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1 Jurnal f the Krean Ceramic Sciety Vl. 44, N. 5, pp. 60~65, 007. Develpment f Black Clr Spinel Pigment fr High Temperature Kwang-H Lee, Min-S Myung, and Byung-Ha Lee Department f Ceramic Engineering, Myungji University, Yng-In , Krea (Received March 5, 007; Accepted May 15, 007) š v ŸyÁ Á w w œw ( ; ) ABSTRACT This research studied the mst suitable synthesis cnditin f mineral pigments f black spinel, which have a stable chrmgenic characteristic als ata high temperature f 1400 C (it is nt currently prducedin the cuntry) t meet nt nly functinality f ceramics but als an individual s aesthetic. It was synthesized by the plastic synthetic methd n the basis f basic frmatin f Fe, Cr, Quartz, Kalin, CO, MnO, and plasticity was made at 1500 C, 1550 C, 1600 C, 1650 C. We researched the mst suitable cnditin f plasticity and cmpsitin which make crystallizatin f spinel system and chrmgenic characteristic clse t black in every cmpsitin. And fr the experiment f applicatin t Zircnia, after adding synthesized pigments t Zircnia and plasticizing them, we analyzed their clr and prperty f matters. The mst suitable synthesis cnditins f mineral pigments f black spinel system require cmpsitin f Fe -3.01%, Cr %, Quartz-9.66%, Kalin-18.53%, CO-3.71%, MnO -5.6% and cnditin f plasticity kept fr 1 h at 1600 C. When we added pigments synthesized in this way t Zircnia with 5 wt% and plasticized them at 1410 C, the result was that the degree f strength-3.6 kgf/mm, absrptance-0.108%, luminsity-l*:37.54, clr-a*:1.31, b*:.61 and their use suited fr artificial jewelry r decratin Zircnia gds. Key wrds : Black clr, Pigment, Spinel, Zircnia 1. w ü, ü, ü w ƒ š» t y š.» š w w k ƒ t w. 1) w w ƒƒ š œ t š. ) p w», yw p w w ùkü» w v. œ ƒ š š š w š» š w» w Õ w p. y š š ƒ Crrespnding authr : Byung-Ha Lee lbh@mju.ac.kr Tel : Fax : w spinel x w ƒ. q ƒw» œ š w» w spinel ƒ ww. 5) Spinel» w w ƒ» y, y š m ³ w yww z» w w t w ƒ. w, x ü š 1300 C w ùküš š v w t w» w, š w š š w ƒ v w. zircnia alumina š w» p j t t ƒ w ùkü» w y 1400 C š w w š spinel w ³ wš w. 60

2 . x.1. spinel C š w w spinel» w w» w» Fe, Cr, ³, Kalin, CO, MnO w. x w Fe, Cr, MnO (Duksan, Krea, 99%), CO(Junsei, Japan, 99%) ü q š w š, Kalin w š m œ, ³ ( ) œ w Kalin ³ Table w w ³ w» w w Y. Shirakiƒ» w. 4) w Y. Shiraki w kalin ³ CO w w š Fe Cr 1:1mle ƒ w. w ƒƒ ƒ spinel w e w» w Table ww. Table x Spinel w Table BP 1 w MnO ~8% y g.(table 3) w Table 4 ùkü Table 3 BM 4 w ³ 16.6~0¾ y g x ww. w w ƒƒ y e w k ƒw ywwš Dry Oven 60 C w. yw z» w 35 mm Diskx š v 61 Table 1. Cmpsitins f Kalin and Silica Supplied by Hanheung Kalin C. and Puye Material C. SiO Al Fe MgO CaO Na O K O P O 5 TiO MnO Hanheung Kalin Pu Ye Quartz Table. Cmpsitins f Black Clr Spinel Pigment Cmpsites Fe Cr Pu Ye Quartz Hanheung Kalin CO MnO BP BP BP BP BP w ƒ x xw. Super Kanthal Furnace w 700 C ~ 1650 C¾ 50 C w. 900 C¾ 5 C/min, z š ¾ 3 C/min g, š 1 k z þw p Tables, 3, 4 w yww z y» w DT-TGA ww. w w UV-vis Spectrmeter(UV-401PC, Shimadzu, Japan) w z(cie: Cmmissim Internatinale de I Eclairage) t (L *, a *, b * ) d w. CIE-L *, a *, b t * * L, (L =100) * (L =0) * ùküš, a* ( a * ) (+a ) ùkü * *, b ( b ) y * Table 3. Cmpsitin f BP 1 by Changes MnO Fe Cr Pu Ye Quartz Table 4. Cmpsitin f BPM 4 by Changes Pu Ye Quartz Fe Cr Pu Ye Quartz Hanheung Kalin Hanheung Kalin CO MnO BM BM BM BM BM BM BM CO MnO BPP BPP BPP BPP BPP BPP BPP BPP BPP «5y(007)

3 6 ŸyÁ Á w Table 5. Measurement Cnditin f XRD Scan range Theta 10 ~70 Scan speed 10 (deg/min) X-ray target Cu X-ray vltage & current 30 kv(15ma) (+b ) ùkü * w. 700 C~1650 C w y w» w xr w 00 mesh w m g. XRD(X-Ray Diffractmeter, XRD- 7000, Shimadzu, Japan) w w XRD Table 5... w Zircnia x..1. xr w Zircnia ƒw Zircnia t w» w Zircnia ƒƒ 5wt% ƒw k wì yww. w Zircna t,,,» w ƒƒ 35 mm Diskx, mm barx, 17 mm diskx w ƒ x w xr w. Silicnite Muffle Furnace 1410 C w. 900 C¾ 5 C/min, z 1410 C¾ 3C/min g, 1410 C 1 k z þw. 3)... p w xr x UV-vis Spectrmeter(UV-401PC, Shimadzu, Japan) w d w. 3 UTM(Universal Testing Machine : Ez Test, Shimadzu, Japan) w 0.5 mm/min KS 1591 d» d w š, KSL 3114 w d w. 3. š 3.1. Spinel w DT-TGA Fig. 1 Tables, 3, 4 DT-TGA. y w ù BP 1 yw w ùkü. 400 C~1100 C j s peak k w peak spinel Cr 1.3 Fe 0.7» w peak XRD y» w BP 1 yw 700 C, 1000 C, 1150 C, 1400 C, 1500 C, 1550 C, 1600 C, 1650 C 1 w XRD w. Fig. 700 C w Cr, Fe quartz peak w C l spinel» w 1150 C l 1550 C¾ Cr 1.3 Fe 0.7 w ƒ 1600 C l spinel ë 1600 C z l spinel cristbalite. 6) spinel w w» w 1600 C ƒ v w w w kaline ³, MnO w Spinel w spinel v w mineralizer Fig. 3 Table ƒ 1600 C w z y XRD mw ùkü. cristbalite peakƒ w. w w BP 1 wš Cr peak Fig. 1. TG-DTA curve f black clr spinel pigment cmpsitin. w wz

4 고온용 검정색 스피넬 안료의 개발 Fig XRD patterns f Table 3 cmpsitin added MnO ~ 8% calcined at 1600C. 하였다. 이것으로 단일상의 spinel 안료를 합성하기 위해 서는 Fe O, Cr O, 규석, Kalin, CO, MnO 를 모두 사 용하여야 함을 알 수 있다. 또한 미 반응된 cristbalite 가 존재하지 않게 하기위해서는 mineralizer로 작용하는 MnO 의 양을 변화시켜 볼 필요가 있음을 알 수 있다. 그 래서 Table 의 BP 1 조합에서 다른 원료의 조성은 고정 한 후 MnO 의 함량만을 Table 3에서와 같이 %에서 8% 까지 변화시켜 보았다. Table 3의 안료 조합들을 1600 C에서 1시간 소성한 후 생 성된 결정상을 분석하기 위하여 XRD 분석하였으며 그 결 과를 Fig. 4에 나타내었다. 그 결과 전조성에 걸쳐서 미 반 응 Cr Fe O 의 결정은 존재하지 않았으나 BM 1~BM 5 의 조성에서 미 반응 cristbalite peak가 존재하였다. 그러 나 MnO 가 7%이상 첨가된 BM 6과 BM 7의 조합에서는 미 반응 원료는 존재하지 않고 spinel의 단일상만 존재하였다 ) Fig.. XRD patterns f BP 1 cmpsitin at varius calcinatin temperature Fig. 3. XRD patterns f Table cmpsitin calcined at 1600C. Fig. 5. UV analysis f Table 3 cmpsitin. 제 44 권 제 5호(007)

5 64 ŸyÁ Á w Fig. 6. XRD patterns f Table 4 cmpsitin added quartz 16.6 ~ 0% calcined at 1600 C. w,,» w UV w Fig. 5 ùk ü. 37 z w ùkûš BM 3, 4 ƒ À ùkû. w XRD spnel ùkù BM 6, 7 MnO ƒ ùkù w» w w. XRD spinel ùk ü w w» w UV ùk ü ƒ ƒ¾ BM4» ³ w Table % 0¾ y g. Table 4 w 1600 C 1 w» w XRD ww Fig. 6 ùkü. Table 4 w ³ ƒ 8.6% w l cristbalite peakƒ š spinel w. w w,,» w UV ww š Fig. 7 ùkü. BPP 5 wš 38 ùkû. Fig. 5 ùkü w w w» ww ùkü. spinel w w» w Fe -3.01%, Cr %, ³ %, Kalin-18.53%, CO-3.71%, MnO -5.6% w 1600 C w ƒ w. Fig. 7. UV analysis f Table 4 cmpsitin. Fig. 8. UV analysis f cmpunds that add each cmpsitin 5% t ZrO. 3.. w Zircnia x 1600 C w w spinel ùkû š UV Table 4 4ƒ zircnia w w zircnia w j w zircnia t y w» w x., Table 4 BPP 5 ~ 9 w 1600 C w w w w 35 mesh m g. 5ƒ t ƒ ( m, ƒ ) zircnia ƒƒ 5wt% ƒw yww z diskx barx xw z 1410 C 1 w. w wz

6 š v 65 Fig. 9. Water absrptin and bending strength f cmpunds that add each cmpsitin 5% t ZrO. xr,, w» w UV w Fig. 8 ùkü. L * 3.7 ~ 3.9 a * : 1.3 ~ 1.4, b * :.6 ~.7 ùkù w w w t x š w t w ùkü ù w. Fig % w yw. ù m ƒ ƒw kgf/mm d ù BPP 5 w 3.6 ù kû. ù zircnia t w» w BPP 5, Fe %, Cr %, ³ -9.66%, Kalin-18.53%, CO- 3.71%, MnO -5.6% 1600 C 1 w w 35 mesh wƒ w w z ƒ C š w w spinel» w w» w w w š, w w Zircnia w e zircnia x w C w w spinelx» w w» w Fe -3.01%, Cr %, ³ -9.66%, Kalin-18.53%, CO-3.71%, MnO -5.6%, 1600 C.. w w UV L * : 38.45, a * : 0.18, b * :.33 ww. 3. w w 5wt% Zircnia ƒw 1410 C w z UV w L * :37.54, a * :1.31, b * :.61 zircniaƒ 0.108%, 3.6 kgf/mm ùkù w ù zircnia t w» ww. REFERENCES 1. Y. Shiraki Glaze and Pigment, Deakwang, pp. 685 (1980).. K.-H. Lee, Develpment f Clred Zircnia Ceramics, pp. 1-3, 16-18, Myng-Ji Univ Graduate, J.-S. Lee and E.-S. Lee, Synthesis f Spinel Pigment n ZnO- Fe System(in Krean), J. Kr. Ceram. Sc., 6 [] (1989). 4. D.-J. Kim, H.-L. Lee, and H.-J. Jung, Effect f Surface Grinding n Lw Temperature Degradatin f 3Y-TZP(in Krean), J. Kr. Ceram. Sc., 30 [] (1993). 5. Y.-H. Baik, Study n Synthesis f MgAlO 4 Spinel and Characteristics(in Krean), J. Kr. Ceram. Sc., [6] 9-36 (1985). 6. Escardin-A, Mestre-S, Barba-A, Beltran-V, and Blasc-A, Synthesis Mechanism f an Irn-Chrmium Ceramic Pigment, J. Am. Ceram. Sc., 83 [1] 9-3 (000). 7. C.-W. Park, J.-S. Lee, and E.-S. Lee, Frmatin and Clr f the Spinel Slid-Slutin in ZnO-Fe -Ti -SnO System(in Krean), J. Kr. Ceram. Sc., 31 [] (1994). 8. E.-S. Lee and J.-S. Lee Frmatin and Clr f the Spinel Slid Slutin in CO-ZnO-Fe -TiO -SnO System(in Krean), J. Kr. Ceram. Sc., 8 [11] (1991). 9. E.-S. Lee, C.-W. Park, and S.-Y. Hwang, A Study n the Frmatin f Spinel Pigment(in Krean), J. Kr. Ceram. Sc., 1 [1] 9-36 (1975). 44«5y(007)