z, z w z 60 C 30 w z þƒw. 3. š 3.. XRD Table W ww sample w willemite peak» w 00, 50, 300, 350, š, 00 C¾ w. XRD Fig. ùkü. Ÿ y w š willemite w w 00 C 3 w z w. w û š, g» w Ÿy 9) H 3,, 3, wt% ƒw 350 C 3 w Fig.. Ÿy wt% š w z Table Zn C eyw 350 C 3 w þƒw. w willemite C š» w XRD w wz
C-Dped Willemite q w» 605 Fig.. XRD patterns f samples synthesized at 350 C/3 h with (b), (c), (d) 3, and (e) wt/% f mineralizer. Fig. 3. XRD patterns f samples synthesized at 350 C/3 h with (b) 0.0, (c) 0.03, (e) 0.05, (f) 0.07, and 0.0 mle f CO. w + Zn 0.07(Å) + C 0.07(Å) w XRD š. Fig. 3 ùkü. 3.. Raman spectrscpy Willemite C š» w Raman spectrscpy w. Fig. (a) CO 0.0 mle ey¾ - 395, 870, 905, 95 cm willemite p )ƒ ùkû. ù, CO ey - 95 cm ùkù willemite p peak wš CO š w shiftƒ d û. š, COƒ 0.07 mle eyw Fig. (b) HWC š CO w CO p peak ùkû. willemite CO eyw š w 0.05 mle. 3.3. SEM w x» w SEM w. Willemite (hexagnal) w HWC3 xk Fig. 5 ƒx 5~7 µm ùkû. 3.. d w ƒƒ» z z 70 C/ h w š wz w 60 C/30 min w. w xr UV-vis spectrmeter(0-pc, shimadzu, Japan) d w Fig. 6 ùkü. q 3d xk C(II) x 7 Fig.. Raman spectrscpy analysis f samples fired at 350 C/3 h. 7«6y(00)
황동하 한경섭 이병하 606 Fig. 5. SEM analysis f HWC3 sample fired at 350 C/3 h. Fig. 7. CIE Lab clurimetric parameters f samples fired at 70 and 60 C/30 min. Fig. 8. Fig. 6. Optical absrptin spectra f under glaze(xidatin firing) at 60 C/30 min and ver glaze at 70 C/ h samples fired at 350 C/3 h and 350 C/6 h. 은 3개의 spinallwed 전이를 보여 준다. 사면체 리간드 장 에서의 C에 관한 spinallwed 전이는 다음과 같다. V : A (F) T (F) V : A (F) T (F) V : T (F) T (P) 이 3개의 밴드는 Bamfrd 에 따르면 Jahn-Teller 구조 로부터 일그러짐에서 기인하고 Bates 에 따라서 L과 quantic numbers 사이에 상호 작용에 따른다. 그런 까닭 에 높은 파장대(50~60 nm)에서 세 번째 spin-allwed 전 이의 이동은 스펙트라의 비대칭성 결정모양과 함께 적외 선에서 한 개의 밴드 또는 두 개 밴드의 CO 배위 사면 체와 팔면체를 구별하는데 사용 할 수 있다. Visible 범위에서 높은 파장대에 V 밴드의 C(II)의 면 체 배위 willemite 구조가 확립된다. UV-vis 측정결과 willemite가 안정하게 생성된 HWC3(350 C/3 h) 조성에서 3 ) 3) ) 7) 3 한국세라믹학회지 Clring results f under glazed and ver glazed samples fired at 70, 60 C/ h (a) CO-0.03 mle/ 3 h, (b) CO-0.05 mle/3 h, and (c)co-0.05 mle/6 h (xidatin firing). CIE-Lab Clurimetric Parameters f Samples (a) Over Glaze Stain, (b) Under Glaze Stain (Oxidatin Firing) Sample Applicatin L a b -9.99.55 HWC-3 h 3.6-59.93.03 HWC3-3 h (a) 9.5-59.83.5 HWC3-6 h 7.83-6.03 3.7 HWC-3 h.39-60.03 36. HWC3-3 h (b) 37.03-5. 9.30 HWC3-6 h 0.5 Table 3. 합성된 안료에서 나타내는 50 nm, 590 nm 그리고 60 nm 의 흡수밴드는 Tanabe-Sugan diagram, A (F) T (F)에 의 한 것으로 willemite 결정의 주 발색요인으로나타났다. 또한, UV분석 결과 Fig. 7과 Fig. 8 그리고 Table 3에서 와 같이 상회 안료에 적용된 발색결과 L 값이 9.5으로 5-7)
C-Dped Willemite q w» 607 ƒ ûš a.03 b -59.93 q ƒ ùkù w q. wz L 37.03, a 36., b -60.03 z w q. z Fig. 8 ùkü.. ZnO SiO w Willemite w w Ÿy H 3 wt%ƒ, w 350 C 3 w w. Willemite ZnO CO ey w, š 0.05 mle. 5% ƒw z wz w L, a, b z 9.5,.03, -59.93 w z 37.03, 36., -60.03 q ùkü. Acknwledgment 009 ( w» ) w w w. (N. ROA-006-000-0-0) REFERENCES. M. S. H. Katu, A Study n the Synthesis f Red Ceramic Pigments, Nagya Institute f Technlgy, Reprt N. 88, Nagya, 000.. U. G. Ime, A Study n the Internatinalizatin f Traditinal Techniques Krea:Pttery (in Krean), G pp. -3, Natinal Research Fundatin f Krea,G Seul, 99. 3. K. M. Lee, Intrductin f Pigment, pp. -30,G Krea Plastic Technical Infrmatin Centet,G Seul, 989.. R. A. Eppler, Classificatin f Mised Oxide Inrganic Pigments, J. Am. Ceram. Sc., 6 [9] 00-3 (983). 5. G. T. Chandrappa, S. Ghsh, and K. C. Pattil, Synthesis and Prperites f Willemite, Zn, and M + : Zn (M=C and Ni), J. Mater. Synth. Prcess., 7 [5] 73-79 (999). 6. S. G. Sn, J. H. Lee, J. M. Lee, and Y. D. Kim, Lw Temperature Synthesis f Willemite Pwder (in Krean), J. Kr. Ceram. Sc., 5 [7] 0- (008). 7. G. N. Maslennikva, N. P. Fmina, and A. I. Glebycheva, Study f the Effect f Substitutin f SiO by SnO, TiO, f ZrO in Pigments, Stekl i Keramika, 7 [8] 8-30 (976). 8. A. Fres, M. Llusar, J. A. Badenes, J. Tena, M. A. Tena and G. Mnrs, Cbalt Minimizatin in Willemite(C x Zn -x ) Ceramic Pigments, Green Chem., 93-00 (000). 9. J. K. Lee, J. O. Kim, Y. H. Baek, J. S. Lee, B. H. Lee, and D, W. Shin, Ceramics Raw Materials, pp. 3-, Inf. Tech. Cr., Seul, 967. 0. S. N. Lee, S. C. Nh, and S. G. Kim, Clrimetric Analysis and Matching the Ntin f the Munsell System fr Reprduced Clrs with Variable Dt Area Rates (in Krean), Pukyng Natinal University, Pusan, 3 [] 89-53 (98).. D. D. Waal, Micr-Raman and Prtable Raman Spectrscpic Investigatin f Blue Pigments in Selected Delfts Plates (7-0th Century), J. Raman Spectrscpy., 0 6-70 (009).. C. R. Bamfrd, phys. The Aplicatin f the Ligand Field Thery t Clured Glasses, Chem. Glasses., 3 [6] 89-0 (96). 3. M. C. Wittels, Mdern Aspects f the Vitreus State, J. Phys. Chem. Sl., 3 [5] 95-5 (960).. F. Crma and V. Lambies, Investigatin f Sme Inrganic Pigments f C(II), J. Rev. de Chim. Minre., 7 0-7 (980). 5. F. A. Cttn and G. Wilkinsn, Advanced Inrganic Chemistry; pp. 6-68, Inc. 3rd ed., Jhn Wiley & Sns, New Yrk, 97. 6. J. Fergusn, D. L. Wd, and L.G. Uitert, Crystal-Field Spectra f d 3,7 Ins. V. Tetrahedral C + in ZnAl O Spinel, J. Chem. Phy., 5 90-0 (969). 7. T. C. Brunld, H. U. Gudel, and E. Cavalli, Absrptin and Luminescence Spectrscpy f Zn Willemite Crystals Dped with C +, J. Chem. Phy. Lett., 5 [] -0 (996). 7«6y(00)