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64 Surface Modication of Magnesium and its Alloys for Biomedical Applications
Figure 2.14 Surface morphology of untreated (a, b) and ion-implanted (titanium (c, d) and titaniumeoxygen (e, f)) WE43 magnesium alloys after immersion in simulated body uid for 3 h. Insets in (a) and (c) are the energy-dispersive X-ray spectroscopy analysis performed at the white corrosion products marked with a red þ. Adapted from Zhao, Wu et al. (2013) with permission from Elsevier.
modications, the surface of Mg alloys treated by PIII always exhibited pitting corro­sion, and their ability to provide a long-term corrosion resistance remains open. Based on the characteristic properties of the PIII-treated Mg alloys, it seems that the window of opportunity of using this method for surface engineering Mg toward the develop­ment of degradable implants is rather limited.
Surface modication of magnesium and its alloys: opportunities and challenges 65
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2.6 Laser surface modication
Depending on the kind of interactions between the laser and the material being treated, as well as the type of microstructural/compositional changes induced at the surface, laser-based surface modication can be classied as follows: laser sur­face hardening, laser surface melting (LSM), laser surface alloying (LSA), laser com­posite surfacing, laser surface cladding (LSC), and laser shock peening (LSP) (Dahotre, 1998; Singh & Harimkar, 2012). The role of laser surface engineering of Mg alloys was reviewed by Singh and Harimkar (2012). The effect of different ty pe s of laser treatments on improving the corrosion resistance of Mg alloys is addressed by Dutta Majumdar and Manna (2013, chap. 6). Th e importance of surface modifi- cation of biomaterials by lasers has been addressed by Dahotre, Paital, Samant,
and Daniel (2010), Narayan and Goering (2011),andBandyopadhyay, Balla, Roy, and Bose (2011). Pulse d l as er deposition is another useful approach to modify t he
surface of Mg alloys.
2.6.1 Laser surface melting
LSM involves heating materials using a high-power laser source, namely, neodymium-doped yttriumeAlegarnet or carbon dioxide lasers, to their melting point followed by rapid solidication of the melted zone. Optimizing the conditions to avoid oxidation of the metal surface is necessary du ring LSM. The common aims of LSM are (1) renement of the surface microstructure; (2) homogenization of composition; and (3) dissolution of precipitates (Dutta Majumdar & Manna,
2011). LSM has been explored as a surface modication method for many Mg alloys. Guo, Yue, and Man (2005) report ed that the surface of aWE43Mgalloysubjectedto
LSM was free of corrosion even after 4 h of immersion in 3.5% NaCl, whereas its untreated counterpart showed signicant pitting under similar conditions. Abbas,
Liu, and Skeldon (2005) reported that after LSM, the corrosion rate of AZ31,
AZ61, and WE43 alloys in 5% NaCl with a pH of 10.5 at 20 30%, 66%, and 87%, respectively. The improvement in corrosion resistance exhibited by these three alloys was due to the renement of a-Mg grains and uniform redistribution of the b-phase after LSM. Among them, the ability of the AZ61 Mg alloy to offer a better corrosion resistance than the AZ31 Mg alloy was primarily due to the higher percentage of Al in it. The s upe rior corrosion resistance off ered by the WE43 Mg alloy was due to the presence of a rare earth element on the surface. In addition, in the case of the WE43 Mg alloy, the entire melted layer was not consumed during the t es t period.
Guan, Zhou, and Zheng (2009) studied the corrosion behavior of LSM of an
AZ91D Mg alloy in SBF. The general and pitting corrosion resistance of the laser­treated AZ91D Mg alloy surface was signicantly enhanced by the rened continuous network of b-Mg
phases and the increased Al concentration in the laser-melted
17Al12
zone. Banerjee, Singh Raman, Durandet, and Mcadam (2011) observed a marginal improvement in the resistance of an ZE41 Mg alloy to corros ion in 0.001 M NaCl only during the initial periods of immersion (1 h), which is nullied with a further
C was reduced by about
66 Surface Modication of Magnesium and its Alloys for Biomedical Applications
increase in time. The main reason for the lack of improvement in corrosion resistance of the LSM ZE41 Mg alloy was because of the formation of surface cracks following the high thermal stress created by the high input energy of the laser irradiation. This was substantiated by the smaller extent of surface cracking at a laser power of 820 rather than 1856 W. Another major issue in LSM is the change in microstructural features and surface roughness in the overlapping tracks during treatment. Coy et al.
(2010) showed a change in microstructure, increase in surface roughness, and forma-
tion of microcracks in the overlapping tracks, as well as the presence of trapped pores, during LSM of an AZ91D Mg alloy, which increased with an increase in number of laser pulses (Figure 2.15). Guan et al. (2009), Guan, Zhou, Zheng, and Li (2010),
Figure 2.15 Secondary electron (aec) and backscattered (def) scanning electron micrographs showing the surface appearance and cross-sectional microstructure of an AZ91D magnesium alloy after laser treatment using 10 (a, d), 25 (b, e), and 50 pulses (c, f). Adapted from Coy et al. (2010) with permission from Elsevier.
Surface modication of magnesium and its alloys: opportunities and challenges 67
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and Guan, Zhou, Li, and Zheng (2013a) reported that the formation of a coarse struc­ture in the overlapped area caused by scanning speed provided preferential sites for pitting corrosion in SBF. According to Guan, Zhou, Zheng, and Li (2013), an increase in laser power from 40 to 70 W led to the formation of cauliower-like clusters with protruding particles on the surface of an AZ31B Mg alloy, which increased its average surface roughness from 0.11 to 2.69 mm. Trapping of light on the rough surface has led to a darkening effect of the treated alloy. LSM has been explored as a pretreatment for PEO of an AZ91D Mg alloy (Wang, Zhou, Liang, & Chen, 2012). The renement of microstructure, enrichment of Al, and redistribution of the b-phase (Mg
17Al12
) on the AZ91D Mg alloy matrix after LSM has enabled the formation of a more compact PEO coating with fewer cracks on the surface and a higher amount of MgAl
phase in the
2O4
resultant coating. The corrosion resistance of the LSMePEO-treated Mg alloy was found to be much better than those without the LSM pretreatment. Hence, it is evident that LSM could offer an improvement in corrosion resistance of Mg alloys in chloride­containing environments, including SBF, provided necessary precautions are taken during treatment to avoid the formation of a coarse microstructure in the overlapping areas and cracks due to the high thermal stress induced by the laser irradiation. In addi­tion, LSM can be used as a pretreatment for Mg alloys for chemical conversion treat­ments and PEO to improve the reactivity of the alloy, to facilitate a homogeneous reaction at the surface, and to promote uniformity of the coating.
2.6.2 Laser surface alloying
LSA invol ves adding the preferred alloying elements to the melt pool either by direct injection or by a preplaced coating followed by laser irradiation of the surface to melt the alloying elements (injected or preplaced) and the surface of the base material, generating an enriched melt pool that subsequently solidies to form an alloyed sur­face layer. Very high cooling rates (up to 1011 K/s) during resolidication enabled the formation of a rened microstructure in the alloyed surface. The depth of the alloyed layer and extent of alloying depends on laser processing parameters such as laser power, scan speed, laser spot size, and injection rate of alloying elements (or thickness of the preplaced layer) (Dahotre, 1998). The laser processing parameters need to be carefully optimized to ensure complete melting of alloying elements and the formation of strong metallurgical bonding between the alloyed layer and the substrate (Singh & Harimkar, 2012). It has been reported that an increase in laser power decreases the average alloying element co ntent in the alloyed zone due to increased dilution. Also, an increase in scan speed decreases the average composition distribu­tion due to the lower power input at a low interaction time (Dutta Majumdar & Manna,
2013, chap. 6). Galun and Mordike (1996) showed that LSA of Mg with Al and nickel
(Ni) offers better resistance against corrosion. According to Ming, Da, and Chang
(2008), LSA of an AZ91D Mg alloy with AleSi improved its corrosion resistance
in 3.5% NaCl. Paital et al. (2012) reported that LSA of an AZ31B Mg alloy with Al enabled an improvement in corrosion resistance. In spite of the ability of LSA to improve the corrosion resistance of Mg alloys in chloride-containing environments, a proper choice of alloying elements and laser processing conditions is essential to
68 Surface Modication of Magnesium and its Alloys for Biomedical Applications
ensure a defect-free alloyed zone (Dutta Majumdar, & Manna, 2013, chap. 6). In addi­tion, while choosing LSA of Mg alloys for use in biomedical applications, it is impor­tant to consider the toxicity of the alloying elements in the human body.
2.6.3 LSC and laser composite surfacing
LSC involves melting the material to be clad on the substrate without signicant dilu­tion from the substrate. The rapid solidication of the cladding material led to grain renement, extension of solid solubility, and formation of nonequilibrium phases in the clad layer without signicant changes in the microstructure of the substrate (Subramanian, Sircar, & Mazumder, 1991). In laser composite surfacing, hard ceramic particles are introduced in the laser-melted surface of the substrate to form a composite layer after subsequent resolidication. LSC of an MgeZr alloy onto Mg and its alloys showed improved resistance against corrosion (Su bramanian et al., 1991). LSC of an AS41 Mg alloy with an AleSi eutectic alloy and its composite with C-short bers increased the corrosion resi stance of the Mg alloy by 100 times (Neubert, Bakkar,
& Huang, 2006). In addition, a graded multilayer coating of Ni/copper (Cu)/Al with
good metallurgical bonding at the interfaces between the MgeAl, Ale Cu, and CueNi layers was succes sfully deposited on Mg by LSC. The LSC-treated Mg specimen exhibited a large span of passivity of over 500 mV, in contrast to the untreated Mg substrate, which showed no signs of passivation.
2.6.4 Laser shock peening (LSP)
LSP involves rapid irradiation of the components surface with a very high power laser (power density w10 generation of shock waves (due to expansion of the volume of the plasma plume formed on the surface) and subsequent alteration of the microstructure/state of stress. The substrate being treated is usually covered with a thin insulating or absorbing layer (paint, metal, or plastic tape) and a transparent material (water). Upon laser irradiation, the generation of plasma induces shock waves, causing plastic deformation at the sur­face and introducing compressive residual stresses. In addition, the introduction of a high density of dislocations (Banas, Elsayed-Ali, Lawrence, & Rigsbee, 1990; Banas,
Lawrence, Rigsbee, & Elsayed-Ali, 1990) and the formati on of other phases or twins
(Chu, Rigsbee, Banas, & Elsayed-Ali, 1999) during the process helped to increase the hardness and yield strength of metallic materials. Moreover, the presence of compres­sive residual stresses in the material led to a remarkabl e improvement in the fatigue strength and fatigue life of metallic materials. Because the laser spot size can be tailored suitably, the LSP can be successfully used for treating components of complex geometry, and this attribute would be benecial in treating metallic implants such as stent materials.
The corrosion behavior of laser peened materials has been addressed by many researchers. Zhang, You et al. (2010) reported that an AZ31B Mg alloy subjected to LSP effectively reduced the initiation of stress corrosion cracking (SCC) of the alloy in 1 wt% NaOH for 500 h at room temperature. Jiang, Zhou, Fan, Huang, and Zhao
9
e1012W/m2) applied at a short pulse (1e50 ns), resulting in the
Surface modication of magnesium and its alloys: opportunities and challenges 69
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(2009) conrmed an improvement in the fatigue life of AZ31B and ZK60 Mg alloys
after LSP. Sealy and Guo (2010) studied LSP of a biodegradable MgeCa alloy to understand the change in surface integrity and process mechanics and developed a three-dimensional semi-innite simulation to predict the topography and residual stress elds produced by sequential peening. Guo, Sealy, and Guo (2012) reported that LSP induced unique surface topographies, high compressive residual stresses, and extended strain hardening, which helps to control the corrosion rate of MgeCa alloys by more than 100-fold in SBF. According to them, with LSP, the subsurface of an MgeCa alloy could be strain hardened up to 500 mm, and the maximum compressive residual stress of the peened surface in the planar direc tion might have contributed to the decrease in the corrosion rate of the MgeCa alloy. The ability of LSP to induce compr essive residual stress, to improve fatigue life, and to reduce the susceptibility of Mg alloys to SCC will be useful in the development of Mg-based degradable load-bearing implants.
2.6.5 Laser-assisted coloring/darkening and surface patterning
Guan, Zhou, Li, and Zheng (2013b, 2014) studied the effect of femtosecond and
krypton uoride excimer laser irradiation on the surface evolution of an AZ31 Mg alloy, resulting in coloration and darkening of its surface following changes in surface prole and composition. According to them, by adjusting laser parameters according to the thermal properties of materials and the environmental conditions (oxygen or argon atmosphere), this type of laser irradiation offers potential applications for the develop­ment of Mg-based bio-optical implant devices. Foroozmehr, Alemohammad, Wang,
Toyserkani, and Esmaeili (2011) studied patterning of Mg with silver (Ag) nanopar-
ticles printed by a laser-assisted maskless microdeposition process. The laser-assisted maskless microdeposition process involves two steps: (1) microdeposition, in which the deposited material in the form of suspended nanoparticles is atomized to an aerosol and injected on a moving substrate in a layer-by-layer fashion; and (2) laser postpro­cessing, in which the laser beam is scanned over the deposited tracks of nanoparticles for sintering. The Ag lm has a relatively uniform thickness with a root mean square roughness of 48 nm. It is well known that surface patterning of biocompatible materials could promote cell adhesion, inltration, and proliferation. Being a bioactive material, Ag provides better biocompatibility and it is well known for its antibacterial effects. However, the formation of cracks on the Ag lms during sintering is considered a major limitation in terms of its wide applicability for biomedical applications.
2.7 Other methods of surface modication
2.7.1 Cold spray deposition
Cold spray (CS) coating is a viable method to engineer the surface of Mg and its alloys. The deposition of CS coatings involves the ballistic impingement of particles, usually in the size range of 1e100 mm, that are accelerated by a high-velocity stream of gas on
70 Surface Modication of Magnesium and its Alloys for Biomedical Applications
the substrate surface. Upon impact with the substrate, the particles undergo severe plastic deformation, resulting in attened splats, which is also accompanied by peen­ing of the substrate. As the temperature of the expanded gas stream that exits the spray nozzle is relatively lower than the conventional thermal spray processes, it is called a cold sprayprocess. Hence, it is particularly suitable for coatings and substrate ma­terials that are sensitive to heat or oxidation and that would transform or react under the conditions of a conventional thermal spray process (Champagne, 2007). The perfor­mance of CS coatings is largely a function of bond strength between the coating and the substrate and the residual stress, porosity, and density of the coating. To achieve a better bond strength, it is important that the mean velocity at which the par­ticles are accelerated exceeds the minimum critical velocity so that the particles have sufcient kinetic energy to generate extensive plastic deformation of the substrate and to promote interlocking of the spray splats (Champagne, 2007). Because the particles are sprayed at relatively lower temperatures, there is little temperature-driven dimen­sional change, and hence the resultant coatings usually are in a state of compressive residual stress, which is benecial to prevent delamination of the coating. The porosity of CS coatings is generally low, on the order of 1e 5%, and most of them are identied on the top surface. The following factors, either individually or in combination, are considered responsible for the occurrence of porosity in CS coatings: (1) rebound of particles with a velocity lower than the critical velocity; (2) large particles that do not undergo enough plastic deformation upon impact, generating porosity at the particlee particle boundaries; (3) the absence of a signicant peening effect on the particles that are already deposited, particularly at the top of the coating; and (4) the sudden incompatibility in terms of localized heating, stresses, and plastic deformation (Balani,
Laha, Agarwal, Karthikeyan, & Munroe, 2005; Bu, Yandouzi, Lu, & Jodoin, 2011).
Most of the studies of CS coatings on Mg and its alloys concentrate on the depo­sition of Al and AleAl
composite coatings, particularly to understand the micro-
2O3
structural and interfacial characteristics, to improve the bond strength and density, to promote formation of intermetallic compounds by heat treatment after coating, and to improve the corrosion behavior (Bu et al., 2011; Spencer, Fabijanic, & Zhang, 2009;
Spencer, Luzin, Matthews, & Zhang, 2012; Spencer & Zhang, 2009; Tao et al., 2010; Wang, Qiu, Xiong, Birbilis, & Zhang, 2014; Wang, Spencer, Birbilis, & Zhang, 2010).
Zhang et al. address the role of CS coatings on Mg in Chapter 14 of Volume 2 of this book. Noorakma, Zuhailawati, Aishvarya, and Dhindaw (2013) recently studied the deposition of HA on an AZ51 Mg alloy by a modied CS process in which the Mg alloy was preheated to 400
C for 1 h and the HA powder (average particle size,
4 mm) was sprayed using a high-pressure (10 bar) air nozzle spray at room tempera­ture. According to them, this modication helped to retain the characteristics of HA, which would otherwise undergo a phase change at high temperature. In addition, the combination of a higher impact velocity of HA particles and preheating of the AZ51 Mg alloy enabled better bonding of the HA particles with the Mg alloy and the formation of a uniform coating. The average thickness and modulus of the resultant HA coating was 25 mm and 9 GPa, respectively. Immersion in SBF for up to 14 days showed that the HA-coated AZ51 Mg alloy is bioactive and facilitated apatite formation.
Surface modication of magnesium and its alloys: opportunities and challenges 71
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Being a low-temperature process, CS is particularly suitable for the deposition of bioactive coatings such as HAP on Mg and its alloys, in which it would be possible to limit the extent of oxidation of the substrate as well as the phase transformation of HAP. As long as the powder particles a re accelerated at a speed that exceeds the min­imum critical velocity, the bonding strength between the substrate and the coating would be good. Peening of the substrate as well as the deposited coatings is likely to induce compressive residual stress, which would be benecial in improving the fatigue strength of the substrate as well as in preventing delamination of the coating e both attributes are critical in biomedical implant applications. Porosity of the CS coating is a matter of concern (Figure 2.16). Fortunately, none of these pores is continuous from the outermost surface of the coating down to the substrate, suggesting that the coating is impermeable to solution (Tao et al., 2010), which is an important feature for considering them for magnesium and its alloys in the develop­ment of degradable implants. Adopting after spraying a heat treatment at temperatures closer to the melting point of the substrate for a longer treatment time would offer the benets of increasing the bond strength and relaxing the compressive residual stress (Spencer et al., 2009; Spencer & Z hang, 2009), both of which increase the adherence of the coating and prevent its delamination. This methodology has many positive attributes for surface modication of Mg and its alloys toward the development of
(a) (b)
(c) (d)
Figure 2.16 Backscattered scanning electron microscopy images of unreinforced aluminum (Al) and AleAl prepared by cold spray deposition: (a) Unreinforced Al coating cold sprayed at 65 (b) unreinforced Al coating cold sprayed at 125 cold sprayed at 65 Adapted from Wang, Spencer et al. (2010) with permission from Elsevier.
composite coatings showing the presence of porosity in the coatings
2O3
C; and (d) Ale50 vol% Al2O3composite coating cold sprayed at 65C.
C; (c) Ale25 vol% Al2O3composite coating
C;
72 Surface Modication of Magnesium and its Alloys for Biomedical Applications
degradable implants. Being a line-of-sight process, the difculty in coating complex shapes and the internal surfaces of implants is a major limitation of the CS process (Champagne, 2007).
2.8 Summary and concluding remarks
This chapter provides a detailed outline of the various surface modication methods available to modify the surface of Mg alloys and discusses the opportunities and limitations of each in the development of Mg-based degradable biomaterials. The salient features are summarized below.
Imparting self-passivation of Mg alloys through selective oxidation of alloying elements such as scandium and yttrium is indeed an effective method to control the rate of degradation of Mg alloys. This approach will be useful when the implant geometry restricts the use of any coatings. However, the alloying elements should not exhibit any signicant toxicity in the human body.
Microstructural modication of AZ-type Mg alloys by developing a continuous b-phase network on the alloys surface could also be used to impart a self-passivation mechanism after the corrosion process. The formation of galvanic cells and an increase in the corrosion rate are believed to promote deposition of Mg(OH) and Mg the porous nature of Mg(OH)
(PO4)2as the primary and secondary corrosion products, respectively. However,
3
would allow permeation of the body uid and limit the
2
long-term ability of the Mg alloy to protect against corrosion.
Hydrothermal treatment of Mg alloys enables the formation of an Mg(OH) hydrophilic and adherent and offers a higher resistance to corrosion than their untreated counterparts. However, the ability of the Mg(OH) for the Mg alloys against corrosion in SBF is a matter of concern.
AHT has the ability to reduce the rate of degradation of Mg alloys. The dense and compact nature and the amount and crystallinity of MgO are the decisive factors in controlling the rate of degradation of Mg alloys in SBF.
Passivation in 1 M NaOH or in m-SBF has limited potential in the surface modication of Mg and its alloys in the development of degradable implants because of the insufcient thickness and compactness of the passive lms formed in them.
The difculty imposed by the intrinsic heterogeneity of Mg alloys, slow reaction kinetics, and the defective nature of the surface conversion layer formed by the reaction between the Mg alloys and ILs suggest that there remains much to be explored in generating robust passivating lms using ILs.
The formation of well-ordered and closely packed SAMs with a high homogeneity, good order, and better chemical stability is indeed promising. However, the rapid decrease in the contact angle of some of the SAM-modied Mg alloy surfaces in aqueous solutions within a short duration of time has raised questions on their long-term chemical stability in the human body.
The difference in reactivity imposed by the intrinsic heterogeneity of Mg alloys, the forma­tion of a porous coating with a typical mud crackpattern, possibly due to the release of hydrogen gas and/or dehydration of the coating after deposition, limits the extent of protec­tion against corrosion offered by conversion coatings. Among them, uoride conversion coating is promising in terms of its biocompatibility. However, modication of the existing
and Ca3(PO4)2(or Ca10(PO4)6(OH)2)
2
coating, which is
2
coating to provide long-term protection
2
Surface modication of magnesium and its alloys: opportunities and challenges 73
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methodologies to prepare MgF2coatings with desirable characteristics and with a better understanding of the mechanism of deposition and the inuence of volume fraction of Mg(OH)
on the resistance of the resultant coatings against corrosion needs to be
2-xFx
explored for its potential utility.
The susceptibility of the sol-gel-deposited BGC coatings for cracking after immersion in SBF is the major drawback that limits their acceptance as a suitable surface coating of Mg alloys in the development of degradable implants.
Silane coating offers only a short-term protection for Mg alloys against corrosion. Alkalin­ization at the interface during corrosion promotes swelling and decomposition of the SiO network, while accumulation of corrosion products promotes delamination and blistering of the coating, thus exposing the Mg alloy to degrade further. However, silane coatings will be useful for functionalizing compounds with biofunctional properties. Hence, increasing the bond strength and hydrolytic stability of silane coatings becomes critical in achieving reasonably good protection of Mg alloys against corrosion.
It is possible to coat or bind bioactive compounds such as gelatin or albumin. However, the inability of the precoatings to form a completely dense layer on Mg alloys and the detach­ment/delamination of the precoating and/or bioactive molecule coating is a matter of concern in realizing their potential utility.
Degradable polymer coatings deposited by both dip and spin coating methods did not offer a long-term corrosion protection. Bulk erosion/degradation leads to detachment of coatings, resulting in the formation of many micro-/macropores and cracks in the early stage of degra­dation. Surface-eroding polymer coatings exhibit homogeneous surface erosion from exte­rior to interior, and this type of coating is benecial for the development of fully biodegradable cardiovascular stents.
The ability to load anti-inammatory drugs in conducting polymer coatings such as PEDOT and its subsequent release by electrical stimulation conrmed its potential application in degradable implant materials with drug delivery applications. However, the inability of PEDOT coatings to completely prevent the Mg from corrosion, its detachment after multiple electrical stimulations of drug release, and the mode of degradation of PEDOT under in vivo conditions are the major concerns.
Anodizing is useful in developing a passive oxide layer on Mg alloys. However, the adverse effect on fatigue properties caused by oxidation-induced surface tensile stress, structural defects in the oxide layer, and substrate age softeningfollowing the heat associated with oxide lm formation restrict their widespread acceptance. MAO is considered an option to reduce this risk of fatigue failure. However, because of the higher pore density on the surface of the MAO coatings of Mg alloys, the effective surface area and the tendency of the corrosive medium to adsorb and concentrate into these pores are increased, thus limiting the protection against corrosion offered by them.
ED is a useful method for depositing HA, calcium-decient HA, and uoride-, strontium-, Zn-, and Si-doped HA coatings. Because Mg alloys have a lower melting point, the difculty associated with heat treatment at high temperatures to improve the adhesion of the coatings is a major limitation in EPD. However, MAO coatings could be used as a pretreatment for deposition of a variety of inorganic materials with a better adhesion by EPD.
The major limitation of the coatings deposited by PVD is the presence of pores and pinholes, which in most cases are difcult to eliminate completely. The formation of a transition layer to buffer the stress developed by the mismatch between the Mg alloy and the coatings, and an improvement in deposition methodology by implementing ltered cathodic arc deposition, could not completely prevent penetration of the electrolyte or sustain their protective prop­erties after long-term exposure in SBF.
2