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 449-78, Krea (Received March 5, 007; Accepted May 15, 007) š v ŸyÁ Á w w œw (007 3 5 ; 007 5 15 ) 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 -30.47%, 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 E-mail : lbh@mju.ac.kr Tel : +8-31-330-6461 Fax : +8-31-330-6457 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
. x.1. spinel.1.1. 1400 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 1..1.. 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 48.47 33.49 0.5 0.1 4.17 1.58 0.45 0.3 0.11 0.01 Pu Ye Quartz 99.61 0.09 0.03 0.0 0.09 0.04 0.01 - - - Table. Cmpsitins f Black Clr Spinel Pigment Cmpsites Fe Cr Pu Ye Quartz Hanheung Kalin CO MnO BP 1 8.5 7.13 16.6 16.5 3.3 BP 8.5 7.13 16.6 16.5 3.3 - BP 3 8.5 7.13 16.6 16.5 - BP 4 8.5 7.13 16.6-3.3 BP 5 8.5 7.13-16.5 3.3 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..1.3. 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 1 8.5 7.13 16.6 16.5 3.3 BM 8.5 7.13 16.6 16.5 3.3 3 BM 3 8.5 7.13 16.6 16.5 3.3 4 BM 4 8.5 7.13 16.6 16.5 3.3 5 BM 5 8.5 7.13 16.6 16.5 3.3 6 BM 6 8.5 7.13 16.6 16.5 3.3 7 BM 7 8.5 7.13 16.6 16.5 3.3 8 CO MnO BPP 1 8.5 7.13 16.6 16.5 3.3 5 BPP 8.5 7.13 14.6 16.5 3.3 5 BPP 3 8.5 7.13 1.6 16.5 3.3 5 BPP 4 8.5 7.13 10.6 16.5 3.3 5 BPP 5 8.5 7.13 8.6 16.5 3.3 5 BPP 6 8.5 7.13 6.6 16.5 3.3 5 BPP 7 8.5 7.13 4.6 16.5 3.3 5 BPP 8 8.5 7.13.6 16.5 3.3 5 BPP 9 8.5 7.13 0 16.5 3.3 5 44«5y(007)
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, 40 6 5mm 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 3.1.1. 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. 3.1.. 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. 1000 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. 3.1.3. 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
고온용 검정색 스피넬 안료의 개발 Fig. 4. 63 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. 3 3 7-9) Fig.. XRD patterns f BP 1 cmpsitin at varius calcinatin temperature. 1.3 0.7 3 Fig. 3. XRD patterns f Table cmpsitin calcined at 1600C. Fig. 5. UV analysis f Table 3 cmpsitin. 제 44 권 제 5호(007)
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 4 16.6% 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 -30.47%, ³ - 9.66%, 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
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. 9 0.11% w yw. ù m ƒ ƒw 30.4 31.4 kgf/mm d ù BPP 5 w 3.6 ù kû. ù zircnia t w» w BPP 5, Fe - 3.01%, Cr -30.47%, ³ -9.66%, Kalin-18.53%, CO- 3.71%, MnO -5.6% 1600 C 1 w w 35 mesh wƒ w w z ƒ. 4. 1400 C š w w spinel» w w» w w w š, w w Zircnia w e zircnia x w. 1. 1400 C w w spinelx» w w» w Fe -3.01%, Cr -30.47%, 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, 003. 3. J.-S. Lee and E.-S. Lee, Synthesis f Spinel Pigment n ZnO- Fe System(in Krean), J. Kr. Ceram. Sc., 6 [] 187-94 (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 [] 164-68 (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 [] 13-19 (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] 897-907 (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)