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Corrosion of Nano-hydroxyapatite Coating on Titanium Alloy Fabricated by Electrophoretic Deposition

P.K. Wong, C.T. Kwok Department of Electromechanical Engineering, University of Macau, Macao, China

Abstract Titanium and its alloys are often used in orthopedic surgery and dentistry due to their excellent corrosion resistance, high mechanical strength and low density. However, their inertness and low biocompatibility are the most serious drawbacks for biomedical applications. In order to improve their biocompatibility, hydroxyapatite (HAP) is often coated on surface of metallic implants by plasma spraying. However, the plasma-sprayed HAP coatings suffer from various problems such as high degree of porosities, poor bond strength, nonstoichiometric composition and amorphous structure. In the present study, nanocrystalline HAP (n-HAP) coating was fabricated on titanium alloy Ti-6Al-4V by electrophoretic deposition followed by sintering at 1000 oC. Surface morphology, compositions and phases of the n-HAP coating were analyzed by means of optical microscopy and scanning electron microscopy, energy dispersive spectrometry and Xray diffractometry respectively. In addition, the corrosion behavior of the n-HAP coated Ti-6Al-4V in Ringer’s solution at 37 oC was investigated by means of open-circuit potential measurement and potentiodynamic polarization technique. By X-ray diffractometry analysis, the crystallite size of the sintered n-HAP coating was about 25 nm. The results of electrochemical corrosion studies illustrated that the sintered n-HAP coated Ti-6Al-4V possessed a nobler open circuit potential but a higher corrosion current density due to the presence of micro-cracks and pores in the coating. Keyword: Corrosion, titanium alloy, hydroxyapatite coating, nanomaterial, electrophoretic deposition Introduction Hydroxyapatite (HAP), or Ca10(PO4)6(OH)2 is a bioceramic which resembles the mineral constituents of human bones and teeth. It has been widely used as the coatings on orthopaedic and dental metallic implants due to its excellent biocompatibility, high chemical and biological affinity with bone tissue. The nanometer size inorganic component (HAP) in natural bone of human being is considered to be important for the mechanical properties of the bone. In addition, protein adsorption and osteoblast adhesion for the nano-sized ceramic materials are higher than those of the traditional micron-sized ceramic materials [1]. To produce high quality HAP bioceramics for artificial bone substitution, nanocrystalline HAP is usually employed.

It is well known that a bulky HAP component formed by sintering is not suitable for biomedical applications especially under load-bearing conditions because it is too brittle and weak. Because of its simplicity and versatility, plasma spraying is currently the only commercial process for fabricating HAP coatings on the metallic implants. Nevertheless, long-term stability of the plasma-sprayed coatings is an exigent problem because of their high degree of porosities, poor bond strength, non-stoichiometric composition and amorphous structure [2-4]. Owing to the drawbacks of plasma spraying, other techniques such as laser surfacing, sol– gel, magnetron sputtering, ion-beam deposition, pulse-laser deposition, electrochemical deposition and electrophoretic deposition (EPD) have been proposed and developed to fabricate HAP coatings [5]. Among the different fabrication methods, EPD was reported to be the most promising technique because it has advantages of short formation time, simple apparatus and little restriction of the shape of substrate [6]. EPD is a colloidal process in ceramic production which offers easy control of the thickness and morphology of a deposited ceramic layer through simple adjustment of the deposition time and applied potential [6]. In EPD, charged powder particles dispersed or suspended in a liquid medium are attracted and deposited onto a conductive substrate of opposite charge on application of a DC electric field as shown in Fig. 1. Nowadays, EPD of n-HAP coatings on the metallic implants for biomedical applications is being increasingly recognized by scientists and technologists. EPD offers advantages in the n-HAP coatings such as dense packing, good sinterability and homogeneous microstructure [7]. The agglomerate-free structures made from close-packed fine particles can be densified at lower sintering temperature about 875 to 1000 oC. Then the mechanical strength of the n-HAP coatings, its bond strength on the substrate alloys, and their corrosion resistance are expected to be improved. Technical studies on EPD of HAP coatings on different implant alloys have been investigated by several investigators [8-13]. Electrochemical studies of the EPD HAP-coated 316L stainless steel in Ringer’s solution exhibited higher corrosion resistance than the uncoated 316L, with the nobler open-circuit potential and higher breakdown and protection potentials [14]. Zhang and his co-workers reported that the nanostructured HAP coating on Ti-6Al-4V formed by EPD has corrosion resistance 50-100 times higher than the plasma-sprayed HAP coating [15]. However, corrosion behavior and mechanism of these HAP

6 x 10-6 oC-1).244V versus SHE at 25 oC) as the reference electrode. Figure 1: Schematic of EPD process. using a heating rate of 100 oC/h. Voltage of 200 V during 30 minutes was applied using a power supply. nHAP powder was mixed in 75% ethanol by a magnetic stirrer for obtaining a homogeneous colloidal suspension. The low bond strength of the n-HAP coating on Ti-6Al-4V sintered at 1000 oC was reported to be 115 MPa which was attributed to the thick oxidized layer [18]. V. The coated specimens were allowed to dry in air for 24 hours. The work area of both electrodes was approximately 1 cm2.42). The aims of present study is to study the surface morphology and compositions of and phases present in the nHAP coating on Ti-6Al-4V fabricated by EPD after sintering.167 mV s-1.19] and Bioglass coatings [20] formed by EPD followed by sintering was reported. The compositions and phases of the sintered coatings were analyzed by energy dispersive spectroscopy (EDS) and X-ray diffractometry (XRD) respectively. From the polarization curve.coated alloys are not elucidated with respect to their surface morphology. probably as a result of expansion and shrinkage during heating and cooling. exposing a surface area of 1 cm2. Ti-6Al-4V with and without sintered n-HAP coating were embedded in cold-curing epoxy resin.0 g/l NaHCO3). toxic and carcinogenic effects. 2. All potentials were measured with respect to a saturated calomel electrode (SCE. The separation distance between the electrodes was 1 cm. starting from 200 mV below the open-circuit potential. 0. the greater the susceptibility to cracking.2 x 10-6 oC-1) and Ti-6Al-4V (8. The surface morphology of the coating at low and high magnification is shown in Fig. The specimen is designated as nHAP-Ti-S. Two parallel graphite rods served as the counter electrode for current measurement. the corrosion current density (Icorr) was evaluated by Tafel extrapolation method by software (PowerCORR. After the open-circuit potential measurement for 2 hours.2. The scan was then reversed at a current density of 5 mA/cm2. which produced plate-like particles with a 2. open to air at 37±1 oC. The surface morphology of the sintered n-HAP coating were investigated by optical microscope (OM) and scanning electron microscope (SEM). the potential was increased at a rate of 0. 0. a dwell time of 2 h. severely cracked coatings were formed on Ti-6Al-4V after sintering [18]. Results and Discussion Microstructural and Metallographic Analysis The n-HAP coating was uniformly deposited on the surface of Ti-6Al-4V by EPD and followed by sintering at 1000 oC. because their quality will directly affect the service life in vivo and the degree of release of metallic ions into the human body for causing allergic. 1. 0. .9λ/B cos θ was used to determine the crystallite sizes D along (002) direction. Moreover. Experimental details To investigate electrochemical corrosion behavior. and aggravated by the difference in thermal expansivity between the n-HAP coating (15. The Debye-Scherer equation [16]: D = 0.17 g/l CaCl2. Small pores up to 1 µm were also observed in the coating [Fig. 2(b) and (c) respectively. The nHAP particles prepared by acid base method.5:1 aspect ratio. Black and thick oxidized layer is observed on the uncoated area and also the interface between the substrate and coating although sintering was done in argon-purged atmosphere. The sintered n-HAP coating is relatively dense and adherent to the substrate. 2(c)]. 2(b)]. it was reported that the thicker the coating [18] and the less equiaxed the nano-particles [20]. where λ is the wavelength of the Cu Kα radiation. The substrate alloy (working electrode) and the platinum counter electrode are immersed in the suspension in a 500-cm3 beaker as shown in Fig. The thickness of n-HAP coating is about 100 µm. Sintering of the coatings was carried out at 1000 oC in an argon-purged atmosphere. Numerous surface micro-cracks can be observed throughout the surface of nHAP-Ti-S [Fig. ® The commercially available reagent grade n-HAP powder (Riedel-de Haën) was used as the coating material and implant grade alloy Ti-6Al-4V was used as the substrate for EPD. were performed using a PAR VersastatII potentiostat according to ASTM Standard G61-86 [17]. 2(a). and a cooling rate of 100 oC/h. B is the half-width in radian and θ is the Bragg angle for the peak. In addition. Similar surface morphology of the n-HAP [18.04 g/l KCl. Corrosion study of n-HAP coated implants is fundamental important. the corrosion behavior of the n-HAP coated Ti6Al-4V in the Ringer’s solution at 37 oC is investigated. The cross-sectional appearance of nHAP-Ti-S is shown in Fig. Open-circuit potential measurement and cyclic potentiodynamic polarization test in Ringer’s solution (9 g/l NaCl.

and (c) location A (SEM). the average crystallite sizes of the n-HAP powder and the sintered n-HAP Fig. and nHAP-Ti-S are shown in Fig.879o. it is evident that the brighter contrast region (location A) is the nHAP coating whereas the darker contrast region (location B) possesses high Ti content. Fig. The overlapped peaks with the highest intensity for HAP are found in nHAP-Ti-S at 31. 3. 4(c) shows a secondary electrons image taken for obtaining the compositional maps for the elements Ca. (b) surface morphology (SEM). No phase change is observed in the XRD spectra for the nHAP coatings before and after EPD. In addition to the peaks of Ca and P. . 4(a) and (b) shows the EDS spectra obtained by point analysis from the ‘island’ (location A) and the micro-crack (location B). (b) n-HAP powder. Strong peaks of Ca and P were detected in the spectrum from location A. The XRD spectra for Ti-6Al-4V. and (c) nHAP-Ti-S. This further shows that the underlying substrate was exposed at the cracking regions. 3(b) and (c) shows that the n-HAP powder and nHAP-Ti-S possess high crystallinity as indicated by sharp peaks and low background. n-HAP powder. By comparison to the secondary electrons image. This indicated that the structure and compositions of the coating remained the same [18]. P and Ti. This shows that the sintered n-HAP coating did not completely cover the entire substrate and the exposed regions were thermally oxidized. Low-intensity peaks for Ti-6Al-4V and titania (TiO2) are detected in the XRD spectrum for nHAP-Ti-S.774o and 32. strong peaks of Ti and V are observed in the spectrum from location B.(a) __ ↑ Coating ↓ Substrate 50 µm (b) coating are calculated to be about 33 nm and 25 nm respectively. A ←B (c) ← Pore Figure 3: XRD spectra for (a) Ti-6Al-4V.197o of 2θ . By the Debye-Scherer equation and 2θ = 25. Fig. Figure 2: Micrographs of the sintered n-HAP coated Ti-6Al4V (nHA-Ti-S) showing (a) cross-sectional view (OM).

and nHAP-Ti-S in Ringer’s solution (open to air) at 37 oC is shown in Fig. the OCP increases until the film reaches its limiting protective capacity and then reaches a steady value. (b) location B and (c) compositional maps of the surface of nHAP-Ti-S. Thus. After two hours. their OCP become stable and the steady values are summarized in Table 1. The ranking of the OCP for the specimens is: nHAP-Ti-S > oxidized Ti-6Al-4V > Ti-6Al-4V For Ti-6Al-4V. the passive air-formed oxide film becomes more protective after immersed in the solution for 2 hours due to the increase in thickness. the OCP of oxidized Ti-6Al-4V and nHAP-Ti-S significantly shifted towards noble direction and reached the potentials of -0. This shows the higher thermodynamic stability of these specimens in Ringer’s solution at 37 oC. 5. Compared to the oxidized Ti6Al-4V.P (a) Ti (c) Figure 4: EDS Point analysis at (a) location A. the nobler OCP exhibited for nHAP-Ti-S appears to be associated with the presence of more protective n-HAP coating despite of the micro-cracks and pores. ←B A Ca .07 to 0 V respectively. Compared with Ti-6Al-4V (OCP = -0. Whereas the OCP for the oxidized Ti-6Al-4V and nHAP-Ti-S (with the thermally oxidized layer and also the n-HAP coating) are very stable. oxidized Ti-6Al-4V (uncoated and treated with the same condition as sintering). (b) Corrosion Behavior The plot of OCP against time for Ti-6Al-4V (uncoated).55 V).

36 Figure 6: Potentiodynamic polarization curves of various specimens in Ringer’s solution at 37 oC.+ H2O Owing to the poor circulation of H+ out of the interface.36 µA/cm2 respectively. 0. Corrosion parameters of various specimens. cracks and amorphous phases [15]. the corrosion proceeds very quickly. Ti and V are detected in the micro-cracks.07 Icorr (µA/cm2) µ 0.07 1. Compared to Ti6Al-4V. Similar to nHAP-TiS. The coating then fails at the coating and substrate interfacial area. Zhang and his coworkers reported that the corrosion mechanism involved with two steps [15]: (1) the H+ produces at the interface area when corrosion occurs: Ti + 2 H2O TiO2 + 4H+ + 4e(2) HAP dissolves in the high H+ concentration area: Ca10(PO4)6(OH)2 + 2H+ 10 Ca2+ + 6 PO43. to a minor extent. direct paths between the corrosive medium and the substrate are eventually formed. The coating cannot be a perfect insulating barrier to avoid corrosion of the substrate and simply acts as a semi-insulating barrier and its corrosion rate is higher than that of the Ti-6Al-4V.55 -0. Although the thickness of the n-HAP coating are much thicker than the TiO2 (in nm). The breakdown potentials (Eb) for all specimens are very close. oxidized Ti-6Al-4V and nHAP-Ti-S are 0. the reverse scan takes an entirely different path when compared to the forward scan. → The Icorr of Ti-6Al-4V.07 0. The substrate is not completely covered by the coating. Dissolution of nHAP automatically speeds up and this corrosion is a selfcatalytic process.19 0.Figure 5: Plot of OCP vs time of various specimens in Ringer’s solution at 37 oC. it cannot stop until the entire interfacial n-HAP is dissolved. In the case of the oxidized Ti-6Al-4V. by tiny amount of pores in the n-HAP coating. The improved corrosion resistance of the oxidized Ti6Al-4V can be attributed to the fact that the thickened oxide film formed by thermal oxidation [22. the corrosion resistance of the nHAPTi-S is greatly affected by the extensive micro-cracks. According to the Icorr. This shows that the repassivity of the oxidized Ti-6Al-4V is not as good as Ti-6Al-4V and nHAP-Ti-S.23].08 1. unreactive and tenaciously adherent oxide films spontaneously formed over its surface.9 times whereas the Icorr of the oxidized Ti-6Al-4V decreased by 2. the oxidized Ti-6Al-4V and nHAP-Ti-S in Ringer’s solution at 37 o C are shown in Fig. and. Since the electrolyte can easily go through the connective cracks of the coating. the corrosion resistance of the specimens can be ranked as: Oxidized Ti-6Al-4V > Ti-6Al-4V > nHAP-Ti-S → Potentiodynamic polarization curves of Ti-6Al-4V. Specimens Ti-6Al-4V Oxidized Ti-6Al-4V nHAP-Ti-S OCP (V) -0. No hystersis loop is observed for Ti-6Al-4V and nHAP-Ti-S. the Icorr of n-HAP-Ti-S is increased by 1. The transient microscopic breakdown of the oxide films are induced by the presence of chloride ions in vitro [21]. The passivity of Ti-6Al-4V is acribed to the very stable. the plasma-sprayed HAP coating on Ti-6Al-V also has many defects such as porosity.7 times. 6 and the corrosion parameters are extracted and summarized in Table 1. Owing to the existence of micro-cracks and pores in nHAP-Ti-S. The coating cracks were formed due to large difference in coefficients of thermal expansion resulting in low corrosion resistance similar to the present findings. So the Icorr of nHAP-Ti-S is found to be higher than that of Ti-6Al-4V. .07 0 Eb (V) 1. the local pH of the interface is extremely low.07 and 0. Table 1. From the result of EDS analysis. Whenever the corrosion starts.19.

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