Nghiên cứu tổng hợp điện hóa và đặc trưng màng HAp trên nền hợp kim ti6al4v và cocrnimo

B GIO DC V O TO TRNG I HC S PHM H NI o0o BI DUY THNH NGHIấN CU TNG HP IN HểA V C TRNG MNG HYDROXYAPATIT TRấN NN HP KIM Ti6Al4V V CoCrNiMo Chuyờn ngnh : Húa lý thuyt v Húa lý Mó s : 60.44.01.19 LUN VN THC S KHOA HC HểA HC Ngi hng dn khoa hc: PGS.TS inh Th Mai Thanh H Ni - 2017 LI CM N Em xin trõn trng cm n cỏc thy cụ Trng i hc s phm H Ni, cỏc thy cụ Vin K thut nhit i Vin Hn lõm Khoa hc v Cụng ngh Vit Nam ó ging dy, cung cp kin thc khoa hc, to iu kin cho em hc v nghiờn cu thi gian qua Em xin by t li cm n sõu sc ti PGS.TS inh Th Mai Thanh, phú vin trng Vin K thut nhit i - Vin Hn lõm Khoa hc v Cụng ngh Vit Nam ó hng dn tn tỡnh, sõu sỏt v giỳp em quỏ trỡnh thc hin v hon thnh lun ny Tụi xin gi li cm n n cỏc cỏn b phũng n mũn bo v kim loi: Ch Nguyn Th Thm, Phm Th Nm, Nguyn Thu Phng v cỏc anh ch hc viờn, cỏc bn sinh viờn ó luụn ng viờn giỳp tụi quỏ trỡnh thc hin ti nghiờn cu ca mỡnh Tụi xin gi li cm n n gia ỡnh, bn bố ó to iu kin v vt cht, tinh thn v luụn ng viờn, khuyn khớch tụi thi gian hc v thc hin lun H Ni, thỏng nm 2017 Tỏc gi lun Bựi Duy Thnh DANH MC CC Kí HIU V CH VIT TT DCPD : icanxi hidrophotphat ihyrat (CaHPO4.2H2O) HAp : Hydroxyapatit HAp/CoCrNiMo : Mng hydroxyapatit ph trờn nn CoCrNiMo HAp/Ti6Al4V : Mng hydroxyapatit ph trờn nn Ti6Al4V IR : Ph hng ngoi EOCP : in th mch h SEM : Kớnh hin vi in t quột SBF : Dung dch mụ phng dch c th ngi SCE : in cc calomen bóo hũa TCP : Canxi photphat Ca3(PO4)2 V/SCE : n v in th so vi in cc calomen XRD : Nhiu x tia X OCP : Octacanxi photphat MC LC M U 1 Lý chn ti Mc ớch nghiờn cu i tng nghiờn cu Nhim v nghiờn cu Phng phỏp nghiờn cu Nhng úng gúp mi CHNG 1: TNG QUAN 1.1 Tng quan chung v hydroxyapatit (HAp) 1.1.1 Tớnh cht ca HAp 1.1.1.1 Tớnh cht vt lý 1.1.1.2 Tớnh cht hoỏ hc 1.1.1.3 Tớnh cht sinh hc 1.1.2 Vai trũ v ng dng ca HAp 1.1.2.1 ng dng ca HAp bt 1.1.2.2 ng dng ca HAp dng gm xp 1.1.2.3 ng dng ca HAp dng composit 1.1.2.4 ng dng ca HAp dng mng 1.2 Tỡnh hỡnh nghiờn cu tng hp HAp trờn th gii v nc 10 1.2.1 Tỡnh hỡnh nghiờn cu trờn th gii 10 1.2.1.1 Phng phỏp vt lý v phng phỏp húa hc 10 1.2.1.2 Phng phỏp in húa 13 1.2.2 Tỡnh hỡnh nghiờn cu nc 26 CHNG 2: THC NGHIM V PHNG PHP NGHIấN CU 29 2.1 Húa cht 29 2.2 Tng hp in húa HAp/CoCrNiMo v HAp/Ti6Al4V 29 2.2.1 Chun b vt liu nn 29 2.2.2 iu kin tng hp mng HAp 29 2.2.3 Th nghim dung dch mụ phng dch c th ngi (SBF) 30 2.3 Cỏc phng phỏp nghiờn cu 31 2.3.1 Phng phỏp quột th ng 31 2.3.2 Phng phỏp o in th mch h theo thi gian 32 2.3.3 Phng phỏp tng tr in húa 32 2.4 Cỏc phng phỏp phõn tớch 33 2.4.1 Phng phỏp ph hng ngoi (IR) 33 2.4.2 Kớnh hin vi in t quột (SEM) 33 2.4.3 Nhiu x tia X (XRD) 33 2.4.4 Xỏc nh lng v chiu dy mng 34 CHNG KT QU V THO LUN 35 3.1 Tng hp mng HAp/Ti6Al4V 35 3.1.1 ng cong phõn cc catụt ca Ti6Al4V 35 3.1.2 nh hng ca khong quột th n tng hp HAp/Ti6Al4V 36 3.1.3 nh hng ca s ln quột n tng hp HAp/Ti6Al4V 41 3.1.4 nh hng ca tc quột th n tng hp HAp/Ti6Al4V 43 3.1.5 nh hng ca nng H2O2 n tng hp HAp/Ti6Al4V 44 3.1.6 nh hng ca nhit n tng hp HAp/Ti6Al4V 46 3.1.7 nh hng ca pH n tng hp HAp/Ti6Al4V 47 3.2 Tng hp mng HAp/CoCrNiMo 48 3.2.1 nh hng ca khong quột th n tng hp HAp/CoCrNiMo 48 3.2.2 nh hng ca khong quột th n tng hp HAp/CoCrNiMo 49 3.2.3 nh hng ca s ln quột n tng hp HAp/CoCrNiMo 52 3.2.4 nh hng ca pH dung dch n tng hp HAp/CoCrNiMo 54 3.2.5 nh hng ca nng H2O2 n tng hp HAp/CoCrNiMo 55 3.2.6 nh hng ca tc quột n tng hp HAp/CoCrNiMo 56 3.2.7 nh hng ca nhit tng hp n tng hp HAp/CoCrNiMo 57 3.3 Th nghim in vitro 63 3.3.1 Xỏc nh pH ca dung dch SBF theo thi gian ngõm 64 3.3.2 Xỏc nh tn hao lng ca mu ngõm SBF 65 3.3.3 in th mch h 66 3.3.4 o in tr phõn cc 68 3.3.5 Tng tr in húa 71 3.3.6 Phõn tớch c trng húa lý ca mng apatit hỡnh thnh dung dch SBF 74 KT LUN 79 DANH MC TI LIU THAM KHO 80 DANH MC BNG Bng 2.1: Thnh phn cỏc nguyờn t ca vt liu nn CoCrNiMo v Ti6Al4V 29 Bng 2.2 Thnh phn ca lớt dung dch SBF 31 Bng 3.1: Chiu dy mng HAp tng hp cỏc khong quột th khỏc 38 Bng 3.2 Khi lng v chiu dy mng HAp ti nhng khong th khỏc 51 Bng 3.3: S bin i in lng ca quỏ trỡnh tng hp, lng, bỏm dớnh v chiu dy ca mng thay i s ln quột 53 Bng 3.4: Khi lng v chiu dy mng HAp tng hp pH khỏc 55 Bng 3.5: Khi lng v chiu dy ca mng HAp vi s cú v khụng cú mt ca H2O2 dung dch tng hp 55 Bng 3.6 S bin i lng v chiu dy ca mng HAp theo tc quột 57 Bng 3.7: Khi lng v chiu dy mng HAp tng hp cỏc nhit khỏc 58 Bng 3.8 Thnh phn húa hc ca mng HAp 60 Bng 3.9: Thnh phn cỏc nguyờn t ca b mt mng HAp/Ti6Al4V xỏc nh bi XPS 62 Bng 3.10: Thnh phn cỏc nguyờn t ca b mt mng HAp/CoCrNiMo xỏc nh bi XPS 62 DANH MC HèNH Hỡnh 1.1: nh hin vi in t ca cỏc tinh th HAp Hỡnh 1.2: Cu trỳc ca HAp [3] Hỡnh 1.3: Cụng thc cu to ca phõn t HAp [33] Hỡnh 1.4: Hỡnh nh vt liu cy ghộp c ph Hap [3] 10 Hỡnh 1.5: Ph IR ca mng HAp v HAp pha Mg 11 Hỡnh 1.6: Hỡnh nh AFM ca HAp v HAp pha Mg trc v sau cy t bo ngy 12 Hỡnh 1.7: Hỡnh nh TEM ca Mn-HAp tng hp (a) v ti 4500C (b) 12 Hỡnh 1.8: nh SEM ca vi khun P gingivalis nuụi cy trờn TiN, FHAp v ZnFHA 13 Hỡnh 1.9: nh SEM nn CoCrMo (trỏi) v mng HAp/ CoCrMo tng hp iu kin [Ca2+] = 0,05M, [PO43-] = 0,04M v H2O2 22,11 ml/L (phi) [50] 14 Hỡnh 1.10: nh SEM mng HAp/CoCrNiMo tng hp ti cỏc in th khỏc nhau: -1,4 (a), -1,6 (b), -1,8 (c), -2,0 (d) v -2,2 V (e) 15 Hỡnh 1.11: Gin XRD ca mng HAp tng hp ti in th khỏc [51] 16 Hỡnh 1.12: Hỡnh nh AFM ca HAp vi thi gian tng hp 15 phỳt (a) v 30 phỳt (b) 16 Hỡnh 1.13: nh SEM ca HAp vi thi gian tng hp 10 phỳt (a) v 20 phỳt (b)17 Hỡnh 1.14: Gin XRD (a) v IR (b) ca HAp thay i thi gian tng hp 17 Hỡnh 1.15: nh SEM ca mng HAp/CoCrMo tng hp pH dung dch khỏc nhau: (a, b) pH = 4,5, (c, d) pH = 4,7 (e) pH = 5,1, (f, g) pH = 5,5, (h, i) pH = 6,3 18 Hỡnh 1.16: ng cong Tafel ca mng HAp/CoCrMo tng hp pH khỏc nhau19 Hỡnh 1.17: nh SEM mng HAp/CoCrMo tng hp iu kin ti u 19 Hỡnh 1.18: XRD ca HAp/Ti6Al4V sau ngõm SBF: mu (a) v mu (b) 22 Hỡnh 1.19: Gin nhiu x tia X ca mng HAp 23 Hỡnh 1.20: Hỡnh nh SEM: A1-HAp (a), A2-HAp (b) v A3-HAp (c) 23 Hỡnh 1.21: Hỡnh nh SEM ca mng HAp tng hp trờn nn Ti v Ti6Al4V dung dch MCPM (a, b) v SCPC (c, d) 24 Hỡnh 1.22: nh SEM ca TiO2/Ti6Al4V v mng HAp/TiO2/Ti6Al4V 26 Hỡnh 1.23: Hỡnh nh AFM ca Ti6Al4V (a), TiO2/Ti6Al4V (b) v mng HAp/TiO2/Ti6Al4V (c) 26 Hỡnh 3.1: ng cong phõn cc catụt ca in cc Ti6Al4V dung dch tng hp HAp 35 Hỡnh 3.2: S bin i lng mng HAp thay i khong quột th 37 Hỡnh 3.3: Ph IR ca HAp tng hp cỏc khong quột th khỏc nhau: (a) ữ -2,5 V/SCE; (b) ữ -2,2 V/SCE; (c) ữ -2 V/SCE; (d) ữ -1,9 V/SCE; (e) ữ -1,8 V/SCE; 38 Hỡnh 3.4: Gin nhiu x tia X ca HAp tng hp cỏc khong th khỏc 39 Hỡnh 3.5: Hỡnh nh SEM ca mng HAp tng hp cỏc khong quột th khỏc nhau: (a) ữ -1,8; (b) ữ -1,9; (c) ữ -2,0; 40 (d) ữ -2,2 v (e) ữ -2,5 V/SCE 40 Hỡnh 3.6: S bin i lng HAp thu c thay i s ln quột 41 Hỡnh 3.7: Hỡnh nh SEM ca mng HAp tng hp thay i s ln quột th: (a) 1; (b) 3; (c) 5; (d) v (e) 10 ln 42 Hỡnh 3.8: S bin i lng mng HAp tng hp theo tc quột th 44 Hỡnh 3.9: S bin i lng HAp theo nng H2O2 45 Hỡnh 3.10: Hỡnh nh SEM ca mng HAp tng hp nng H2O2 khỏc nhau: 0% (a), 3% (b), 6% (c), 9% (d) 46 Hỡnh 3.11: Hỡnh nh SEM ca mng HAp tng hp cỏc nhit : 25 0C (a), 350C (b), 500C (c), 600C (d) 47 Hỡnh 3.12: S bin i lng mng HAp tng hp theo pH 48 Hỡnh 3.13 ng phõn cc catụt ca CoCrNiMo dung dch cht in phõn49 Hỡnh 3.14 S bin i lng mng HAp vi nhng khong th khỏc 50 Hỡnh 3.15 Ph FTIR ca mng HAp tng hp ti cỏc khong quột th khỏc 52 Hỡnh 3.16: Hỡnh nh SEM ca mng HAp tng hp dung dch vi khong quột th ữ -1,7 V/SCE, mV/s, 50oC vi s ln quột khỏc nhau: ln quột (a), ln quột (b) v ln quột (c) 53 Hỡnh 3.17: ng cong phõn cc catot ca CoCrNiMo dung dch tng hp pH khỏc 54 Hỡnh 3.18 ng phõn cc catụt ca CoCrNiMo dung dch in phõn vi tc quột khỏc 56 Hỡnh 3.19 S bin i lng mng HAp theo tc quột 57 Hỡnh 3.20: Khi lng ca mng HAp tng hp ti cỏc nhit khỏc 58 Hỡnh 3.21 Gin nhiu x tia X ca mng HAp tng hp ti cỏc nhit khỏc nhau: 35, 50 v 70oC 59 Hỡnh 3.22 Ph tỏn x nng lng tia X ca mng HAp tng hp 50oC 60 Hỡnh 3.23: Hỡnh nh SEM ca mu HAp/CoCrNiMo 61 Hỡnh 3.24: Ph XPS ca HAp/Ti6Al4V (a) v cỏc nguyờn t Ca (b), P (b) v O (c) di nng lng liờn kt t n 1200 eV 63 Hỡnh 3.25: Ph XPS ca HAp/CoCrNiMo (a) v cỏc nguyờn t Ca (b), P (b) v O (c) di nng lng liờn kt t n 1000 eV 63 Hỡnh 3.26: S bin i pH ca dung dch SBF theo thi gian ngõm mu: (a) CoCrNiMo, (b) Ti6Al4V, (c) HAp/Ti6Al4V v (d) HAp/CoCrNiMo 64 Hỡnh 3.27: S bin i lng mu CoCrNiMo, Ti6Al4V, HAp/CoCrNiMo v HAp/Ti6Al4V theo thi gian ngõm SBF 66 Hỡnh 3.28: S bin i in th mch h theo thi gian ngõm mu SBF ca: (a) CoCrNiMo, (b) Ti6Al4V, (c) HAp/CoCrNiMo v (d) HAp/Ti6Al4V67 Hỡnh 3.29: S bin i Rp ca mu CoCrNiMo (a), Ti6Al4V (b), HAp/CoCrNiMo (c) v HAp/Ti6Al4V (d) theo thi gian ngõm mu dung dch SBF 69 Hỡnh 3.30: S bin i icorr ca CoCrNiMo (a), Ti6Al4V (b), HAp/CoCrNiMo (c) v HAp/Ti6Al4V (d) theo thi gian ngõm dung dch SBF 70 Hỡnh 3.31: Ph tng tr dng Bode ca mu CoCrNiMo, Ti6Al4V, HAp/CoCrNiMo v HAp/Ti6Al4V theo thi gian ngõm mu dung dch SBF72 Nh vy, vt liu cú ph mng HAp (HAp/CoCrNiMo, HAp/Ti6Al4V) cú mụ un tng tr luụn ln hn hai vt liu nn CoCrNiMo, Ti6Al4V Ti mi thi im ngõm, giỏ tr mụ un tng tr ti tn s 10mHz ca vt liu c sp xp nh sau: HAp/Ti6Al4V > HAp/CoCrNiMo > Ti6Al4V > CoCrNiMo Cỏc kt qu ny phự hp vi kt qu o in tr phõn cc trờn 3.3.6 Phõn tớch c trng húa lý ca mng apatit hỡnh thnh dung dch SBF Hỡnh 3.33, 3.34, 3.35 v 3.36 gii thiu hỡnh nh SEM ca bn loi vt liu CoCrNiMo, Ti6Al4V, HAp/CoCrNiMo v HAp/Ti6Al4V trc v sau ngõm dung dch SBF vi thi gian khỏc Trờn b mt cú th quan sỏt thy s hỡnh thnh mng apatit sau ngõm SBF i vi c bn vt liu Vi hai vt liu nn CoCrNiMo, Ti6Al4V, sau 21 ngy ngõm dung dch SBF quan sỏt thy cú s hỡnh thnh cỏc tinh th apatit trờn b mt, nhiờn cỏc tinh th apatit khụng nhiu, khụng che ph hon ton b mt nn Hỡnh nh SEM quan sỏt thy cỏc v trớ ca nn Hỡnh 3.34 th hin hỡnh nh SEM ca HAp/CoCrNiMo trc v sau ngõm dung dch SBF vi thi gian khỏc nhau: 7, 14 v 21 ngy Trc ngõm dung dch SBF quan sỏt thy cỏc tinh th HAp cú dng tm v sp xp khỏ ng nht trờn b mt nn Sau ngy ngõm dung dch SBF, cỏc mm tinh th apatit ó c quan sỏt Dng tm ca HAp trc ngõm ó c bao ph hon ton bi cỏc tinh th apatit mi, to thnh cỏc cm ging nh san hụ Khi ngõm vi thi gian di hn, s phỏt trin ca cỏc tinh th apatit tng Sau 14 ngy ngõm, cỏc tinh th apatit phỏt trin vi mt dy hn c bit hỡnh nh SEM quan sỏt c sau 21 ngy ngõm cho thy cỏc tinh th apatit phỏt trin to thnh mt dy trờn b mt vt liu Mng HAp trờn b mt nn Ti6Al4V trc ngõm dung dch SBF cú dng hỡnh vy, chỳng sp xp co cm to thnh nhng ht ln Sau 74 ngõm dung dch SBF, hỡnh thỏi cú s thay i rừ rng Nú cho thy s hỡnh thnh ca cỏc tinh th apatit trờn b mt ca vt liu Cỏc tinh th apatit quan sỏt c cú dng hỡnh tr v chỳng cm li thnh nhúm ging nh hỡnh dng ca cõy xng rng Tng t nh vi vt liu HAp/CoCrNiMo, hỡnh nh SEM ca vt liu HAp/Ti6Al4V sau 21 ngy dung dch SBF, tinh th apatit phỏt trin to thnh mt dy trờn b mt ca vt liu Cỏc kt qu v s hỡnh thnh ca cỏc tinh th apatit l phự hp vi s gim pH v s tng lng mu quỏ trỡnh ngõm Kt qu cho thy kh nng tng thớch sinh hc ca cỏc vt liu trong dung dch SBF, c bit l vi hai vt liu c ph mng HAp (HAp/CoCrNiMo v HAp/Ti6Al4V) Hỡnh 3.33: nh SEM ca CoCrNiMo trc v sau 21 ngy ngõm dung dch SBF 75 Hỡnh 3.34: nh SEM ca HAp/CoCrNiMo trc v sau ngõm dung dch SBF vi thi gian khỏc Hỡnh 3.35: nh SEM ca Ti6Al4V trc v sau 21 ngy ngõm dung dch SBF 76 Hỡnh 3.36: nh SEM ca HAp/Ti6Al4V trc v sau ngõm dung dch SBF vi thi gian khỏc khng nh kt qu phõn tớch bng SEM v s hỡnh thnh mng HAp dung dch SBF, tin hnh phõn tớch thnh phn pha ca vt liu CoCrNiMo v Ti6Al4V sau 21 ngy ngõm mu dung dch SBF (hỡnh 3.37) Trờn gin pha thy xut hin hai pic c trng quan trng nht ca HAp gúc 26o v 32o, ngoi cũn nhng pic c trng cho hai vt liu nn CoCrNiMo, Ti6Al4V C- ờng độ nhiễu xạ *: HAp o: Ti CoNiCrMo * * (b) * * 20 * 30 40 (độ) 50 (a) * 60 70 Hỡnh 3.37: Gin nhiu x tia X ca apatit hỡnh thnh trờn CoCrNiMo (a) v Ti6Al4V (b) SBF sau 21 ngy ngõm mu Nh vy, kt qu th nghim dung dch SBF ca bn loi vt liu CoCrNiMo, Ti6Al4V, HAp/CoCrNiMo v HAp/Ti6Al4V cho thy cú s hỡnh thnh mng apatit sau 21 ngy ngõm mu, mng apatit cú cu trỳc tinh th 77 dng xng rng hay san hụ, cu trỳc phõn t v thnh phn pha tng t nh HAp tng hp in húa Vt liu cú ph mng HAp cú hot tớnh sinh hc tt hn vt liu khụng ph HAp 78 KT LUN - ó tng hp thnh cụng mng HAp trờn hai nn hp kim y sinh Ti6Al4V v CoCrNiMo bng phng phỏp in húa - La chn c iu kin thớch hp tng hp mng HAp/Ti6Al4V: khong quột th ữ V/SCE, ln quột vi tc quột mV/s, nhit 50C dung dch cht in phõn cú thnh phn Ca(NO3)2.4H2O 3x10-2 M, NH4H2PO4 1,8x10-2 M, NaNO3 0,15 M Mng HAp/Ti6Al4V thu c cú chiu dy khong 7,8 àm Cỏc kt qu phõn tớch IR, XRD cho thy phõn t HAp cú cha cỏc nhúm chc c trng: OHv PO43-, mng HAp cú cu trỳc tinh th, n pha vi gúc c trng khong 26o v 32o Hỡnh nh SEM cho thy mng HAp cú dng hỡnh vy, chỳng sp xp thnh cỏc cm ging san hụ - La chn c iu kin thớch hp tng hp mng HAp/CoCrNiMo: khong quột th ữ 1,7 V/SCE, ln quột vi tc quột mV/s, nhit 50C dung dch cht in phõn cú thnh phn Ca(NO3)2.4H2O 3x10-2 M, NH4H2PO4 1,8x10-2 M, NaNO3 0,15 M Mng HAp/CoCrNiMo thu c dng tm, chiu dy khong 8,8 àm, cú cu trỳc tinh th, n pha ca HAp - Kt qu nghiờn cu din bin n mũn ca loi vt liu CoCrNiMo, 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đặc biệt nhà khoa học C.F.Koch cộng nghiên cứu tổng hợp màng HAp kim loại hợp kim titan phương pháp mạ xung laze Những kết nghiên cứu màng HAp. .. nhiệt độ để tổng hợp màng HAp chất lượng cao Mục đích nghiên cứu - Xác định điều kiện thích hợp để tổng hợp HAp hợp kim Ti6Al4V CoCrNiMo - Xác định tính chất đặc trưng màng HAp tổng hợp - Xác định... Pháp: nghiên cứu tổng hợp điện hóa màng HAp trên hợp kim Ti6Al4V CoCrNiMo CHƯƠNG 1: TỔNG QUAN 1.1 Tổng quan chung hydroxyapatit (HAp) 1.1.1 Tính chất HAp 1.1.1.1 Tính chất vật lý Hydroxyapatit (HAp) ,