M U Hin nay, ngnh phu thut chn thng v chnh hỡnh cú nhiu loi vt liu khỏc c dựng lm np vớt c nh xng quỏ trỡnh thay th v hn gn xng nh: thộp khụng g 316L, hp kim ca Coban (CoNiCrMo), titan kim loi v hp cht ca titan (Ti6Al4V, TiN, TiO 2) Nhng vt liu ny nhỡn chung cú bn c lý húa v kh nng tng thớch sinh hc cao vi mụi trng dch c th ngi Tuy nhiờn, mt s trng hp cy ghộp c th, nhng vt liu bng kim loi v hp kim ớt nhiu b n mũn dn n cỏc phn ng o thi lm gim tui th ca vt liu v gõy nhng khú chu nht nh cho bnh nhõn Chớnh vỡ lý ny, vt liu s dng quỏ trỡnh cy ghộp xng phi ỏp ng c cỏc yờu cu c bn: cú c tớnh chng n mũn cao, bn c hc, cú s thớch nghi tt vi c th, khụng b bin dng tit trựng nhit cao v d s dng [1-5] Trong nhng nm gn õy, cỏc chn thng bnh lý v tai nn gõy ngy cng nhiu, nhu cu s dng vt liu y sinh ngy cng tng, c bit nhu cu s dng vt liu y sinh cht lng cao Chớnh vỡ vy, hng nghiờn cu mi nhm nõng cao cht lng cho vt liu y sinh trờn c s kim loi v hp kim ngy cng c phỏt trin m rng Nhiu nghiờn cu v mng y sinh c ph trờn cỏc vt liu tr sinh hc ang c tin hnh nõng cao tớnh tng ng sinh hc gia cỏc mụ ca c th ngi vi b mt vt liu v ỏp ng cỏc yờu cu c bn ca vt liu s dng lnh vc cy ghộp xng, nhiu cụng trỡnh ó nghiờn cu tng hp mng hydroxyapatit (HAp) lờn b mt kim loi, hp kim nhm mang li cỏc sn phm y sinh cht lng cao phự hp nhu cu ca ngi [6] HAp cú cụng thc húa hc l Ca10(PO4)6(OH)2 Trong t nhiờn tn ti dng khoỏng cht, thuc h apatit v l khoỏng cht chớnh khung xng, rng ca ngi v ng vt HAp cú nhiu ng dng y sinh hc c tớnh quý giỏ ca chỳng: cú hot tớnh v tng thớch sinh hc cao vi cỏc t bo, cỏc mụ, khụng b c th o thi, tn ti nhiu trng thỏi hp Mt mng HAp mn, mng ph trờn xng nhõn to cú tỏc dng tng cng kh nng liờn kt vi cỏc mụ v xng t nhiờn Cú rt nhiu phng phỏp khỏc c s dng tng hp mng HAp trờn nn kim loi v hp kim nh: phng phỏp vt lý (plasma chõn khụng, phun nhit, phng phỏp phỳn x magnetron, phỳn x chựm ion, lng ng pha hi ), phng phỏp húa hc (sol-gel, nhỳng, ngõm, ộp núng ) v phng phỏp in húa [1, 7, 8] Mi phng phỏp u cú u v nhc im riờng Mng HAp tng hp bng phng phỏp in húa ang thu hỳt cỏc nh khoa hc bi vỡ: nhit phn ng thp, cú th ph lờn cht nn cú hỡnh dng phc tp, iu khin chiu dy mng, cú th tng hp c mng cú tinh khit cao [9-11] Chớnh vỡ u im ny nờn tờn ti c la chn: Nghiờn cu tng hp mng hydroxyapatit bng phng phỏp in húa trờn nn thộp khụng g 316L cú v khụng cú mng titan nitrua vi mc ớch gúp phn vo quỏ trỡnh nghiờn cu tng hp cng nh nh hng ng dng ca vt liu ph mng HAp lnh vc cy ghộp xng * Mc tiờu ca lun ỏn: Ch to thnh cụng mng HAp trờn nn thộp khụng g 316L (TKG316L) v thộp khụng g 316L ph TiN (TiN/TKG316L), cú hot tớnh sinh hc dung dch mụ phng dch c th ngi (SBF) * Ni dung nghiờn cu chớnh ca lun ỏn: Trờn c s mc tiờu nghiờn cu ó ra, ni dung nghiờn cu ca lun ỏn gm ba ni dung chớnh sau: Kho sỏt la chn cỏc iu kin thớch hp (nng dung dch, nhit , tc quột th, s ln quột, nng H2O2) v nghiờn cu c trng húa lý ca mng HAp tng hp trờn nn TKG316L Ch to mng TiN trờn nn TKG316L bng phng phỏp phỳn x manegtron mt chiu v kho sỏt la chn cỏc iu kin thớch hp (in th ỏp t, nhit , pH, nng H2O2, thi gian) tng hp mng HAp trờn nn TiN/TKG316L Nghiờn cu hot tớnh sinh hc ca bn loi vt liu TKG316L, HAp/TKG316L, TiN/TKG316L v HAp/TiN/TKG316L dung dch mụ phng dch c th ngi (SBF) CHNG 1: TNG QUAN 1.1 Tng quan chung v titan nitrua(TiN) 1.1.1 Tớnh cht ca TiN [12-14] 1.1.1.1 Tớnh cht vt lý TiN l hp cht ca titan v nit, cú mu ca kim loi vng, cng, bn nhit v bn n mũn cao, nhit núng chy 2950C, oxy húa chm (bt u oxy húa 800oC) v cú in tr sut khỏ nh (20-30 à.cm2), phn x cao vựng hng ngoi TiN nhit phũng tn ti trng thỏi rn v cú t l 5,22 g/cm3, gp ụi t ca thy tinh, nhng thp hn so vi hu ht cỏc kim loi TiN rt cng, nú c so sỏnh vi vt liu corundum (vt liu s dng cỏc cht mi mũn nh giy nhỏm ) Tớnh cht ca TiN ph thuc mt phn vo hm lng nit, hỡnh thỏi cu trỳc v kớch thc ht TiN cú cu trỳc tinh th ca mng tinh th mui, ú cỏc nguyờn t titan to thnh mt mng tinh th lp phng tõm din cũn cỏc nguyờn t nit nm cỏc hc bỏt din (hỡnh 1.1) Hỡnh 1.1: Cu trỳc mng tinh th ca TiN [14] 1.1.1.2 Tớnh cht húa hc TiN cú bn húa hc cao Trong khụng khớ ch b tn cụng dn dn nhit trờn 600oC v nhit 1200oC bu khớ quyn O2 hoc CO2 b oxy húa nhanh chúng Trong dung dch kim núng TiN b phõn hy v to amoniac 1.1.2 Mt s phng phỏp tng hp mng TiN TiN l vt liu cú tớnh cht c lý tt ú nú rt thớch hp lm lp trung gian h thng mng a lp Tuy nhiờn, tựy thuc vo mc ớch s dng khỏc m mng TiN c tng hp bng nhiu phng phỏp khỏc trờn cỏc loi vt liu nn khỏc nhau: lng ng hi húa hc (CVD), lng ng hi vt lý (PVD) [15] Nguyờn tc ca cỏc phng phỏp ny da trờn tin cht d bay hi hỡnh thnh mng trờn vt liu nn Phng phỏp PVD c thc hin bung kớn cha khớ tr vi ỏp sut thp khong di 10-2 bar nhit t 400oC 500oC thớch hp cho vic ch to cỏc dng c ngnh cụng nghip nh cỏc cụng c ct, cỏc dng c cy ghộp y sinh Cỏc phng phỏp PVD ph bin l phng phỏp phỳn x, h quang chõn khụng, xung laze [16-21] Phỳn x magnetron l k thut phỳn x (s dng c vi xoay chiu v mt chiu) ci tin t cỏc h phỳn x thụng dng bng cỏch t bờn di bia cỏc nam chõm nhm nõng cao hiu sut phỳn x T trng ca nam chõm cú tỏc dng by cỏc in t v ion li gn bia v tng hiu ng ion húa, tng s ln va chm gia cỏc ion, in t vi cỏc nguyờn t khớ ti b mt bia ú lm tng tc lng ng, gim s bn phỏ ca in t v ion trờn b mt mng, gim nhit v cú th to s phúng in ỏp sut thp hn [22] Mng mng TiN c tng hp trờn Si bng phng phỏp phỳn x Magnetron Kt qu nghiờn cu cu trỳc hỡnh hc v cu trỳc pha ó cho thy cú s thay i cu trỳc pha thay i iu kin to mng nh t l hn hp khớ argon v nit g gh b mt ca mng tng hp iu kin 100% nit tinh khit nh hn so vi mng TiN tng hp vi hn hp hai khớ nit v argon [23] Y.L Jeyachandran ti khoa Vt lý, i hc Bharathiar, n v C.Y Bao trng i hc Sichuan ó nghiờn cu tng hp lp ph titan v titan nitrua trờn kớnh bng phng phỏp phỳn x magnetron v tng hp mng HAp cú mt ca ion F- (FHAp) v cú mt c F- v Zn2+ (Zn-FHAp), trờn nn titan kim loi bng phng phỏp nhỳng dung dch cú cha Ca(CH3COO)2.2H2O + Zn (CH3COO)2.4H2O + 85% H3PO4 v 40% HF, pH =9, iu chnh bng NH4OH sau ú lm khụ 150oC v nhit 650oC thi gian 15 phỳt Kt qu chp AFM ca Ti v TiN cho thy b mt lp ph khỏ phng v ng u gh gh b mt ca Ti thay i t 2,1 n 2,8 nm v ca TiN t 1,3 n 3,5 nm (hỡnh 1.2) S phỏt trin ca cỏc vi khun Porphyromonas gingivalis ó c nghiờn cu trờn nhng vt liu tng hp c [24] Cỏc nghiờn cu ca h cho thy s phỏt trin ca vi khun l khỏc trờn mi loi vt liu Tựy vo tng iu kin c th cú th ng dng nhng vt liu ny ngnh cụng ngh sinh hc TiN Ti Hỡnh 1.2: Hỡnh nh AFM ca lp ph Ti v TiN [24] Mng TiN c ch to bng phng phỏp phỳn x magnetron mt chiu trờn thy tinh, h chõn khụng lm vic cú ỏp sut ti hn l 10-4 torr vi bia lm vt liu l Ti 99,96% kớch thc bia 10106 (mm) Khớ lm vic l khớ Ar (99,99%) v khớ hot tớnh l N2 (99,99%) chỳng c trn ln vi t l cho trc v c a vo bung chõn khụng bng h van kim T trng bờn ngoi mt bia c to bng nam chõm vnh cu ferit, cng t trng khong 350 Gauss Quỏ trỡnh to mng tin hnh vi ỏp sut 3.10-3 n 3.10-6 torr Th phỳn x thay i t 350 650 V, t l khớ N2/Ar thay i t 15% Kt qu cho mng TiN cú cu trỳc tinh th cao, tn ti cỏc mt mng (111), (200) v (311) (hỡnh 1.3) Mng cú in tr sut thp = 35 .cm ng vi cỏc thụng s to mng ti u: Th phỳn x ngng Up = 550 V, t l N2/Ar = 10%, khong cỏch gia bia v h = 4,5cm, ỏp sut phỳn x ton phn P = 3.10-3 torr, nhit 200oC Chit sut v h s tt ca mng bc súng 550nm l 1,14 v 2,13 [25] Hỡnh 1.3: Ph nhiu x ca cỏc mng TiN c to ti: Up=550 V; t l N2/Ar 10%; ỏp sut lm vic p=3 mtorr, nhit 200oC, khong cỏch bia v thay i: h=3,5cm; h=4,5cm; h=5,5cm [25] M H Islam v cỏc ng nghip S Y t vKhoa Sinh hc, i hc Cụng ngh Sydney ó tng hp mng Ti xen TiN trờn nn Si v thy tinh bng phng phỏp phỳn x mangetron mt chiu bung chõn khụng cha hn hp khớ Ar v N2 cú tinh khit cao, ỏp sut bung 510-6 Torr Bia Ti ( tinh khit 99,999%) ng kớnh cm, cỏch nn cm, Ti v TiN c tng hp nhit phũng vi in nng cung cp 1,5 kV [26] Mng Ti vi chiu dy khong 60 nm, sau ú mng TiN cú chiu dy 1ữ2,5 àm c tng hp bng cỏch thay i ỏp sut riờng phn ca N2 t lờn mTorr (ỏp sut tng ca Ar v N2 l 2,4 mTorr) v nng lng phỳn x bia Ti t 100 lờn 250 W Kt qu cho thy lu lng nit nh hng ti thnh phn ca TiN Vi ỏp sut 0,4 mTorr < N2< 0,8 mTorr, mng TiN cú mu vng, ngoi khong ỏp sut ny mng TiN cú mu vng sỏng Hỡnh thỏi hc b mt TiN thụ rỏp hn v kớch thc ht tng ỏp sut N2 tng (hỡnh 1.4) (a) (b) Hỡnh 1.4: Hỡnh nh SEM b mt TiN thay i ỏp sut N2: 0,4 mTorr (a) v 0,8 mTorr (b) [26] 1.1.3 ng dng ca TiN Vỡ TiN cú mu kim loi vng, bn húa, bn c lý v c bit cú cng cao nờn nú c ng dng nhiu cụng nghip lm mi khoan, lm li dao ct, lm vt liu trang trớ bo v, vt liu linh kin in t v vt liu np vớt xng dựng phu thut cy ghộp [27] Mng TiN c ch to trờn Si, cú in tr sut khong 25 .cm c ng dng lm hng ro khuch tỏn cụng ngh in t IC Vi u im ca tớnh cht c hc nh: cú mu kim loi vng, cng cao c ng dng cho mc ớch trang trớ v c to trờn thy tinh hoc MgO, mng cú in tr sut khong 13-192 .cm [25] Cỏc cụng c ct gt, khuụn ỳc, bỏnh rng, bi thng chu ng sut c hc v ng sut nhit rt cao lm vic, ú d b hng Khú khn ny c khc phc nu dựng cỏc vt liu cú cng cao Trong cụng ngh siờu ct hin ch cú lp ph kim cng c ng dng Tuy nhiờn lp ph ny khỏ t v him Bng phng phỏp phỳn x magnetron vi hm lng nit thay i ữ 30% mng TiN dy 20 m trờn li dao ct cú cng v chu mi mũn tt hn mng Ni c dựng trc ú Kt qu nghiờn cu cho thy lp ph TiN vi hm lng 3% N2 ỏp ng yờu cu cụng ngh siờu ct v dn thay th mng kim cng [28] Mng TiN ngoi ng dng sn phm cụng nghip, in t, trang trớ gia dng cũn c ng dng lnh vc y sinh nh cụng ngh lm rng, lm np vớt xng bi vỡ nú cú mụ un n hi thp, tng thớch sinh hc v bn n mũn cao mụi trng sinh lý Titan v hp kim ca titan (Ti6Al4V, Ti6Al7Nb) cng c cỏc nh khoa hc nghiờn cu v ng dng lm vt liu y sinh Cỏc kt qu nghiờn cu cho thy cỏc vt liu ny cú tớnh tng thớch sinh hc cao hn so vi cỏc vt liu kim loi v hp kim khỏc ó s dng trc ú nh: Cr-Ni, hp kim Co [29, 30] Tuy nhiờn, giỏ thnh ca titan v hp kim ca nú khỏ cao ú vic ng dng vo thc t gp nhiu khú khn Cỏc lp ph titan nitrua (TiN) v titan cú hot tớnh sinh hc v chng n mũn tt mụi trng dch sinh hc, c ph trờn cỏc chi tit, thit b, c vớt ch to bng thộp khụng g dựng sa cha, cy ghộp chnh hỡnh u gi, xng hụng v np vớt xng [26] Trong khong 10 nm tr li õy, cỏc kt qu th nghim lõm sng cho thy lp ph titan v TiN cú hot tớnh sinh hc dung dch mụ phng dch c th ngi Mng TiN dy m c ph trờn thộp 316L bng phng phỏp PVD, sau ú ngõm dung dch mụ phng c th ngi ca Hank 28 ngy Kt qu cho thy vt liu thộp cú ph TiN cú kh nng chng n mũn tt hn vt liu thộp khụng cú TiN, ng thi kt qu o phõn cc Tafel v tng tr in húa cho thy mng TiN l lp ph phự hp trờn nn kim loi cho cỏc ng dng y sinh [31] 1.2 Tng quan chung v hydroxyapatit (HAp) 1.2.1 Tớnh cht ca HAp 1.2.1.1 Tớnh cht vt lý Hydroxyapatit (HAp), Ca10(PO4)6(OH)2, tn ti trng thỏi tinh th, cú mu trng, trng ng, vng nht hoc xanh l, tu theo iu kin hỡnh thnh, kớch thc ht v trng thỏi tn ti HAp cú nhit núng chy 1760 oC v nhit sụi 2850oC, tan nc 0,7 g/L, lng mol phõn t 1004,6 g, lng riờng l 3,08 g/cm3, cng theo thang Mohs bng Bng phng phỏp hin vi in t SEM hoc TEM cú th nhn bit c tinh th HAp tn ti cỏc dng khỏc nhau: dng hỡnh que, hỡnh kim, hỡnh vy, hỡnh si, hỡnh cu, hỡnh tr (hỡnh 1.5) [7, 32] (a) (b) (c) (d) (e) (f) Hỡnh 1.5: nh hin vi in t ca cỏc tinh th HAp [32-34] (a) - Dng hỡnh que (b) - Dng hỡnh tr (c) - Dng hỡnh cu (d) - Dng hỡnh si (e) - Dng hỡnh vy (f) - Dng hỡnh kim HAp cú hai dng cu trỳc l dng lc phng (hexagonal) v dng n t (monoclinic) Khi c iu ch nhit t 25 n 100 oC HAp cú dng lc phng v cú dng n t nung dng lc phng 850oC khụng khớ sau ú lm ngui n nhit phũng Tuy nhiờn, gin pha X-ray ca hai dng ny ging c v s lng v v trớ ca cỏc pic nhiu x, ch khỏc v cng pic i vi dng n t cng cỏc pic yu hn so dng lc phng khong 1% [36] Cu trỳc ca HAp tng hp, HAp cú thnh phn ca xng v ng rng thng cú dng lc phng v thuc nhúm khụng gian P6 3/m vi cỏc hng s mng a = 0,9417 nm, b = 0,9417 nm v c = 0,6875 nm, = = 90o v 10 TI LIU THAM KHO Dong-Yang Lin, Xiao-Xiang Wang Electrodeposition of hydroxyapatite coating on CoNiCrMo substrate in dilute solution Surface & Coatings Technology 204 (2010) 3205-3213 S Tamilselvi, V Raman, N Rajendran Corrosion behaviour 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