Tp ch Ha hc, T. 47 (6B), Tr.

300 - 304, 2009

NGHIN CU CH TO HYDROXYAPATIT DNG KHI XP T V S BNG PHNG PHP PHN NG THU NHIT
n Ta son 18-10-2009 V DUY HIN, O QUC HNG, PHAN TH NGC BCH, PHNG TH KIM THANH Vin Ho hc, Vin Khoa hc v Cng ngh Vit Nam ABSTRACT
. The hydrothermal method was used for preparation porous hydroxyapatite (HA) ceramics from cockle-shell, in two ways: synthesized directly from cockle-shell (aragonite CaCO3) and synthesized from CaO, which was product of cockle-shell thermal decomposition. Determined conditions of hydrothermal reaction are 180oC and 4 atm pressure in 22 hours. The obtained samples were characterized by techniques including XRD, SEM and FTIR. The analytical results confirmed that porous structured ceramics of single phase HA was formed by the indirect synthesis from fresh cockle-shell obtained CaO. Keywords: hydroxyapatite, ceramics, cockle-shell, hydrothermal, porous structure XRD, SEM, FTIR.

I - M U Do c cng bn cht v thnh phn ho hc, HA t nhin v nhn to cc dng (bt, xp, mng mng) u l nhng vt liu c tnh tng thch sinh hc cao. dng dng gm xp, HA c cc c tnh ging xng t nhin, cc l xp lin thng vi nhau lm cho cc m si, mch mu d dng xm nhp. Chnh v vy m vt liu ny c tnh tng thch sinh hc cao vi cc t bo v m, c tnh dn xng tt, to lin kt trc tip vi xng non dn n s ti sinh xng nhanh m khng b c th o thi[1]. Nh c kh nng c bit ny m ngy nay, gm xp HA cc dng c ng dng rt rng ri trong y sinh hc nh: ch to rng gi v sa cha nhng khuyt tt ca rng, ch to mt gi, lm xng nhn to, ch to nhng chi tit ghp xng v sa cha nhng khuyt tt cho xng, lm ng dn mu hoc lm in cc sinh hc cho th nghim sinh hc, lm vt liu truyn dn v nh chm thuc...[2]. 300

Gm HA c th c ch to bng cc phng php khc nhau nh: phng php nn p - thiu kt HA bt [3], phn ng pha rn, phn ng thu nhit[2,4]. HA xp t khung xng ca mt s ng vt nh san h, mai mc, v s c ch to bng phng php phn ng thu nhit ni chung vn gi nguyn hnh thi v cu trc xp ging nh khung xng t nhin ban u ca chng. Vi cu trc xp sinh hc nh vy, vt liu ny c kh nng tng thch sinh hc vi c th con ngi tt hn so vi gm xp HA ch to bng nhng phng php khc [5, 6]. Vit Nam, vic nghin cu ch to gm xp HA c cu trc xp ging khung xng ca ng vt thn mm vn cha c cp n. Tip theo cc nghin cu v ch to HA xp t khung xng san h v mai mc [7, 8], trong bi ny, chng ti trnh by nhng kt qu nghin cu ch to gm xp HA bng phn ng thu nhit t khung xp t nhin ca v s sn c trong nc.

II - THC NGHIM Vic ch to HA t v s c th nghim theo hai hng: trc tip t v s t nhin v qua giai on trung gian phn hu v s thnh CaO. V s c ct thnh nhng vin nh kch thc khong 10 10 mm, c luc ra nhiu ln bng nc ct v etanol loi b cc tp cht c hc, cc hp cht hu c v sy kh nhit 100oC. Sau mu c a vo bnh phn ng chu p xut cao cng vi dung dch mui (NH4)2HPO4 bo ho. Lng canxi v phtpho trong cc cht tham gia phn ng c tnh sao cho t l Ca/P l 1,7. B sung mt lng nh NH4OH m bo dung dch c pH 9 - 10. Phn ng thu nhit c tin hnh trong khong nhit 180 - 200oC, trong mi trng kh nit c p sut thay i t 8 n14 atm, thi gian phn ng t 24 n 62 gi. Tip theo, mu c ra k bng nc ct v sy kh. i vi hng thng qua giai on phn hu v s thnh CaO, cc vin mu sau khi s l v sy, c nung n khong 800oC trong 1 gi CaCO3 phn hu hon ton thnh

CaO v thc hin ngay phn ng thu nhit gi nguyn trng thi khung xp ca CaO. Phn ng c tin hnh nhit 180 200oC, cc iu kin cn kho st l p sut phn ng (4 - 12 atm), thi gian phn ng (24, 36 v 62 gi) v lng nc c mt trong qu trnh phn ng. Mu HA nhn c iu kin thch hp tip tc c thiu kt n nhit 850 - 1000oC trong 1 gi to gm HA. Cc mu c c trng bng cc phng php: nhiu x tia X (XRD), hin vi in t qut (SEM), hp th hng ngoi (FTIR). III - KT QU V THO LUN 1. Mt s c trng ca v s a) Mt s c trng ca v s t nhin V s t nhin cha t 98% n 99% l CaCO3. Gin XRD ca v s (hnh 1a) cho thy CaCO3 tn ti dng aragonit. y l dng km bn nht trong ba dng th hnh ca CaCO3 (dng canxit, vaterit v aragonit), do vy chng c th d dng chuyn ha thnh hp cht HA trong phn ng thy nhit p sut cao hn hai dng cn li.

Hnh 1: Gin XRD (a) v nh SEM (b, c) ca v s t nhin nh SEM ca v s t nhin cho thy chng gm c cu to bi cc cc lp mng xp chng kht ln nhau (hnh 1b). Cc lp ny bao gm nhng khi a din khng u cu to t CaCO3 dng aragonit nm cnh nhau, khng theo mt trt t nht nh. Gia cc khi a din tn ti cc l xp khng c hnh dng c trng kch thc thay i t 10 n 20 m (hnh 1c). b) Mt s c trng ca v s sau khi nung phn hu thnh CaO Hnh 2 l nh SEM ca v s sau khi nung phn hu CaCO3 CaO 800oC trong 1 gi. C th nhn thy cc lp mng mt i, to thnh cc ht khng c hnh dng xc nh. Cc ht sp xp khng theo mt trt t nht nh, gia cc ht c tn ti nhng l xp vi kch 301

thc thay i. Ni cch khc v s sau khi phn hu nhit thnh CaO, hnh thi v kch thc ca cc ht v l xp thay i r rt, xp v din tch b mt tng ln. iu ny c th gii thch ti sao v s sau khi phn hu thnh CaO d dng chuyn ho thnh HA trong phn ng thu nhit p sut cao.

thp. Do vy, ch to HA cn thc hin bng phn ng gin tip thng qua chuyn ho CaCO3 thnh CaO.

Hnh 2: V s nung 850oC 2. Phn ng thu nhit ch to HA xp a) Ch to HA xp trc tip t v s t nhin Phn ng thu nhit chuyn ha v s t nhin (CaCO3 dng aragonit) thnh HA bng phn ng thy nhit trong iu kin p = 10 atm, t = 180 - 200oC, thi gian phn ng l 48 gi. 10CaCO3 + 6(NH4)2HPO4 + 2H2O Ca10(PO4)6(OH)2 + 6(NH4)2CO3 + 4H2CO3 (1) Kt qu ca mu (hnh 3) cho thy sn phm thu c ch yu vn l CaCO3 dng aragonit. HA ch c to thnh vi hm lng rt nh (th hin trn ph XRD bng cc pic c trng rt yu vi gc nhiu x 2 = 25,88o, 31,77o, 32,20o theo JPCDS#24-0033 [9]). iu ny c th gii thch nh sau: mc d v s c cu to t CaCO3 dng aragonit l loi km bn vng nht, d chuyn ho thnh HA trong phn ng thu nhit p sut cao nhng do cu to c kht, din tch b mt rt nhdung dch mui bo ho khng khuch tn c vo su bn trong v s. Do vy, ch xy ra phn ng d th gia v s ( dng rn) vi dung dch mui bo ho (NH4)2HPO4 trn b mt vo v s to thnh mt lp HA mng. Cn bn trong khi v s, vn tn ti CaCO3 dng aragonit. Nh vy c th kt lun l vic ch to HA bng phn ng thu nhit p sut cao xut pht t CaCO3 dng aragonit c hiu sut rt 302

Hnh 3: Gin XRD ca mu b) Ch to HA xp qua giai on trung gian chuyn CaCO3 thnh CaO Phn ng thy nhit xy ra gia CaO vi dung dch (NH4)2HPO4 din ra theo phng trnh: 10CaO + 6(NH4)2HPO4 + 4H2O Ca10(PO4)6(OH)2 + 12NH4OH (2)

Sn phm ca phn ng thu nhit (phng trnh 2) nhn c cc iu kin khc nhau c nh gi bng gin XRD nhm xc nh n pha ca HA cng nh hiu sut ca phn ng. Kt qu cho thy, p sut v thi gian phn ng khng nh hng nhiu n sn phm phn ng. Trong phn ng thu nhit p sut cao, nc c nh hng quyt nh n s hnh thnh sn phm HA. Nc l mt thnh phn tham gia phn ng ng thi ng vai tr dung mi ho tan mui (NH4)2HPO4, gip mui khuch tn su vo bn trong khi CaO rn, lm cho phn ng d th rn - lng xy ra hon ton. Ngoi ra, nc cng c nh hng quan trng n xp v cu trc xp ca sn phm HA, do nc phn ng d dng vi CaO to thnh Ca(OH)2 c kch thc v xp ln hn. Chng ti cng tin hnh mt s th nghim ch to HA xp t v s p sut cao v khng c nc. Kt qu cho thy sn phm HA khng c to thnh, vn tn ti cc cht phn ng

ban u l CaO v mui (NH4)2HPO4. Kt qu thc nghim cho thy, sau thi gian phn ng l 22 gi p sut 4 atm vi mt lng nc rt nh c th thu c HA n pha, vi kt tinh cao. 3. c trng ca HA c ch to thng qua phn ng trung gian to CaO a) c trng XRD Gin XRD ca mu HA (p = 14 atm, t = 180 - 2000C, thi gian 22 gi, t nc) c a ra trn hnh 4. Sn phm thu c ch yu l HA, th hin tt c cc vch vi cng v v tr c trng cho HA. Bn cnh , xut hin mt lng rt nh Ca(OH)2, th hin qua vch nhiu x c trng v tr 2 = 18,10 (JCPDS#4-0733) [9], c th do mt phn nh CaO tc dng vi nc trong qu trnh phn ng to thnh Ca(OH)2. Trong mt s th nghim trn cng c th mt lng rt nh CaCO3 dng canxit th hin cc vch 2 = 29,40 (JCPDS#5-0586). Trong thnh phn ca xng ngi cng c cha mt lng rt nh Ca(OH)2 v CaCO3 nn s c mt ca chng trong cc mu HA ch to c khng nh hng nhiu n kh nng tng thch sinh hc ca sn phm HA.

Trn ph c tn ti mt vch khong 1412,11 - 1454,72 cm-1, c th gn cho nhm CO32-. iu ny ch ra s c mt ca CaCO3 trong mu. Tuy nhin vch ny rt yu, chng t rng lng CaCO3 rt nh. Kt qu ny ph hp vi d liu XRD.

Hnh 5: Ph FTIR ca mu HA c) c trng SEM nh SEM (hnh 6a) cho thy sau phn ng thu nhit p sut cao, cc tinh th HA to thnh c dng c trng nhit cao l hnh tr c ng knh 40 - 50 nm, di 100 - 200 nm sp xp khng theo mt trt t nht nh. Cc tinh th hnh tr ny khng lin kt vi nhau m tn ti mt cch ri rc, khng kt dnh vi nhau. Cc l xp gia cc ht khng c hnh dng v kch thc c trng r nt. Hnh 6b l nh SEM ca mu HA sau khi thiu kt 850oC. nh SEM cho thy cc tinh th sau khi thiu kt, khi xp HA c s thay i v hnh thi v cu trc. Tinh th HA hnh tr chuyn thnh cc khi a din c kch thc thay i t 0,2 n 1 m. Cc khi a din ny kt dnh vi nhau, gia cc khi khng tn ti cc bin ht r rt. Gia cc khi a din l cc mao qun xp lin thng ba chiu vi nhau v phn b tng i ng u trong ton khi. Cc mao qun c ng knh thay i trong khong 0,2 - 0,5 m. Khi xp HA sau khi ngm tm vi cht kt dnh PVA v thiu kt 850oC c cng cao hn hn so vi mu HA khng x l bng PVA v thiu kt. IV - KT LUN ch to c HA xp n pha bng phn 303

Hnh 4: Gin XRD ca mu HA b) c trng FTIR Ph FTIR c a ra trn hnh 5 ca mu HA, cho thy cc vch c trng ca HA: cc vch dao ng ca PO43- 1 471,94 cm-1, 2 876,62 cm-1, 3 gia 960,74 - 1033,49 cm-1, 4 567,43 - 603,81 cm-1 v vch dao ng ca lin kt O-H 3569,62 cm-1.

Hnh 6: nh SEM ca HA trc (a) v sau x l nhit (b) ng thy nhit p sut cao i t khung xp t nhin ca v s. p sut v thi gian phn ng khng nh hng nhiu n cht lng HA xp. Nc ng mt vai tr quan trng, va l cht tham gia phn ng va l dung mi ho tan v khuch tn mui (NH4)2HPO4 vo trong phn ng d th. xc nh thnh phn pha, cu trc xp ca sn phm HA bng cc phng php XRD, FTIR v SEM. TI LIU THAM KHO 1. T. Masahiko, K. Yoshihisa, A. Kuniyoshi, A. Yasuo, K. Tsuyoshi, K. Kiyoshi, M. Akio. J. Biomed Mater Res., Spine, Vol. 28, 637 - 644 (2003). 2. Jyrki Vuola. Natural Coral and Hydroxyapatite as Bone Substitutes, Academic dissertation, University of Helsinki (2001). 3. E. Peron, G. Fuentes, J. A. Delgado, L. Morejon, A. Almirall, R. Garca. Latin American Applied Research, Vol. 34, 225 228 (2006). 4. Roderic S. Lakes. Composite Biomarerials, Taylor & Francis Group, LLC, Biomaterials, 96 - 109 (2007) 5. Argyrios Kasioptas, Christina Perdikouri, Christine Putnis and Andrew Putnis. Geochim. Cosmochim. Vol. 71 (15), 467 (2007). 6. H. G. Rocha, A. F. Lemos, S. Kannan, S. Agathopoulos. J. Mater. Chem., Vol. 15, 5007 - 5011 (2005). 7. V Duy Hin, o Quc Hng, Phan Th Ngc Bch. Tp ch Ha hc, T. 46, 118 123 (2008). 8. Hien Vu Duy, Huong Dao Quoc, Bich Phan Thi Ngoc. Study of the Formation of Porous Hydroxyapatite Ceramics from Corals via Hydrothermal Process, International scientific conference Chemistry for development and integration, Vietnam, 1007 - 1013 (2008). 9. M. Markovic, B. O. Fowler, M. S. Tung. Journal of Research of the National Institute of Standards and Technology, Vol. 109, 553 - 568 (2004).

304