16 1 Vol 16 No 1 2010 2 ELECTROCHEMISTRY Feb 2010 1006-3471 2010 01-0074-05 TiO 2 /HA Tyrode s * 361005 Tafel EIS TiO 2 HA TiO 2 Tyrode s TiO 2 O646 A 1 1 1 TiO 2 10 mm 10 mm 2 mm 400 # 600 # 800 # 1200 # 1500 # 10 mi 20 V 10 0 12 mol /L NaF 0 5 mol /L H 3 PO 4 45 mi 1-9 TiO HA Hydroxyapatite 2 /Ti 1 2 HA TiO 2 TiO 2 /Ti HA 2 5 10-3 mol /L CaCl 2 1 67 10-3 mol /L NH 4 H 2 PO 4 0 15 mol /L NaCl 0 05 TiO 2 mol /L Tris Tris hydroxylmethyl -amio-methae ph 7 2 HA HA Tyrode s 80 10 μa / cm 2 10 s 2009-08-19 2009-08-30 * Tel 86-592 2189354 E-mail cjli@ xmu edu c 20773100
1 TiO 2 /HA Tyrode s 75 1 Fig 1 TiO 2 a HA b SEM SEM top-view ad cross-sectioal iset images of the TiO 2 aotubes arrays a ad the HA coatig b j 10 ma /cm 2 0 2 s 100 1b TiO 2 10 ma /cm 2 SEM 4000 s Autolab PGSTAT 30 HA 110 m HA 8 μm 2 HA / HA /TiO 2 /Ti TiO 2 /Ti XRD Ti 1 3 HA HA Autolab TiO 2 SCE 13-14 TiO 2 Ti TiO 2 /Ti HA /TiO 2 / Ti Tafel ± 120 mv 0 167 mv s - 1 10 4 ~ 10-2 Hz 10 mv Tyrode s 11 NaCl 8 00 g + KCl 0 20 g + CaCl 2 0 20 g + NaHCO 3 1 00 g + MgCl 2 0 10 g + NaH 2 PO 4 0 05 g + 1 00 g + H 2 O 1 L ph 7 4 37 SJH-4S 2 HA /TiO 2 /Ti XRD Fig 2 XRD patter of the HA /TiO 2 /Ti 2 2 1 2 2 1a TiO 2 3 Ti TiO 2 /Ti HA /TiO 2 /Ti SEM ph = 7 4 Tyrode s TiO Tafel 2 12-13 80 ~ 100 m Ti - 0 159 V vs SCE 650 m Ti TiO 2 Ti TiO 2 /Ti
76 2010-0 279 V HA /TiO 2 / 4 TiO 2 /Ti HA /TiO 2 /Ti Ti TiO 2 /Ti 60 ph = 7 4 Tyrode s mv Ti Nyquist c Ti TiO 2 TiO 2 /Ti TiO 2 HA HA Tyrode s TiO 2 1 3 Tafel R p TiO 2 /Ti TiO 2 HA HA /TiO 2 /Ti TiO 2 /Ti Bode a TiO 2 /Ti HA /TiO 2 /Ti Ti HA /TiO 2 /Ti TiO 2 /Ti Bode b Ti 1 TiO 2 /Ti 2 HA /TiO 2 /Ti 3 5 2 R 1 R 2 Q 1 3 TiO a TiO 2 /Ti b HA /TiO 2 /Ti c 2 /Ti R 3 TiO 2 Q 2 ph = 7 4 Tyrode s HA /TiO 2 /Ti R 3 R 4 HA Fig 3 Polarizatio curves of the Ti a TiO 2 /Ti b ad HA /TiO 2 /Ti c electrodes i Tyrode s solutio TiO 2 Q 2 Q 3 HA TiO 2 W Warburg Tab 1 1 TiO 2 /Ti HA /TiO 2 /Ti ph = 7 4 Tyrode s Tafel Corrosio fittig parameters from Tafel curvers for Ti TiO 2 /Ti ad HA /TiO 2 /Ti i Tyrode s solutio Samples i corr /A cm 2 R p / b c /V dec - 1 b a /V dec - 1 E corr /V vs SCE Ti 2 23 10-8 5 42 106 0 123 0 572-0 159 TiO 2 /Ti 4 90 10-8 2 46 106 0 095 0 315-0 279 HA /TiO 2 /Ti 5 78 10-8 1 59 106 0 079 0 342-0 223 Tab 2 Samples 2 TiO 2 /Ti HA /TiO 2 /Ti Tyrode s Fittig parameters of EIS usig the equivalet circuits for Ti TiO 2 /Ti ad HA /TiO 2 /Ti i Tyrode s solutio R 1 / Q 1 Y 0 / Q R 2 / 2 W / Y 0 / R 3 / Q 3 Y 0 / Ti 1302 19 10-5 093 310 10 6 - - - - - - TiO 2 /Ti 987 77 10-5 067 194 10 3 142 10-5 784 10-5 082 119 10 4 - - - HA/TiO 2 /Ti 1504 84 10-5 086 542 10 5 139 10-4 084 160 10 4 164 10-4 086 978 R 4 /
1 TiO 2 /HA Tyrode s 77 4 4 Fig 4 Fig 4 TiO 2 /Ti HA /TiO 2 /Ti ph = 7 4 Tyrode s a Bode b c Nyquist The EIS of Ti TiO 2 /Ti ad HA /TiO 2 /Ti electrodes i Tyrode s solutio a Bode Z modulus b phase agle plots c Nyquist plots 5 Fig 5 3 Tyrode s a b TiO 2 /Ti c HA /TiO 2 /Ti Equivalet circuits proposed for fittig EIS of the three samples i Tyrode s solutio a Ti b TiO 2 /Ti c HA /TiO 2 /Ti 2 Ti HA TiO 2 /Ti HA / TiO 2 /Ti R 2 5 42 10 5 TiO 2 TiO 2 /Ti R 2 1 94 10 3 TiO 2 /Ti HA Tafel HA TiO 2 /Ti Tyrode s TiO 2 /Ti HA 3 Refereces 1 Thair L Mudali U K Bhuvaeswara N et al Nitroge io implatatio ad i vitro corrosio behavior of as-
78 2010 cast Ti-6Al-7Nb alloy J Corrosio Sciece 2002 44 11 2439-2457 2 Coelho P G de Assis S L Costa I et al Corrosio resistace evaluatio of a Ca-ad P-based bioceramic thi coatig i Ti-6Al-4V J Joural of Materials Sciece- Materials i Medicie 2009 20 1 215-222 3 Pa J Leygraf C Thierry D et al Corrosio resistace for biomaterial applicatios of TiO 2 films deposited o titaium ad stailess steel by io-beam-assisted sputterig J Joural of Biomedical Materials Research 1997 35 3 309-318 4 Aparicio C Gil F J Foseca C et al Corrosio behaviour of commercially pure titaium shot blasted with differet materials ad sizes of shot particles for detal implat applicatios J Biomaterials 2003 24 2 263-273 5 Fadl-Allah S A El-Sherief R M Badawy W A Electrochemical formatio ad characterizatio of porous titaia TiO 2 films o Ti J Joural of Applied Electrochemistry 2008 38 10 1459-1466 6 Hoche H Scheerer H Probst D et al Developmet of a plasma surface treatmet for magesium alloys to esure sufficiet wear ad corrosio resistace J Surface ad Coatigs Techology 2003 174 1018-1023 7 Yildiz F Yetim A F Alsara A et al Wear ad corrosio behaviour of various surface treated medical grade titaium alloy i bio-simulated eviromet J Wear 2009 267 5 /8 695-701 8 Nie X Leylad A Matthews A Depositio of layered b- ioceramic hydroxyapatite /TiO 2 coatigs o titaium alloys usig a hybrid techique of micro-arc oxidatio ad electrophoresis J Surface ad Coatigs Techology 2000 125 1 /3 407-414 9 Kim H W Koh Y H Li L H et al Hydroxyapatite coatig o titaium substrate with titaia buffer layer processed by sol-gel method J Biomaterials 2004 25 13 2533-2538 10 Kar A Raja K S Misra M Electrodepositio of hydroxyapatite oto aotubular TiO 2 for implat applicatios J Surface ad Coatigs Techology 2006 201 6 3723-3731 11 Xie J T Zhao J Experimetal physiology M Beijig Higher Educatio Press 2002 210 12 Gog D Grimes C A Varghese O K Titaium oxide aotube arrays prepared by aodic oxidatio J Joural of Materials Research 2001 16 12 3331-3334 13 Lai Y K Su L Zuo J et al Electrochemical fabricatio ad formatio mechaism of TiO 2 aotube arrays o metallic titaium surface J Acta Physico-chimica Siica 2004 20 9 1063-1066 14 Macak J M Gog B G Hueppe M et al Fillig of TiO 2 aotubes by self-dopig ad electrodepositio J Advaced Materials 2007 19 19 3027-3031 Electrochemical Corrosio Behavior of TiO 2 /HA Composite Coatig o Medical Titaium i Tyrode s Physiological Solutio KONG Li-li LIN Log-xiag HU Rog-gag ZHANG Fa LIN Chag-jia * State Key Laboratory for Physical Chemistry of Solid Surfaces ad Departmet of Chemistry College of Chemistry ad Chemical Egieerig Xiame Uiversity Xiame 361005 Fujia Chia Abstract Titaium ad its alloys have bee widely used as medical implat materials because of their good mechaical properties ad biocompatibility However the physiological corrosio of metal will release metal ios resultig i toxic ad side effects I this paper i order to improve the corrosio resistace of titaium ad to ehace its bioactivity ad osseoitegratio the surface modificatio of titamum were performed Usig eletrochemical methods Tafel polarizatio ad electrochemical impedace spectroscopy EIS were applied to study the electrochemical corrosio behavior of TiO 2 /HA composite coatig It is idicated that the corrosio resistace of the prepared TiO 2 /Ti material i Tyrode's physiological solutio is improved because of the ehaced surface barrier Key words medical implat materials physiological corrosio titaium TiO 2 aotube arrays electrodepostio