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1 Jurnal f the Krean Ceramic Sciety Vl. 46, N. 6, pp. 602~608, DOI: /KCERS Develpment f Ceramic Bdy using Waste Celadn Jea-Il Lee, J-Sek Park*, Yng-Sek Lee, and Byung-Ha Lee Department f Ceramic Engineering, Myngji University, Yngin , Krea *Krea Institute f Ceramic Engineering and Technlgy, Seul , Krea (Received April 6, 2009; Revised July 13, August 24, 2009; Accepted August 24, 2009) q» y w» Á *Á Á w w œw *w»» x l ( ; , 8 24 ; ) ABSTRACT The yield is increasing as the manufacturing technlgy f ceramics prgresses, hwever, there are many ceramics f pr quality due t variables upn prducing ceramics. Sme f thse waste ceramics are recycled by sanitary ware r tile manufacturers, but mst f them are filled in making envirnmental prblem. Therefre, a research begins t recycle waste ceramic ware as alternative t sme imprted ceramic ware materials and t reduce envirnmental pllutin. This study, succeeding last study which applied waste white ware as ceramic bdy material, aimed t slve prblems f envirnment and materials by recycling waste ceradn generated in specially frmed areas fr ceramic in Gyenggi-d such as Ichen, Yeju and Gwangju as the ceramic bdy material. Cnsequently, the additin f waste ceramic ware int the ceramic bdy was judged t have limit up t 30% accrding t plasticity measurement. As we added shredded waste ceramic ware as much as 30% int basic ceramic bdy and checked its features, the pre rate and absrptin rate were gd t be average 4% and 3% respectively. In additin, it shwed strength mre than 720 kgf/cm 2 which is higher than existing ceradn bdy n the market with gd sinter state; s it is judged t be available r develped as new ceramic bdy. KeyG wrds : Recycle, Waste ceramic, Ceradn, Ceramic bdy, Envirnmental prblem 1. ù y m»- - -» y v š, x» mw w» 1-8) y y w š. w w» œ w,, x, ƒƒ œ w w w š yw ƒ» t wš.», k, s» s» wš. w s» y k,» w, w, Crrespnding authr : Jea-Il Lee seasil2@paran.cm Tel : Fax : w š š, ƒw y š. w s» w y w w» w l»» x 9~16)ƒ w š, p y w ƒ y š ù, ù y š y w s» w w k.» ƒ y w ù q» w» 17) ù» ƒ» q»» y w» ww» w š w. q» w» w w w y w w y, p» y» z q. 602

2 603 Á Á Á w Table 1. Chemical Cmpsitins f Raw Materials fr Standard Pttery Bdies Materials SiO 2 Al 2 O 3 Fe 2 O 3 MgO CaO Na 2 O K 2 O TiO 2 Obu Hampyeng Sesan Sanchung Kalin Ichen Sand Quartz Feldspar 2. x 2.1.» w q š Ÿ e» w, m, w s m, m, e, m, ³, ww. w Table 1, w» Fig. 1 ƒƒ ùkü. q» (W.P.P.: waste pttery and prcelain) š q» w w. q» ww š Table 2 ùk ü. q» flat mill ball mill w 325 mesh t m g w z» ƒƒ ƒw x w. q» s(sald-7101, Shimadzu, Japan) y w, Fig. 2 8~40 µm ùkü s³ 10 µm ùkü. w w q» y w» w X z (XRD-7000, Shimadzu, Japan) ww. Fig. 3 quartzƒ, mullite w.» ƒ w Materials Obu Hampyeng Celadn Bdy Sesan Sanchung Kalin Ichen Sand Quartz Feldspar wt% Fig. 1. Mineral cmpsitins f standard pttery bdy (wt%). Table 2. Chemical Cmpsitins f W.P.P. SiO 2 Al 2 O 3 Fe 2 O 3 CaO MgO K 2 O Na 2 O MnO TiO 2 P 2 O 5 Ig.lss W.P.P w wz

3 q» y w» 604 Fig. 2. Particle size distributin analysis f waste pttery and prcelain(w.p.p.) after ball-milling. Fig. 3. XRD pattern f waste pttery and prcelain. Table 3. Cmpsitins f an Experiment Celadn Bdy W.P.P. CW CW CW CW CW CW w d q q»» ƒ š q x w q» y w w» w Fig. 1 w» q» Table 3 ƒw x ww. ƒ w yw y wwš 16~18% ƒ w z 7 ww r x ƒ w, yw p d w» w šx w xr w. d mm bar type, d φ25 4mm disc type xr w y d mm bar type xr ƒƒ xw xw xr { ù, ƒ w» w 4h, 6 k z dry ven ww. silicnite muffle furnace w ~600 C¾ 2 C/min, 600 C 1240~1260 C¾ 5 C/min g. z 1 jš þƒ ww p ƒ x ƒ t x w ƒ p wù, ƒ d x ¾ ³ y d y»» wwš 18) w d w. d y. ƒ ew ù ƒ ƒ š w d ww ƒ q w. w x d w» ¼ barx z ƒ ³» š ƒ q w ciling d w m 10» w ƒ sƒw DSC-TGA ƒ w w,, y w» w DSC-TGA(STA-MS-Skimmer, Netzsch, Deutschland) 1200 C¾ ww SEM d ƒ w r wš ƒ xr q HF40% 50 ƒ etching ww SEM(SS-550, Shimadzu, Japan) w d»» w x z p, w,,»œ, p w. xr,»œ,» d KS L3114 w, KS L4004 d» d w. w y d xr { d w w, d UTM(MKS Type-PP-650-D, 46«6y(2009)

4 605 Á Á Á w Fig. 4. Result f measurement f plasticity by dry strength and ciling methd. Fig. 5. DSC-TGA curve f each cmpsitins. Scientific Instrument, JAPAN) 3 x d w. 3. š 3.1. ƒ d yww w w ƒ d x d ciling w d wwš Fig. 4 ùkü. t ƒ m ƒ d» w ƒ ƒ w. x d m 47 MPa,» 34 MPa ùkü ù q» ƒ w w w. m d e 10 w z w ciling w ƒ sƒ CW1 9 x w ù, q» ƒ w ƒ x w y. w q» ƒ ƒ ƒ XRD q» ƒ quartz mullite». x q» ƒ 30% ƒ ¾ x ƒ w ù x. ƒ d q» ƒ w 30% š q DSC-TGA q»ƒ ƒ ƒ p y y w» w DSC-TGA wwš Fig. 5 ùkü. Fig. 5.(a) DSC d ƒ y j y, s» ƒ ƒ Fig. 6. Drying shrinkage rate and Firing shrinkage rate f each cmpsitin (Sintering temperature ; 1250 C). ƒ wš š. w Fig. 5(b) TGA d CW1 700 C ¾ m k w ƒ ù, CW3 CW5 300 C ¾ ƒ ù CW1 w s w d Table 3» q» ƒw ww w d wš Fig. 6 ùkü. q» ƒ ƒw w y w. ƒ 1250 C ƒƒ ww z d w w» 15% j ùkû ù, z q» w wz

5 청자 파도자기를 활용한 도자기 소지 개발 Fig. 7. Prsity and Water absrptivity f each cmpsitin sintered at 1250C. 첨가량의 증가에 따라 소성수축율도 점점 감소하여 파도 자기를 30% 첨가한 조성의 경우 약 11%로 낮아지는 것 이 확인되었다. 이는 파도자기 분쇄분이 수축에 대한 반 응이 없는 chamtte로 작용하여 소지 내의 수축율을 크게 낮추는 역할을 하는 것으로 보인다. 흡수율 및 기공율 각 조성의 소지를 1250 C로 소성한 후 시험편의 기공율 과 흡수율을 측정하고, 그 결과를 Fig. 7에 나타내었다. 기 본 소지에 파도자기 분쇄분이 첨가됨에 따라 흡수율과 기 공율은 분쇄분의 첨가량이 증가함에 따라 그 값은 증가 하는 경향이 나타났다. 기공율의 경우, CW1이 3.6% 정도 임에 반해 파도자기 50% 첨가된 CW6는 6% 정도였고, 흡수율의 경우에도 CW1은 2% 정도였지만 CW6 조성은 3.6% 정도로서 나타났다. 이러한 기공율 및 흡수율의 증가에 대한 이유를 확인 해 보고자 기본 소지와 파도자기를 30% 첨가한 소지를 1250 로 소성한 시험편의 미세구조를 관찰하고 그 결과 를 Fig. 8에 나타내었다. 기본소지인 CW1의 경우 치밀한 미세구조를 나타내고 있으나, 이에 비해 파도자기가 30% 첨가된 CW4 조성의 경우에는 기본소지에 비해 기공이 Fig. 8. Fig Bending strength f each cmpsitin sintered at 1250C. 많은 미세구조가 관찰되어 이에 소결이 충분히 이루어지 지 않았음이 보여졌다. 이는 파도자기분이 chamtte로서 작용하여 그 함량 증가에 따라 소결성을 방해하여 그로 인해 흡수율과 기공율이 증가하게 되었다고 보인다. 굽힘강도 및 하중연화 조합된 각 조성에 대한 굽힘강도 측정은 1250 C 소성 시편에 대해 행하고 그 결과를 Fig. 9에 나타내었다. 기 본소지인 CW1 조성의 굽힘 강도값은 665 kgf/cm 로 측정 되었는데 파도자기 분쇄분의 첨가량의 증가에 따라 30% 까지는 증가하여 713 kgf/cm 을 나타내고 있음이 확인되 었다. 하지만 그 이상의 첨가량에서는 큰 강도변화를 보 이지 않고 미미하지만 조금 감소하는 경향을 보였다. 이 는 앞서 흡수율 등의 물성 평가 결과와 같이 파도자기 함 량 증가에 따른 소결성의 저하에 따른 것으로 보여진다. Fig. 10에 나타낸 하중연화 측정 결과에서는 파도자기의 첨가량이 증가함에 따라 변형이 낮아지는 것이 확인되어 졌다 C 소성의 경우 CW1에서 12 mm 정도이던 변 형률이 CW4에서는 6 mm까지 낮아졌고, CW6 조성에서는 2 mm까지 떨어져 거의 변형이 일어나지 않았음이 확인되 었다. 이러한 낮은 하중연화 측정치를 나타낸 파도자기 첨 SEM phtgraphs f each cmpsitin sintered at 1250C. 제 46 권 제 6호(2009)

6 607 Á Á Á w Cmpsitin Results f lad testing (mm) 1240 C 1250 C 1260 C CW CW CW CW CW CW Fig. 10. Result f lad testing f each cmpsitin at varius temperature. Fig. 11. SEM phtgraphs f each cmpsitin bdy sintered at 1250 C. ƒ w» x w j»» ƒ w š ƒ SEM ƒ mullite k y w š SEM wwš Fig. 11 ùk ü. ƒ r HF 40% 50 e ww.,» q» 10% ƒ k CW4 ¾ mullite š y. w mullite w yƒ ƒ» w š q. CW5, CW6 CW4 j. 4. q» w y» w x,. (1) x, q»ƒ ƒ» 1250æ ƒ w. q» sw e w w» q. (2) x, y w ƒ d q» ƒ w 30%. q»ƒ 30% ƒ CW4 1250æ w,»œ s³ 4%, s³ 3% yw ùkü, 720kgf/» q. (3) y» q» w w y w w, ƒ chamtte w x q w p ƒ w wz

7 q» y w» 608» y». REFERENCES 1. J. H. Lee, E. S. Na, and S.C.Chi, A Study n the Effect f Residual Stress between Bdy and Glaze f Pttery n the Mechanical Strength, Kr. J. Mat. Res., 9 [2] (1999). 2. Y. G. Jung, Effect f Firing Temperature n Mechanical Prperty and Cntact Damage in Pttery, J. Kr. Ceram, Sc., 35 [12] (1998). 3. W. M. Carty and U. dnsenapati, Prcelain-Raw Materials, Prcessing, Phase Evlutin and Mechanical Behavir, J. Am. Ceram. Sc., 81 [1] 3-20 (1998). 4. A. W. Nrris, D. Taylr, and I. Thrpe, Range Curve: An Experimental Methd fr the Study f Vitreus Pttery Bdies, Trans. J. Br. Ceram. Sc., (1992). 5. Y. Kbayashi, O. Ohira, Y. Ohashi, and E. Kat, Effect f Firing Temperature n Bending Strength f Prcelain fr Tableware, J. Am. Ceram. Sc., 75 [7] (1992). 6. H. J. Lim, S. C. Chi, E. S. Lee, and J. S. Lee, "Effect f Prcessing Parameters n the Densificatin - Behavirs by Lw Shrinkage in Materials, J. Kr. Ceram. Sc., 33 [7] (1996). 7. E. S. Lee, Studies n the Mechanical Prperties f Prcelain Bdies, J. Kr. Ceram. Sc., 11 [3] (1974). 8. R. C. Bradt, A High-Tech Apprach t a Traditinal Ceramic-The Tughness f Prcelain, pp. 15~22 in prceeding f Internatinal Sympsium n Fine Ceramics Arita 86, F. Andrela, L. Barbieri, A. Crradi, I. Lancelltti, and T. Manfredini, Utilisatin f Municipal Incineratr Grate Slag fr Manufacturing Prcelainized Stneware Tiles Manufacturing, J. Eur. Ceram. Sc., 22 [9-10] (2002). 10. I. Agte, A. Odrizla, N. Gutierrez, A. Santamaria, J. Quintanilla, P. Cupelle, and J. Sares, Rhelgical Study f Waste Prcelain Feedstcks fr Injectin-Mlding, J. Eur. Ceram. Sc., 21 [16] (2001). 11. A. P. Luz, S. Ribeir, Use f Glass Waste as a Raw Material in Prcelain Stneware Tile Mixtures, Ceramics Internatinal, (2007). 12. R. R. Menezes, H. G. Malzac Net, L. N. L. Santana, H. L. Lira, H. S. Ferreira, and G. A. Neves, Optimizatin f Wastes Cntent in Ceramic Tiles Using Statistical Design f Mixture Experiments, J. Eur. Ceram. Sc., (2008). 13. R. R. Menezes, H. S.Ferreira, G. A. Neves, H. de L. Lira, and H. C. Ferreira. Use f Granite Sawing Wastes in the Prductin f Ceramic Bricks and Tiles, J. Eur. Ceram. Sc., 25 [7] (2005). 14. F. A. Csta Oliveira, V. Livrament, F. Delmas, Nvel Mullite-based Ceramics Manufactured frm Inrganic Wastes I. Densificatin Behaviur, J. Mater. Pr. Tech., (2008). 15. J. O. Hng, S. G. Kang, K. G. Lee, Y. T. Kim, Y. J. Kim, J. H. Kim, and M. S. Park, Characteristics f Sintered Bdies Made frm the System f Paper Sludge Ash-Fly Ash-, J. Kr. Ceram. Sc., 38 [10] (2001). 16. S. W. Lee, H. J. Kim, and E. H. Kim, Cntrl f Permanent Shrinking f Recycled Castable Refractries frm Waste Refractries f Al 2 O 3 -SiO, J. Kr. Ceram. Sc., 29 [1] (1992). 17. J. I. Lee, Y. S. Lee, and B. H. Lee Ceramics Bdy Develpment Using Waste Whiteware, J. Kr. Ceram. Sc., 43 [10] (2006). 18. B. S. Han, Test and Characterizatin f Prcelain Bdy, 14th Pttery Sympsium in Krea, (2001). 19. H. Schneider, K. Okada, and J. A. Pask, Mullite and Mullite Ceramics, Jhn Wiley & Sns, G (1994). 20. I. S. Kim, S. W. Kang, J. S. Park, M. W. Lee, B. H. Lee, and K. H. Lee, Influence f Mullite-seed n the Mullite Synthesis frm Varius Cmpsitins, J. Kr. Ass. Crystal Grwth, 10 [1] (2000). 46«6y(2009)

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