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1 Bimaterials Research (2005) 9(2) : Bimaterials Research 7 The Krean Sciety fr Bimaterials Hydrxyapatite TiNx w Fabricatin f Cmpsites Materials f Hydrxyapatite and TiNx ½ 1 *Á«1 Á 1 Á y 1 Á 1 Á 1 Á 2 ÁJ. F. Schackelfrd 3 ÁZ. A. Munir 3 Sungjin Kim 1 *, Wnil Gwn 1, Sungbum Park 1, Yung Hwan Oh 1, Kyeng-Sik Ch 1, N-Jin Park 1, D En Park 2, J. F.G Shackelfrd 3, and Z. A. Munir 3 1 Š g Š, 2 d}(j) 3 Dept. f Chemical Engineering and Materials Science, University f Califrnia at Davis, Davis CA 95616, USA 1 Department f Materials Science and Metallurgical Engineering, Kumh Natinal Institute f Technlgy. 1 Yangh-Dng, Gumi, Gyengbuk , Krea 2 Research Center, NAWOO Tech, Crpratiin Simi-Dng, Gumi, Gyengbuk , Krea 3 Department f Chemical Engineering and Materials Science, University f Califrnia at Davis, Davis CA 95616, USA (Received April 15, 2005/Accepted May 19, 2005) The cmpsites f hydrxyapatite-tinx were prepared using a spark plasma sintering(sps) apparatus. Density f hydrxyapatite-1%tinx cmpsite was decreased with increasing cntent f TiNx in rder f 0.1%, 05% and 1.0% but density f hydrxyapatite-1%~10%tinx cmpsite was increased with increasing cntent f TiNx inrder f 1%, 5% and 10%. The maximum biaxial strength f hydrxyapatite and TiNx f cmpsites was achieved by SPS with a cmpsitin f 0.1% TiNx at 900 C. The decmpsitin f cmpsites hydrxyapatite and TiNx cmpsites were nt detected by XRD at the range f 900 C t 1100 C, this means the decmpsitin f hydrxyapatite was restrained easily by additin f TiNx. Key wrds: Hydrxyapatite, TiNx, Cmpsites, Spark plasma sintering, Decmpsitin Œ ~fƒ(hydrxyapatite: f HAp ) f tf x f j i i fš, t xœ f f, t f Œ Š t Œ f f til Š Šf f f nan Œ~, t, e l z Š d f. 1-4) HAp x tf f f h lf f f e t Œ fff f., HAp tf v i Š 15~165 MPa h Š ~ f. 5,6) f f HApf tf Œ e, i hš Œ fff Š, e f ŒŠi i f d Š fdš f ~ f. f Š f hš rf ~ df j i f d f f l HAp Š Š f lf f Œ d hf l f. f Š Š f fš hš HAp f ŒdŠ e Š Šjf l e hhš Œ~f f ƒ fš, g, Œf e z *sf hf: sjghim@empal.cm g hiš d f. f Š hf Š eš g f ŠŒ Š h ƒ f f lš ff ŠŒ t e l z, -l z, f Œ ~, ~, lœ ~ f f. 7-11) t e j l z t Š d, f d t Š f f x f f f d f Š dœ f f ff, f Œ ~ ~ f t Š d Štf ~ f hšš Œ f Œ f f f. 12,13) ƒ ~ f h f ƒdf d hf tg h f, hf ƒ d Š lf Œ f Œ t f f l d Š gf t f x f v f j f ghf l f d Št hidf f f f lš f ) h Š f j f HApf Š t f Œ fš i f f f lš eš h j l e Š l e j s fš ~ tf 107

2 108 lá efá Á ŒÁi Á lá ÁJ. F. SchackelfrdÁZ. A. Munir f lœ ~ Š tf Š Œ Œ lš lš f. 11,17,18) ~ f Š bwl, ~ ballf v lœ ff f l ~ f planetary millf fdš milling e i f ihš TiNxf hiš f, f l TiNxf milling t ~ f j f millingf lš ~ f ef j TiNxf ef l Š, f l ~ f ŠeŠ TiNx Nf hš ~ l ff HApf Š lš f Nf Š Š fš l f 18) f hf x TiNx HAp Št hiš f Š f ~ i e TiNxf t f t f Š eš 0.01~1.00% lf t i ef Št hiš, f hf Štf ŒŠf xf f i ef 5%, 10%f TiNxf t Š Št hiš Œ Š. Š f Š HApf Š h l Š f Š e Š h gx fdš tf f f h fš l Œ Š t d ~ e 19-21) f fdš } l (spark plasma sintering:sps) fdš ŠŠ f u Š tf i Š tg f f elš Š. f HAp TiNxf Š t t TiNx Štf x t i Š, ƒ f Š. d e HAp(calcium phsphate tribasic, Alfa Aesar, USA) x Š f 34~40% ef, TiNx hid ~ (High Purity Chemicals, Japan)f 99.9%f f 45 µmf f dš f, planetary miling i f Si3N4 bwl 9mmÅf x f ball Š ~ f ŒŠŠ, 400 rpmf f Š hiš f, XRD xf Šd 5, 10, 20 f hiš. f l TiNx f HAp Š 0.01, 0.1, 0.5, 1.00, 5.00, 10.00wt% f e ŒŠŠ 30 ball milling Š ŒŠŠ dry venf fdš 80 C 8 iš d j Š. w i f ŒŠ f l f 30 mmf hwš, SPS(Dr. Sinter 1050, Sumitm Cal Mining C. Ltd., Japan) g dš hiš. } l f Table 1 ~ f 7 Mpaf Š Table 1. Sintering cnditins f spark plasma sintering Sintering apparatus SPS(Dr Sinter 1050, Japan) Sintering temperature Saking time Heating rate Atmsphere Applied pressure Ar-4%H 2 ŒŠ e 200 C/minf 900~1,100 Cf u 5 Š f ~ i f ŠŠ. hiš f whš vš hf f hœš vf Šf whš f Š. h f X- h (Mdel D5005, Bruker, Karlsruhe, Germany)f Š TiNx f f Š whš. whf CKÅ f fdš Schulz f fdš, h f 40 KV, h 30 maf f 2θ= e t elš i f ŠŠ. l TiNx Štf i FESEM(JSM-6500F, JEOL, Japan)f fdš rš f TiNxf Œ HAp Št jf TiNxf f EDX(Energy Dispersive X-ray Spectrscpy : Inca, Oxfrd) fdš whš. Štf micr Vickers f} wh (Mdel-7, MATSUZAWA, Japan) whš, whf Instrn(Mdel 4468, Instrn Crpratin, U.S.A.)f fdš 0.5 mm/minf f fv (biaxial strength test)f whš. 23) š 900~1100 C 5 min 200 C/min Ar-4%H 2 mixed gas 7 MPa TiNx XRD Figure 1 planetary milling fš hi ~ f XRD ~ f Si 3 N 4 bwl 9mmϕf x f ball Š ~ f ŒŠŠ, 400 rpmf i milling f Œ z whš f, XRD wh milling t TiN 0.26f ŒŠ h ŒŠ f Œ fš 5 f milling s TiNf Œ fff ff, 20 f TiN0.26f h peak Š TiNf peakf } Šf f f, fšf Št t Š TiNx TiN 0.26 TiNf Œg 5 hr planetary millingš hiš f jf dš. w Figure 2 f TiNx HAp Štf Œ f TiNxf i Œ Š f t e 0.01% 10% fš hšš TiNx t Bimaterials Research 2005

3 Hydrxyapatite TiNxf Štf hi 109 Figure 1. XRD patterns f pure Ti and TiNx pwder milled fr different times. Figure 2. Density variatin with TiNx cntents f hydrxyapatite-tinx cmpsites by spark plasma sintering. Š Œ Š f. f i Š HAp Š Œ 900 C f 1.53, 1000 C f 1.74, 1100 C f 2.26f Š Š, 12) 900 C 1000 C l Š 25%f l ~ l, 1000 C 1100 C l Š 16%f f ff, f 1100 C f f f CaO f Š lš Š f w f f. TiNx t d i f l Š l Š f ~ f, ƒ 0.01%t f d HApf Š 900 C 50%f l ~ f 1000 C 30%f l Š f ~. ƒ, TiNxf 0.01% t Š 1100 C Š g ~. f TiNxf f t ih f Šf Š TiNxf HApf tf h h f l Š HApf Š hš ff fdš f w. 0.01%-1%i ef TiNxf t Š HAp TiNx Štf Œ Š 0.01% 1% Štjf TiNxf f l Š Š f ~ f f TiNx f t l Š f f Š f g TiNxf } nan size f fif f nan sizef TiNx t Œ f fš f f wš f lš Š f. 1%, 5% 10%f TiNxf t Š HAp TiNx Štf Œ Š 1% 5%, 10% Štjf TiNxf f l Š l Š f ~ f f Štf Œ Šg f ŒŠf xf ff f f, f HAp ~ f 25% f f ŠeŠ g f l ~ f l Š 12) f fxš f ~. w XRD Figure 3f HAp-1.0%f TiNx Štf X- h f j ff, Štf XRD f HAp f t f XRD f h f 1100 C f d HApf peakf f Š f hdš f f f fš XRD f j f ff ff, ~ f t Š HAp-Ti Št 1000 C ~ CaO peakf, 1100 C ~ CaTiO4f 12)f peak ~ l f ff, f TiNxf t fš HApf Š f Š j f f., Figure 4 f HAp-10.0% TiNx Štf X- h 3x f (tricalcium phsphate: TCP)f peak ~Š f HAp Š f ff, f f TiNxf t Š d TCPf Œ f Šf Š fff Š, Figure 3. XRD patterns f hydrxyapatite-1.0% TiNx at varius sintering temperatures. Vl. 9, N. 2

4 110 lá efá Á ŒÁi Á lá ÁJ. F. SchackelfrdÁZ. A. Munir Figure 4. XRD patterns f hydrxyapatite-10.0% TiNx at varius sintering temperatures. f 1100 C f Š fv f Œ f ff f. w x Figure 5 TiNx HAp Štf biaxial strengthf Œ f TiNf i Œ Š f, ƒ 1100 C TiNxf Š f 0.5%f f t d t f f biaxial strength whš. f 1100 C f f f CaO f Š lš Š f e Š f f CaOf fš f lh fš Š f } f f w. ƒ biaxial strengthf Œ f TiNxf i Œ Š Š 900 C 1000 Cf TiNxf t f 0.1% f t biaxial strengthf l Š ff f f, 900 C Figure 5. Biaxial strengths variatin with varius sintering temperatures and TiNx cntents f hydrxyapatite-tinx cmpsites. 0.1% u f ~ f f HAp Š 50% l Š f 1000 C 0.1% u f ~ f f HAp Š 25% l Š f ~ f f. f f ŒŠ i f 11) Œ ~fƒ 900 C f (OH)- f f~ fš ~ ff f 1150 C f 3x f f TCP(tricalcium phsphate), CaO H 2 O Š f h f ŒŠ i f Œ ~fƒf h Œ ~, vš Š i gš f lš f hf f 25-27) f TiNxf t HAp Š fš TCPf h f ~ l f CaO f Š f f l f. f f h Š f f TiNxf t fš HApf Š hš f l ff TiNxf t f HAp Š hf j h TCP f Š CaO f Š hf f l f f. 0.5% Š 1%, 5%,10% TiNx f t fš 1000 C fšf d l Š f Œf Š f f f TCPv f HApf Š f hš 5%, 10%f TiNx f t fš Štf l f x rule f mixturef } fdš f f C f d TiNx 0.1% t Š Š 0.5%f f t l Šl HAp TiNxf Št f biaxial strength whš. f HAp TiNx t d ih fdš v l Š f ~ l, 1100 Ch f f HAp t TiNx TCP Œ tl Š CaOf Štl fš f f tlš ff fdš f vh. w Figure 6f TiNx f 1.0% 10% t HAp-TiNx Štf biaxial strenth f f FESEMf i Š, hthf fff } 10%f TiNx t f d } ~ f f TiNxf t ih f Šf Š f f j f. l TiNx 1.0% t Štf d 150~250 nm e f HAp ff 200~300 nm f f i l fff ff, TiNx 10% t Štf d 250~300 nm ef HAp ff 250~350 nm f f i l fff f. f Šjf 7 Mpa j h j tf ef } Š fš f, f f f f biaxial strength f f ~ dff fdš fff j f. Bimaterials Research 2005

5 와 TiNx의 복합체의 제조 Hydrxyapatite 111 HAp-1.0%TiNx보다 더 큰 결정립을 보여주는 것으로 TiNx가 소결조제로서의 역할을 하고 있다는 것을 의미한다. 4. HAp-TiNx 복합체의 X-선 회절 패턴을 분석한 결과, 거 의 소결 온도에 관계없이 순 HAp만의 소결체의 XRD 패턴과 유사한 XRD 패턴을 보여주고 있으며, TiNx의 첨가에 의해 HAp의 분해 현상이 줄어든 것으로 예측된다. 5. TiNx의 첨가량이 1% 이하의 경우에서는 XRD 패턴은 거 의 같고 HAp의 분해현상은 없었지만, 5% 및 10%의 TiNx가 첨가 된 복합체의 경우는 XRD 분석결과 TCP peak이 관찰되 므로 다량의 TiNx첨가에 의해 HAp가 쉽게 분해 되고 있다는 것을 알 수 있었다. 감사의 글 본 연구는 2003년도 금오공과대학교 학술연구비 지원에 의 하여 연구된 논문으로, 이에 감사드립니다. 참고문헌 1. P. Van Landuyt, F. Li, J. P. Keustermans, J. M. Streydi, F. Delannay, and E. Munting, J. Mater. Sci.: Mater. Med.,, 8-13 (1995). 2. Y. W. Gu, K. A. Khr, and P. Cheang, Bne-like apatite layer frmatin n hydrxyapatite prepared by spark plasma sintering (SPS), Bimaterials,, (2004). 3. H. Li, K. A. Khr, and P. Cheang, Impact frmatin and micrstructure characterizatin f thermal sprayed hydrxyapatite/titania cmpsite catings, Bimaterials,, 6-13 (2003). 4. I. Manjubala and T. S. S. Kumar, Bimaterials,, (2000). 5. V. J. P. Lim, K.A. Khr, L. Fu, and P. Cheang, J. Mater. Prc. Tech.,, (2000). 6. P. Van Landuyt, F. Li, J. P. Keustermans, J. M. Streydi. F. Delannay, and E. Munting, J. Mater. Sci.: Mater. Med.,, 8-13 (1995). 7. M. Jarch, C. H. Blen, M. B. Trmas, J. Bblck, J. E. Kay, and R. H. Dremus, J. Mater. Sci.,, (1976). 8. H. Aki, Medical applicatins f hydrxyapatite, A. Ishiyaku (Ed.), EurAmerican, Inc., 1994, pp 신미정, 김도균, 김교한, 인산과 칼슘 이온을 함유한 수용액 중에 서의 타이타늄 표면처리, Kr. J. Mater. Res.,, (1998). 10. L. L. Hench and J. Wilsn, Biceramics, MRS Bull., September, 1991, pp 김성진, 조경식, 박노진, 수산화아파타이트와 지르코니아의 경사 기능 재료의 제조, 한국결정성장학회지, (2001). 12. 김성진, 박도언, 권원일, 루스탐, 이종홍, 오영환, 조경식, 박노진, 안중호, Hydrxyapatite와 nan-sized TiN 복합재료의 제조 및 기 계적 특성, Bimaterials Research,, (2004). 13. 김성진, 박지환, 조경식, 박노진, Hydrxyapatite와 titanium의 경 사기능재료의 제조, 한국결정성장학회지,, (2002). 14. P. Li, I. Kangasniemi, and K. de Grt, J. Am. Ceram. Sc.,, (1994). 15. A. C. Bent, D. P. Almnd, S. R. Brun and I. G. Tumer, Thermal and ptical characterizatin f calcium phsphate bimaterials hydrxyaptit, J. Appl. Physi.,, (1996) Figure 6. FESEM mrphlgy f hydrxyapatite and TiNx cmpsites. 결 론 19 수산화아파타이트에 0.01%-10% 조성범위의 TiNx을 첨가하 여 혼합체를 스파크 플라즈마 소결(SPS)법으로 제조하여 소결 밀도, XRD분석, 미세구조 및 biaxial strength의 특성분석을 통하여 다음과 같은 결론을 얻었다. 1. HAp-TiNx복합체의 경우, 1% 이하의 TiNx를 미량 첨가 할 경우 0.01%, 0.1%, 0.5%, 1.0%로 TiNx의 함량이 증가할 수록 밀도가 감소하는 것으로 나타났으며, 반면에 TiNx을 1%10%의 범위에서 첨가할 경우 1%, 5%,10%로 TiNx의 함량이 증가할수록 소결체의 밀도가 증가하는 것으로 나타났다. 2. biaxial strength의 변화를 소결 온도와 미량의 TiNx의 조성 변화에 대해 비교해본 결과, 900 C에서는 0.1%에서 최 대강도 값이 나타났으나 1100 C에서도 TiNx가 0.1%이상이 첨가되면 소결 시편에 균열이 형성되어 biaxial strength 값을 측정할 수 없을 정도의 취성을 나타냈다. 3. HAp-10%TiNx 복합체의 미세구조는 250~300 nm 범 위의 HAp 입자와 250~350 nm급의 연결된 기공으로 구성되 어 있었으며, 입자 크기를 비교하면 HAp-10%TiNx 복합체가 , 8(2) 12(3) 77(5) 79(9) Vl. 9, N. 2

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