American Journal of Biomedical Engineering 2012, 2(6): 218-240

DOI: 10.5923/j.ajbe.20120206.02

Biomedical Magnesium Alloys: A Review of Material
Properties, Surface Modifications and Potential as a
Biodegradable Orthopaedic Implant
Gérrard Eddy Jai Poinern* , Sridevi Brundavanam, Derek Fawcett
M urdoch Applied Nanotechnology Research Group, Department of Physics, Energy Studies and Nanotechnology, School of Engineering
and Energy, M urdoch University, M urdoch, Western Australia, 6150, Australia

Abstract Magnesium and magnesium based alloys are lightweight metallic materials that are extremely biocompatib le

and have similar mechanical properties to natural bone. These materials have the potential to function as an osteoconductive
and biodegradable substitute in load bearing applicat ions in the field of hard t issue engineering. However, the effects of
corrosion and degradation in the physiological environ ment of the body has prevented their wide spread applicat ion to date.
The aim o f this review is to examine the properties, chemical stability, degradation in situ and methods of improving the
corrosion resistance of magnesium and its alloys for potential application in the orthopaedic field. To be an effective imp lant,
the surface and sub-surface properties of the material needs to be carefully selected so that the degradation kinetics of the
implant can be efficiently controlled. Several surface modification techniques are presented and their effectiveness in
reducing the corrosion rate and methods of controlling the degradation period are discussed. Ideally, balancing the gradual
loss of material and mechanical strength during degradation, with the increasing strength and stability of the newly forming
bone tissue is the ultimate goal. If this goal can be achieved, then orthopaedic implants manufactured fro m magnesium based
alloys have the potential to deliver successful clinical outcomes without the need for revision surgery.

Keywords Magnesium, Bio logical Co rrosion, Bioco mpatibility, Alloys, Surface Modification

1. Introduction
The skeletal system of the human body is a complex
three-dimensional structure that is important for two main
reasons. The first arises from the need to structurally support
the many body organs and other related tissues. The second
is the attachment of the numerous muscle groups that are
needed for body movement and loco motion. The skeleton is
constructed of two types of tissue, the first is a hard t issue
called bone and the second is a softer tissue composed of
cartilag inous materials. The adult hu man skeleton consists of
206 bones[1]; some provide protection to the internal organs,
while others perform specialized functions such as
transmitting sound vibrations in the inner ear. The bone
matrix also provides a natural reservoir for cells and mineral
ions that play an important role in maintain ing the
biochemical balance within the body. For examp le, calciu m
is an important element involved in muscular action and
nerve conduction and its level in the body is closely
monitored and regulated by a process called homeostasis[2].
*Corresponding author: (Gérrard Eddy Jai Poinern)
Published online at
Copyright © 2012 Scientific & Academic Publishing. All Rights Reserved

Bone is a natural two phase organic-inorganic ceramic
composite consisting of collagen fibrils with an embedded
inorganic nano-crystalline co mponent. The primary organic
phase of the bone matrix is Type I collagen, which is secreted
by osteoblast cells to form self-assembled fibrils[3, 4]. The
fibrils are bundled together and orientate themselves parallel
to the load-bearing axis of the bone. The fibrils are typically
300 n m long, develop a 67 n m periodic pattern in which a 40
nm gap or hole is formed between the ends of the fibrils and
the remain ing 27 n m overlaps the bundle behind[5]. This
pattern creates discrete and discontinuous sites for the
deposition of plate-like nanometre sized hydroxyapatite
(HAP) crystals, which forms the second phase of the bone
matrix. HAP is a mineral predominantly co mposed of
calciu m phosphate which has the general chemical formu la
of[Ca10 (OH) 2 (PO4 )6 ]. It is the main inorganic co mponent of
bone and teeth, accounting for up to 65% by weight of
cortical bone and in the case of teeth it accounts for 97 % by
weight of dental enamel in mammalian hard tissue[6]. The
discontinuous discrete sites limit the growth of the HAP
crystals and force the crystals to grow with a specific
crystalline orientation which is parallel to the load-bearing
axis of the bone and collagen fibrils. The crystal p lates
typically have a length of 50 n m, a width of around 25 n m
and on average a thickness of 3 n m[7-10]. The HAP also has


American Journal of Biomedical Engineering 2012, 2(6): 218-240

trace amounts of potassium, manganese, sodium, ch loride,
hydrogen phosphate, citrate and carbonate[11]. The final
component of the bone matrix consists of the non-collagen
organic proteins such as the phosphor-protein group which
are believed to regulate the formation of the inorganic crystal
phase by influencing the size, orientation and the
depositional environ ment within the spaces between the
collagen fibrils. The phosphor-protein group is also believed
to be the source of calciu m and phosphate ions used in the
formation of the mineral phase[12].
The organic phase gives bone its flexib ility, while the
inorganic phase provides bone with its structural rig idity[13,
14]. The incorporation of organic and inorganic phases in the
matrix g ives bone its unique mechanical properties such as
toughness, strength, and stiffness. It is the combination of
these properties that give bone and the skeletal system in
general, its remarkable ability to withstand the various
mechanical and structural loads encountered during normal
and intense physical activity[15]. Ho wever, not all bone
tissue in the body has the same properties and this is
characterized by the presence of two types of bone. The first
type consists of a hard outer layer of co mpact (cortical) t issue,
while the second type forms the less dense and spongy
(trabecular) tissue which fills the interior of the bone. This
spongy interior contains marrow and the many blood vessels
that supply nutrients and remove waste products from the
bone tissues. Both the cortical bone and the trabecular bone
are co mposed of the same organic and inorganic phases
discussed above, but they differ in the amount of each phase
present. The two bone types also differ in their respective
porosities and in their structural arrangement. The amount of
cortical and trabecular tissue found in bone is dependent on
the external load being applied and the frequency of the
load[16]. Despite its remarkable mechanical and structural
properties bone can fracture fro m three main causes: 1) a
fracture caused by sudden injury; 2) Fatigue or stress
fractures resulting fro m repeated cyclic loads; and 3)
Pathological fractures resulting fro m bone infections and
tumours[17]. The surgical imp lantation of artificial
biomaterials of specific size and shape is an effective
solution in restoring the load bearing capacity and
functionality of damaged bone tissue. The design and
selection of bio materials is highly dependent on the specific
med ical applicat ion. Therefore, it is imperative that new
biomaterials being developed for load bearing orthopaedic
implant applications should have excellent bioco mpatibility,
comparable strength to natural bone, and produce no
cytotoxicity effects[18, 19].
Metallic b io materials have been used since the early 1900s
to replace damaged or diseased hard tissues. And as early as
1907, a magnesium alloy was used by Lambotte, to secure a
bone fracture in the lo wer leg[20, 21]. Metallic imp lants are
generally used in load bearing applications where their high
mechanical strength and fracture toughness make’s them
superior to ceramics, poly meric materials and poly mer /
ceramic co mposites. Metallic implant materials currently
used include stainless steel, cobalt-chro me alloys and

titanium and its alloys. At present there are two major
problems associated with using the metallic imp lants. The
first involves the mis match between the mechanical
properties of the metallic alloy and the surrounding natural
bone tissue. The elastic modulus of both stainless steel and
cobalt-chrome alloys is around ten times greater than that of
bone, while a titaniu m alloy such as Ti-6Al-4V is around five
times greater[22]. Bone tissue is constantly undergoing
remodelling and modification in response to imposed
stresses produced by normal everyday activities. The
mechanical mis match between bone and different metallic
implant materials results in a clin ical phenomenon known as
stress shielding. The stress-shielding phenomenon occurs
when the imp lant carries the bulk of the load and the
surrounding bone tissue experiences a reduced loading stress.
The reduced loading stress experience by the surrounding
bone tissue ultimately leads to bone resorption[23, 24]. The
second problem stems fro m mechanical wear and corrosion
of the implant and results in the release of toxic metallic ions
such as chromiu m, cobalt and nickel into the body. These
harmful metallic ions solicit an inflammatory response from
the body’s immune system and the surrounding tissues
which reduces the biocompatibility of the imp lant[25, 26,
and 27]. This is in total contrast to the corrosion products of
magnesiu m (Mg) wh ich can be considered physiologically
beneficial, with the adult body storing around 30 g of Mg in
both muscle and bone tissue[28]. The importance of Mg to
the body stems fro m the fact it is bivalent ion which is used
to form apatite in the bone matrix and is also used in a
number of metabolic processes within the body[29]. And
recently, Robinson et al. reported the novel antibacterial
properties of Mg metal against Escherichia coli,
Pseudomonas aeruginosa and Staphylococcus aureus[30].
Mg is a lightweight, silvery-white metal that is relatively
weak in its pure state and is generally used as an alloy in
engineering applications. The density of Mg and its alloys
are around 1.74 g/cm3 at 20o C, which is 1.6 and 4.5 times less
dense than alumin iu m and steel, respectively[31].
Interestingly, the density of Mg is slightly less than natural
bone which ranges fro m 1.8 to 2.1 g/cm3 , while the elastic
modulus of pure Mg is 45 GPa and human bone varies
between 40 and 57 GPa[32, 33 and 34]. Because of this close
similarity in the respective elastic moduli, using Mg in hard
tissue engineering applications would greatly reduce the
possibility of stress shielding and prevent bone resorption.
Thus, Mg with its similar mechanical properties to natural
bone, combined with its bioco mpatibility, makes it a
promising material for the development of biodegradable
orthopaedic imp lants[33, 35].
Poly meric materials have also been used in a number of
tissue engineering applications since they have many
attractive properties such as being lightweight, ductile in
nature, biocompatible and biodegradable. Poly mers are
materials with large mo lecules co mposed of small repeating
structural units called mono mers. The mono mers are usually
attached by covalent chemical bonds, with cross-linking
taking place along the length of the molecule. It is the

medical application of Mg based imp lants has been severely limited due to the electrolytic aqueous environment of the chloride rich body fluid (pH ranges between 7. However. However. 2) they are both chemically and thermally stable. Furthermore. So me of these applications include biodegradable sutures. aqueous environments where it rapidly degrades. 3) they exh ibit good wear resistance.Gérrard Eddy Jai Poinern et al. mechanical properties and potential applicat ion of biodegradable Mg based alloys for orthopaedic imp lants. These synthetic biopolymers can also be made into different shapes and structures. In addit ion. polymers. These biopolymers are generally poly-α-hydro x esters that de-esterifies in the body as the polymer degrades to simp le metabolites[79]. rods. Po ly (L-lactic acid). PLA[57-62]. A typical man made examp le of a bio medical co mposite is a b ioactive coating of HA P or a bioactive glass deposited on to the surface of a titanium implant to pro mote bone attachment[87]. have all produced favourable outcomes in a number of tissue engineering applications. Surface M odifications and Potential as a Biodegradable Orthopaedic Implant amount of cross-lin king that gives the polymer its physiochemical propert ies. A good example of a natural co mposite is bone. and 4) they are durable in the body environment[82]. Poly-capro lactone PCL[71-74] and Poly (g lycolic acid ). To slow the degradation rate in situ. non-immunogenic and can be easily sterilised[83]. by co mbin ing one or more phases with differing physical and chemical properties it is possible to create a composite material with superior properties to those of the indiv idual co mponents. and fibres as required for the specific applicat ion. tend to be brittle. so me bioceramics have found application in hip jo ints. When comparing the propert ies of Mg and its alloys with metals. 52] and collagen[53-56]. PGA [75-78]. nontoxic. see Table 1. inorganic materials that are used in hard tissue engineering applications where they are collectively termed bioceramics. with the by-products being easily excreted in the urine. as mentioned above. there are two serious consequences of the rapid corrosion rate of Mg imp lants. which has resulted in them being used in soft tissue reconstruction and low-load bearing applications. This article reviews the biological performance. However. the imp lant would be expected to maintain its mechanical integrity between 12 to 18 weeks while the healing process takes place and then slowly degrade while natural bone tissues replace the implant[92]. bone tissue engineering and drug delivery devices[81. The major advantage that Mg and its alloys have over biopolymers is its superior mechanical strength. These bubbles usually appear within the first week after surgery and can be easily treated by drawing off the gas using a subcutaneous needle[91]. The major advantage of using a composite biomaterial stems fro m the fact a single-phase material may not have all the required properties for a particular applicat ion[86]. The major disadvantage of using Mg in many engineering applications is its low corrosion resistance. Mg has the disadvantage of having a high corrosion rate in the body. However. . 84-86].: Biomedical M agnesium Alloys: A Review of M aterial Properties. The second consequence of the high corrosion rate is the loss of mechanical integrity of the Mg implant being used in the load bearing application. pins.6). Po ly (lactic-co-glycolic acid). 81]. hyaluronic based derivatives[47-50] and protein based materials such as fibrin gel[51. fixation devices and low load bearing applications in orthopaedics[80. factors influencing the corrosion rate such as alloying elements. PLGA[67-70]. maxillofacial reconstruction. coatings on implants. even with their many attractive properties. hemoco mpatible. they are readily available. And as a result. such as a 2-phase HAP-poly mer mixtu re have also been developed to create a bio material with similar p roperties to natural bone for hard tissue engineering applications[88]. plates. biopolymers biodegrade with time and as a result. if not superior. screws. fabricated under controllable formation conditions have produced a variety of tissue scaffolds and imp lants with tuneable and predictable physio-mechanical properties. But unlike Mg and its alloys. Ceramics are non-metallic. chitosan[41-46]. especially in electrolytic. The first is the rap id evolution of subcutaneous hydrogen gas bubbles which are produced at a rate too high fo r the surrounding tissues to handle[89. 90]. Natural poly mers such as polysaccharides[36-40]. which is a composed of Type 1 collagen and HAP. disks. These biopolymers also have low to xicity reactions with the body and their degradation rate can be easily controlled. PLLA [63-66]. they are bioco mpatible. Generally. despite its many advantages. such as pellets. have low fracture toughness and are not as resilient. ceramics and composites it can be shown that Mg and its alloys have many properties that are comparable. which is typically double that of biopolymers. films. biopoly mers have low mechanical strength when compared to ceramics and metals. bioceramics such as HAP. Examp les of synthetic biodegradable polymers include Poly (lact ic acid).4 and 7. the load bearing capacity and fracture toughness of the implant will decline with time. bone and dental cements. Currently available b iodegradable sutures in clinical use are made fro m PLA and PGA. Similar studies using synthetic biopolymers composed of simp le high purity constituent monomers. can be shaped to suit the application. The rapid decrease in mechanical properties resulting fro m exposure to the body fluid environ ment means that the implant is unable to provide the necessary support for the healing bone tissue. 220 A composite material consists of two or more distinct parts or phases[85]. Co mposites. Unfortunately. The important properties of bioceramics that make them highly desirable fo r b io medical applications are: 1) they are physically strong. surface modification and surface treatments are examined and discussed in the follo wing sections. Many polymeric materials have been investigated since the body’s natural processes can easily handle the by-products resulting fro m their degradation. bone grafting materials.

Table 2.3 1.260 230 45 45 45 Other metal alloys Cobalt-Chrome Alloys Stainless Steel Titanium Alloys 7. 126.15 100 .221 American Journal of Biomedical Engineering 2012. The o xidation rate of this protective o xide layer is typically around 0. evolv ing hydrogen gas and consuming the metal substrate surface. 96.5 – 38 35 Trans.h -1) Material In vivo corrosion rate (mg.38 LAE442 - - 0. Some mechanical properties of selected materials Compressive Strength (MPa) Te nsile Strength (MPa) Elastic Modulus (GPa) 1.72 60 1.Hydroxyapatite Alumina Ceramics (Al2O3 80% . magnesium with a negative electrochemical potential o f -2.74 1. 218.115 83 .12 – 1.5 – 9.39 WE43 - 0.75 – 11. see Table 2.99 2000 – 4000 - 260 – 410 1.900 40 – 200 70 – 120 3. 240 Long.99%) Polymers Polymethylmethacrylate (PMMA) Polyethylene.0 3. In magnesium alloys. proteins and electro lytic ions such as chloride and hydroxide. 126. Corrosion Mechanism When unprotected chemically pure magnesiu m is exposed to humid at mospheric air it develops a thick dull gray amorphous layer co mposed of magnesium hydro xide[Mg (OH)2 ].terephthalate (PET) Density (g cm-3 ) Note: Table compiled from references[122.9 4.0 – 1. which forms species that result in the formation of an o xide layer that adheres to the metal surface. chlorides and other compounds. 213. 0. 2(6): 218-240 Table -2. 214 and 215] For orthopaedic applications pure magnesium finds the human body a highly aggressive corrosive environment. hydroxides.0028 - 1.01 – 1.56 Pure Mg (99.37 V.17 AZ91 0. Corrosion rates for some magnesium alloys immersion in various media In vitro corrosion rate (mg. But in reality the electrochemical reaction results in the migration of ions fro m the metal surface into solution.50 -1.78 1. In this environment. controlling the alloying chemistry and the overall microstructure of the alloy can significantly reduce the corrosion rate.038 - AZ31 0.23 Magnesium Alloys Pure magnesium AZ31 (Extruded) AZ91D (Die cast) 1. while the o xidation rate in salt water is around 0.yr-1 ) Hanks Solution Simulated Body Fluid 0. is very susceptible to corrosion and results in free ions migrat ing fro m the metal surface into the surrounding fluid environ ment. 0.085 1.31 – 1. Biological Corrosion of Magnesium 2.1.0 1. The Mg (OH)2 layer fo rmed on the metal surface is slightly soluble and reacts with chorine ions to form highly soluble magnesiu m chlo ride and hydrogen gas[94.05 – 3. The corrosion of Mg in an aqueous physiological environment can be exp ressed in the follo wing equations. at the same time the reduction of protons is exp ressed by the partial reaction occurring at the cathode (2).20 45 – 107 38 – 80 1.8 7.001 1. When the oxide layer fully covers and seals the metal surface. In thermodynamic terms. 220 and 221] 2.8 – 2.960 480 – 620 550 – 985 195 . . 283 Long.4 1.5 Tissue /Material Natural Materials Arterial wall Collagen Collagen(Rat tail tendon) Cancellous bone Cortical bone Ceramics Synthetic.38 65 – 90 42 – 80 2.97 160 90 . These ions can form chemical species.30 – 3. 219.3 160 Trans.230 193 – 200 100 – 125 3. 213. The body flu ids are co mposed of water. the reaction would be very rap id. The primary anodic reaction is expressed by the partial reaction presented in equation (1).5 0.57 5 .2 – 3. it forms a kinetic barrier or passive layer that physically limits or prevents further migration of ionic species across the metal oxide solution interface.011 0.30 mm/yr[93].01 mm/yr. 95]. such as metal oxides. with the assumption that there is no barrier to oxidation of the metal surface.190 241 .81 20 .mm -2.95%) Note: Table compiled from references[92. dissolved oxygen.0065 - 1.4 - 450 .8 – 3.

+ H2 (1) (2) Another undesirable consequence of the corrosion process in Mg and its alloys is the formation of hydrogen gas. see Figure 2. For example.: Biomedical M agnesium Alloys: A Review of M aterial Properties. 2) variations in the pH value. if gold screws are used to attach an Mg plate to bone during reconstructive procedure. inter-granular corrosion does not occur since the grains tend to be anodic. The less noble metal beco mes anodic.2.→ 2OH. The rapid formation o f hydrogen gas resulting fro m the rich chorine environ ment produces subcutaneous gas bubbles. Solid Mg: (3) Mg (s) + 2Cl-(aq) → Mg Cl2 + 2eMg (OH)2 layer: (4) Mg (OH)2 (s) + 2CL-(aq) → MgCl2 + 2OHThe general reaction of the corrosion process is presented in equation (5). Galvanic corrosion resulting from inter-metallic elements 2. while their boundaries are cathodic in nature compared to the interior of the grains. Galvanic corrosion can also result fro m the presence of inter-metallic alloying elements or impurit ies present in the Mg matrix.2. If the oxide layer ruptures during mechanical loading it will expose the pure Mg substrate to body fluids wh ich will result in further corrosion. in the case of Mg alloys. 4) the presence of proteins and protein adsorption on the orthopaedic imp lant. 3) concentration of ions. During the init ial gas formation a subcutaneous needle can be used to draw off the gas.01 ml/cm2 /day can be tolerated by the hu man body and does not constitute a serious threat[96].+ 2eCathodic reaction: 2H2 O + 2e. Therefore. then the implant will not create a gas threat. Galvanic corrosion between dissimilar metals 2. inter-granular corrosion can occur fro m the presence of impurities and inclusions which are deposited in the grain boundary regions during solidification. the fixation screws used to attach an Mg plate during a bone reconstruction procedure should be made of a titanium (Ti) alloy.2. which generally appear within the first week after surgery and then disappear after 2 to 3 weeks[92]. each with a different electrochemical potential. The clinical repercussion of the corrosion process is the loss of mechanical strength and the ultimate failure of the imp lant. (5) Mg (s) + 2H2 O (l) → Mg (OH)2 (s) + H2 (g) Corrosion in the aqueous environment of the body is not as straight forward as corrosion in the industrial environ ment. The reactions of solid Mg and the Mg (OH)2 layer with chorine ions in the aqueous environment are presented in equations (3) and (4). However. Song postulated that a hydrogen evolution rate of 0. Mg is the most reactive metal in the electrochemical series and will always be the anode in any corrosion reaction[101]. since Ti is the closest metal to Mg in the electrochemical series.2. the resulting electrolytic effect of the body fluids (seru m or interstitial flu id) would preferentially attack the Mg plate. Following solidification. nu merous galvanic reactions takes place between the metal matrix and the various impurities and inclusions. 222 metals with similar electrochemical properties when designing implant devices. Galvanic Corrosion Galvanic co rrosion takes place between two dissimilar metals. Typical forms of Mg corrosion encountered within the body environment are d iscussed in the following sections. when they are in contact in the presence of an electrolyte which provides a pathway for the transfer of electrons. . Therefore. Figure 1. The resulting grain boundary corrosion undercuts nearby grains which subsequently fall out of the matrix[102]. In 2007. and 5) the influence of the surrounding tissues[97. The ensuing corrosion rate at the various grain boundary regions exceeds that of the grains and results in an accelerated corrosion rate of the metal matrix. see Figure 1[100]. This is due to the corrosion rate being influenced by a variety of other factors such as: 1) the pH of body fluids. selection of Ti alloy fixation screws to secure the Mg plate ensures the lowest possible corrosion rate. Types of Biol ogical Corrosion An important property of the o xide layer is its ability to remain fixed to the metal surface during a variety of mechanical loading situations. If the Mg corrosion rate can be regulated so that the hydrogen evolution rate is below this value. it would be good design practice to use Figure 2.Gérrard Eddy Jai Poinern et al. Surface M odifications and Potential as a Biodegradable Orthopaedic Implant Anodic reaction: Mg → Mg 2. 2. Granular Corrosion In many metal alloys. 98 and 99].1. For example. corrodes and produces a build up of corrosion by-products around the contact site.

The metallic debris impacts on the surface of the imp lant. Crevice Corrosion Pitting corrosion of Mg results from the rapid corrosion of small-localized areas which damage the protective surface oxide layer. In addition.2. Once formed the crack can propagate into the bulk of the metal mat rix and can lead to the failure of the imp lant. which adds to the accelerating autocatalytic growth of the pit. with an Mg+ ion concentration gradient soon set up between the entrance and the dead end of gap. can be considered physiologically beneficial since these ions can be consumed or absorbed by the surrounding tissues. The fo rmation of stress corrosion cracking and metal fatigue cracks in the pits can lead to failure of the imp lant during normal loading conditions. perforating the metal matrix[103]. see Figure 4.2. In the case of magnesium. see Figure 3. The stagnant flo w results in the build up of Mg + ions.2. exposing fresh metal underneath. Crevice corrosion occurring between magnesium components in a body fluid environment Erosion corrosion occurs from the wearing away of the metal surface or passive layer by the impact of wear debris in the body environment surrounding the implant. the microstructure of the metal o r metal alloys used in the implant and solution chemistry in the region around the fretting zone[109. For example. 26. Crev ice corrosion is local contact corrosion that occurs between metal and metal/non metal co mponents. the micro-motions remove the passive surface layer o f the metallic co mponents in direct contact.4. This form of corrosion is mo re serious than other forms of corrosion since the surface pits are difficu lt to see due to the presence of corrosion products. Then both the fresh metal surfaces and the metallic surface debris undergo o xidation. the resulting fretting motion. the mouth of the pit is s mall and prevents any dilution of the pit contents. During this process. Pitt ing Corrosion 2. electrons flowing fro m the pit make the surface surrounding the pit entrance become cathode-protected and the protective oxide layer is further weakened. Fretting Corrosion Fretting corrosion is the result of damage p roduced by metal co mponents in direct physical contact with each other in the presence of small vibratory surface motions. The environment within the pit is very aggressive. The corrosion rate is dependent on the applied load. the presence of impurit ies in the Mg alloy microstructure often assists in further corrosion due to the galvanic differences in the materials[104. The gap must have sufficient width to allo w the flo w of the body fluids through the gap and prevent any stagnant flow.3. which has the potential to form cracks[106]. 110]. Pitting corrosion site at the surface of a magnesium component 2. 2. During the corrosion process metallic ions are produced which can form a wide range of organic-metallic co mp lexes and some metallic imp lants can release toxic metallic ions such as chromiu m. 105].223 American Journal of Biomedical Engineering 2012. Once pitting starts. During the deformation p rocess the surface becomes work harden to the point where the next impact exceeds the strain required fo r surface fracturing. Another problem associated with pitting arises from localised increase in stress produced by the pit. 2(6): 218-240 2.5. highly corrosive and continue to grow downwards. Fretting corrosion is common in load bearing surfaces and is also capable initiat ing fatigue cracks in the fretting zone. Erosion Corrosion Figure 4. The micro -motions are produced by normal every day activities experienced by the human body which result in mechanical wear and metallic debris between the surfaces of metal components making up the biomedical imp lant[108]. The surface debris has a further detrimental effect by acting as an abrasive agent during subsequent micro-motions. with chlorides species from the body flu ids and Mg + ions from anodic dissolution greatly aggravating the situation. or be dissolved and readily excreted through the kidneys. its load bearing capacity would be greatly reduced to the point of failure. cobalt and nickel. if a magnesium plate is to be fixed in location by a set of screws with a small gap between the screw head and plate. Figure 3. transferring energy into the region of the collision and plastically deforming the surface. . After init ial nucleation at the surface. and 27]. an Mg component can be totally penetrated within a relatively short period of time and in the case of a biomed ical imp lant. metallic ions released during fretting. During daily activ ity. The pits are small. These harmfu l metallic ions significantly reduce the biocompatibility of the imp lant and solicit a major inflammatory response from the body’s immune system[25. The subsequent corrosion cell then starts to attack the metal components of the implant[107].6.2.

2) imp roving the corrosion resistance. a mechanism know as stress corrosion cracking (SCC). Magnesium and its Alloys For bio medical applicat ions. a biodegradable bio medical device should be co mposed of materials or alloys that are non toxic or carcinogenic. or being dissolved and readily excreted through the kidneys.8. 114]. AZ31 and rare earth elements (RE) such as AE21. Corrosion Fatigue Corrosion fatigue is the result of a material being exposed to the combined effects of a cycling load and a corrosive environment[120]. Therefore. Fe (30-50 ppm) and Ni (20-50 pp m)[122]. A ll bio-metals used in implants inevitably corrode at some fin ite rate when immersed in the complex electrolytic environ ment of the body. see Tab le 3. If there are any surface imperfections such as pores or pitting fro m corrosion. Eventually the loading stress exceeds 224 the SCC threshold and the crack grows to a critical size resulting in the fracture of the metallic implant. Th is usually results in the formation of s mall cracks that concentrate stress within the loaded implant. It would also be very advantageous if the material was composed of elements and minerals already present and compatible within the body such as magnesium. Y. Zr and RE in Mg alloys can significantly imp rove the physical and mechanical properties of the alloy by: 1) refin ing the grain structure. Current research suggests that chloride ions produce pitting in the protective surface layer. In the body’s environment the cracks become localized electrochemical cells that promote further corrosion. The progress of SCC is also influenced by the strain rate resulting fro m the implant loading cycles and the presence of hydrogen gas produced by the corrosion process[115. see Table 3. MZ and WZ. The use of alloying elements such Al. The cyclic stress initiates the formation of microscopic cracks on the metal surface and also damages the protective passive layer. Since both Be and Ni are carcinogenic. Ho wever. they become crack nucleat ion sites which can significantly speed up crack g rowth rates. The range of acceptable levels for Be ranges fro m 2 to 4 ppm by weight. the material should have a controllable d issolution rate or slow corrosion rate that permits the biomed ical device or imp lant to maintain its mechanical integrity until the surrounding tissues heal and are capable of carrying the load once again. and the final group consists of the Al free alloys such as Mg-Ca. even Ti alloys with the lowest corrosion rate produce corrosion debris. The debris can significantly influence the wear behaviour and erosion resistant properties of the imp lant.2. capable of being consumed or absorbed by the surrounding tissues. Mg in particular is susceptible to corrosion fatigue due to the presence of chloride ions in the body fluids. The Influence of Alloyi ng Elements on Physical and Mechanical Properties There are three major groups of Mg alloys: the first group consists of pure Mg. Mg SCC can occur in any load stressed implant immersed in the dilute chloride environment of the body fluids. the effects of erosion may not be noticed until there is a significant loss of metal which ultimately leads to the clinical failure of the imp lant. wh ich ultimately leads to a break down in the layer exposing the underlining Mg matrix to the electrolytic flu ids of the body environment. W E. the composition of the material being considered is a crucial factor since many of the elements that make up co mmercially available materials for industrial applications are extremely to xic to the human body. The body environment can significantly reduce the fatigue life of Mg alloys. Mn.: Biomedical M agnesium Alloys: A Review of M aterial Properties.Gérrard Eddy Jai Poinern et al.2. the crack gro wth rate significantly increases. metal fatigue is the damage caused by the repeated loading and unloading of a metal component. Furthermore. usually by two to three times above the normal uniform rate. the material must also be bioco mpatible. Fracture and failu re of the imp lant will occur when the SCC is belo w the normal operating stress of the implant. the numerous impacts result in material loss fro m the metal surface[111]. 3. Surface M odifications and Potential as a Biodegradable Orthopaedic Implant pitting or chip format ion. Stress Corrosion When an electrochemical potential is formed between stressed and unstressed regions of a metal implant under load. their use in b io medical applications should be .7. 3. SCC init iated cracks grow rapidly and extend between the grains throughout the metal matrix[113. the second group consists of aluminiu m (Al) containing alloys such as AZ91. Ideally. 116]. Impurit ies common ly found in Mg alloys are Be. for Mg and its alloys to be used as an effective biodegradable imp lant it is necessary to control their corrosion behaviour in the body flu id environ ment[121]. Zn. there is an increase in the chemical act ivity of the metal. 2. 2. a femo ral head of a Cobalt-Chro miu m imp lant will have numerous scratches after 17 years of imp lantation in a patient[112]. while Cu is (100-300 pp m). producing lo wer failure stresses and considerably shorter failure times. The resulting hydrogen diffuses into the stressed zone of the metal matrix ahead of the crack tip and allows the SCC crack to advance through the zone[117-119]. Fu rthermore. calciu m and zinc. 3) form inter-metallic phases that can enhance the strength. Cu. and 4) assist in the manufacture and shaping of Mg alloys. Corrosion within the crack pro motes crack propagation and in co mbination with cyclic loading. Fe and Ni and the levels of theses impurities are restricted to within specific limits during the production of the alloy. the resultant by-products of the degradation process should be non-toxic. Li. After the healing process has taken place. This stress initiated corrosion mechanism effect ively increases the corrosion rate.1. Ca. With the passage of time. For examp le. in addition to meeting the mechanical properties needed for a particular bio medical applicat ion. In general. Thus. the load bearing properties of the biomed ical implant are no longer required and the imp lant material should then be able to slowly dissolve away.

%) Al Zn Mn Ca Li Nd Zr Y AZ31 3. en zy mes and proteins[133]. but lower values of corrosion resistance and degraded at similar rates[92]. neodymiu m and praseodymiu m {LA E442}[92.004). 126]. the first consisted of 4% yttriu m and a 3% rare earth mixtu re composed of neodymiu m. 4%. 2(6): 218-240 avoided as alloying elements.001) and Be (5 – 15 ppm) AM60 6. 129].008). Cu (0. with co mplete imp lant degradation occurring at 18 weeks. %) Maximum values of trace elements (wt. Si (1.3 - - - - - Fe (max 0. 93. 217 and 218] 0. lanthanum.0 Contains some heavy metal rare earth elements . Also during this period a thin amorphous calciu m phosphate layer formed over the surface of the o xide layer[92. praseodymiu m and yttrium has resulted in severe hepatotoxicity in rats[132]. while a micro -tomography-based technique using X-ray synchrotron radiation was used to characterize the imp lant’s degradation process. Studies by Song have suggested that very small quantities of RE elements and other alloying metals such as Zn and Manganese (Mn) could be tolerated in the human body and could also increase corrosion resistance[123].2 - - - Note: Table compiled from references[92. 216. but in the case of the human body. Table 3. The long term health effects on the rabbits are unknown. Non-toxic alloying elements such as Ca[134] and Zr[135] have the potential to significantly improve the corrosion resistance of the Mg alloy and reduce the degradation rate to make the Mg metal alloy a viab le implant material[33]. Mn is added to many co mmercial alloys to improve corrosion resistance and reduce the harmful effects of impurit ies[124].5 0.025). 127]. the release of Al into the body will create undesirable health problems[130]. While Mg is potentially an ideal bioco mpatible imp lant material due to its non-toxicity to the human body.2 0. Si (0. while the polymer control rods produced a less significant effect. dementia and senile dementia[131].5 1.003). Magnesium based alloys have also been used in vivo. Therefore. Ni (0. Chemical analysis of alloying elements for a selection of magnesium alloys Alloy Nominal element component (wt.5 4.2). In addition two RE alloys were studied. for examp le an AZ91 alloy rods were imp lanted into the femur of a nu mber of rabbit models and the subsequent analysis revealed that after 3 months the implant had degraded and been replaced by new bone tissue[128. Si (0. All Mg based alloy imp lants were found to be beneficial and pro moted new in situ bone tissue format ion.05). which also contained high levels of both calcium and phosphorous. see Table 4.0 4.0 Contains some heavy metal rare earth elements WE43 - - 3. Recent studies by Witte et al. Ni (0. Ni (0. Cu (0.3 - - - - - Fe (max 0.5 0. Mn and Zn are essential trace elements for hu man life and RE elements exhib iting anti-carcinogenic properties should be the first choice for incorporation into an alloy.0 0. During the degradation process the RE elements remained localised in the corrosion layer. At the end of this degradation process most of the alloying elements such as Al would have been released into the bodies of the rabbits. Cu (0.004).2 - - - Fe (max 0. While elements such as Ca. ceriu m and dysprosium {W E43} and the second composed of 4% lithiu m. In hu mans. alu miniu m and a 2% rare earth mixture o f ceriu m. The percentage compositions by weight of the Mg alloys investigated consisted of two alu min iu m-zinc alloys co mposed of 3% Al and1% Zn {AZ31} and 9% Al and 1% Zn {AZ91} with the balance of the alloys composed of pure Mg.001) and Be (5 – 15 ppm) LAE442 4. Furthermore.05). there is a definite requirement to carefully select alloying elements that are non-toxic to the hu man body. The LA E442 alloy had the greatest resistance to corrosion. the administration of RE elements such as cerium.001) and Be (5 – 15 ppm) AZ91 9. the safe long term use of an Mg based alloy needs to be carefully studied.008). Rods of 15 mm d iameter and 20 mm long were inserted into the femu r of guinea p igs and the rods degradation profile monitored. have investigated the degradation behaviour of Mg based alloy rods and polymer based control rods[poly (lactic acid)] in animal models. The imp lants were harvested at 6 and 18 weeks. using heavy metal elements as alloying components are also potentially to xic to the human body due to their ability to form stable co mplexes and disrupt the normal mo lecular functions of DNA. wh ile the other alloys all had similar. Mg alloys containing rare earth elements have also been found to increase the resistance to the flow of Mg 2+ ions out of the Mg matrix via the Mg oxide layer[125]. In addition.4 0. During this time radiographs were regularly taken.0 2.225 American Journal of Biomedical Engineering 2012. Al is a neurotoxicant and its long term accu mulation in brain t issues has been linked to neurological disorders such as Alzheimers disease.

Blood serum level 12. The in itial inflammatory phase usually lasts between 3 to 7 days and this is the natural response of the body’s immune system to the presence of the biomedical device or imp lant. As a consequence. The reparative phase usually takes 3 to 4 months. through a treat ment process that provides a resistive barrier against the body environment. Abundant mineral that is mainly stored in bones and teeth. Surface M odifications and Potential as a Biodegradable Orthopaedic Implant 226 Table 4. however.8 µg/L Tends to diffuse out of Mg matrix Neurotoxic (influences function of the blood brain barrier) Linked to Alzheimer’s disease Accumulates in amyloid fibres/brain plaques. which was discussed in Section 3. can take fro m several months to years to complete[136]. There are t wo methods of reducing the degradation rate. The healing process consists of three phases. Note: Table compiled from references[122. Accumulate in the liver and bone In high concentrations is neurotoxic and can hinder bone development. Accumulates in bone tissue/decreases osteclast viability Blood serum level 0. The final remodelling phase.Gérrard Eddy Jai Poinern et al. Pathophysiology Toxicology Blood serum level 2. Un fortunately. which is the longest phase. The second method is d iscussed in this section and involves the surface modification of the imp lant. Blood serum level <0.: Biomedical M agnesium Alloys: A Review of M aterial Properties.1-4. Fo r Mg to be an effective bio-absorbable implant the degradation rate must be slow enough for the healing process to take place and the new tissues have sufficient time to provide their own structural support before the structural integrity of the imp lant is compro mised. Improves die cast-ability Calcium Adding to improve corrosion resistance in Mg-Ca alloys.4µmol/L Essential trace element Essential to enzymes and immune system Excessive amounts of Mn can produce neurological disorder. Influences metabolic cycle of lipids/amino acids and carbohydrates Blood serum level 2-4ng/g Used in drugs to treat psychiatric disorders Many rare earth elements have anticancerogenic properties and are used in the treatment of cancer. Common alloying elements used in magnesium alloys Alloying Element Aluminium Mechanical Properties Enhancement to Mg Matrix Rapidly diffuses through Mg matrix.8 µg/L Essential trace element Influences cellular functions/immune system/blood clotting/bone growth. surface .919-0. Copper Can increase strength of Mg casts. 225. Activator/stabilizer of enzymes. Mg alloys can completely degrade before the end of this timeframe and as a result there is a need to reduce the biodegradation rate. Manganese Adding to reduce the harmful effects of impurities and improve corrosion resistance Lithium Improvement in corrosion resistance Rare earth Elements Improvement in corrosion resistance Zinc Improves yield stress. Blood serum level 74-131 µmol/L Essential trace element Excessive amounts of Cu have been linked to neuro-degenerative diseases. Levels controlled by Homeostatis of skeleton. An important factor that needs to be taken into account before any surface treatment is investigated is the healing or regenerative processes of bone and other associated body tissues. The bulk propert ies of Mg based alloys dictate its mechanical properties. 213.4-17. inflammatory. the first. it also accelerates corrosion rate when exposed to a NaCl medium. and acts as a passivating element and improves corrosion resistance. Mg alloys containing Zn have an Elastic Modulus similar to bone. impaired kidney function. 226 227 and 228] 4. Surface Modifications and Treatment Processes for Biomedical Mg Alloys The high degradation rate of Mg and Mg alloy implants in the human physiological environ ment would result in the reduction of mechanical integrity of the imp lant before the bone tissues had sufficient time to heal[26]. The minimu m period for this to take place is at least 12 weeks[26]. 222. Involved in blood clotting Metabolic disorder of calcium levels results in the formation of excess calcium in the kidneys (stones). 224. Can produce cellular cytotoxicity. lung dysfunctions. (manganism) Overdose causes central nervous centre disorders.993 mg/L. reparat ive and remodelling. during which t ime integration of the imp lant with the new and regenerated tissues takes place. The presence of Zn can reduce hydrogen gas evolution during bio-corrosion. but it is the surface properties that influence the interaction between the metal and the surrounding tissue environment of the body. involved alloy ing Mg with biocompatible elements that can resist the corrosion process. 223. 134.

During the process a metal or metal alloy is heated in vacuum chamber until it evaporates and then the subsequent vapour condenses onto the cooler substrate. A recent study by Denka et al. wh ile the test samples with the rougher surfaces promoted higher degradation rates.227 American Journal of Biomedical Engineering 2012. at low cutting speeds. The smooth cylinders were machined with no fu rther surface treat ment. while chip removal fro m the surface during machining can direct ly influence the surface topography[144]. Therefore. the protective coating must be uniform. The study also highlighted the need for further investigation into the effects of different surface modifications on other biocompatible Mg alloys.1. For examp le. The suppression of crack formation is also an important factor in improving the fatigue life cycle of a material being considered fo r b io medical applications[146. To date. columns. the most effective way to prevent corrosion is to coat the metal co mponent with a protective barrier that effect ively isolates the metal fro m the surrounding environment. 4. The first test sample was a machined 3 mm diameter s mooth cylinder. the second was like the first. which can induce work hardening of the sub-surface. shot peening. In their study three surface machining treatments were applied to an Mg-Ca (0. the use of rolling operations can also generate high passive forces acting normal to the surface. The presence of the o xide/hydroxide layer will have a detrimental effect on the ability of the coating to adhere to the metal surface and form a unifo rm p rotective layer. numerous surface modification techniques have been developed to change the surface characteristics of biomaterials. cell growth and implant integration. as mentioned earlier. The results indicated that the smoother micro-topographic surface features of the cylinders were suitable for resorbable Mg alloys. in most PVD processes the substrate temperature range is usually between .1. The major problem with Mg. In the case of Ti alloys. scratches and cracks. The sand blasted cylinders had the greatest material loss with the init ial cylindrical shape completely consumed. while the threaded cylinders ranged between these two extremes. 4. Studies of conventional types of permanent imp lant materials have shown that surface roughness can influence both cell morphology. During the rolling operation the sub-surface grain structure is changed by the compressive stresses induced and the resultant micro -topography of the surface is significantly changed[145]. the surface formed by honed cutting tools tends to produce a rougher surface than those of sharp cutting tools. After 6 months of in vivo imp lantation in adult New Zealand white rabbits.8 % wt calciu m) alloy. modification of the surface topography by the physical placement of grooves. except that it was sand blasted for 30 s using particles ranging in size fro m 300 to 400 µm and the final surface topography was a threaded cylinder.2. For Mg alloys. The results of this study clearly indicated that differences in surface roughness of the test samples could significantly influence the in vivo degradation rates. Besides machining techniques for chip removal. 142]. but in the case of Mg there are a number o f problems to overcome. since it is the init ial response of the surrounding tissues to the surface of the implant material that determines whether or not there is effective t issue-biomaterial integration. The importance of surface and sub-surface treatments on Mg alloy implants was recently investigated by Von Der Hoh et al. surface sand blasting and acid etching has revealed that grooved surface features provide superior cell attachment and promote greater cell pro liferation than roughen surfaces[140]. the exact effect on the underlining sub-surface is not fully understood[143]. co mpared to the same alloy that was mach ined[146]. To be effective against corrosion. The alloy was used to make three different geometric sample types. In addition. Also. so they retained the micro-surface topography produced by the cutting tool.2.[148]. during milling and similar metal chip removing processes. well adhered and free fro m any imperfections such as pits. This process has been successfully used on a variety of metals. the smooth cylinders revealed good integration with the surrounding tissues and also had the least structural loss. pits and other depressions can influence cell orientation and attachment[137-139]. 147]. 2(6): 218-240 modifications and treatments can have a significant ro le to play in governing the degradation rate of the implant. Physical Vapour Deposition (PVD) & Chemical Vapour Deposition (CVD) The PVD process involves the deposition of thin layers of metal and metal alloys fro m ato ms or mo lecules fro m the vapour phase onto a substrate surface. 4. Physical and Chemical Modifications Fro m an engineering point of view. In the case of milling. Mechanical processing techniques involve operations such as rolling. surface modifications such as grooves. has revealed a significant reduction in the corrosion rate (a factor of 100 was achieved in corrosion studies) of an Mg-Ca alloy that was deep-rolled. the influence of different mechanical p rocessing operations during fabricat ion has the potential to great ly influence surface and subsurface properties[141. surface cleaning and a suitable pre-treat ment o f the metal surface is a crucial factor in achiev ing an effective surface coating. is its chemical reactivity when exposed to air or an aqueous environmental wh ich results in the formation of an oxide/hydroxide layer over the metal surface. The presence of residual co mpressive stresses after ro lling also has the advantage of reducing micro -crack formation fro m pre-existing crack nucleation points within the substrate. and milling. A brief overview of so me of these surface modificat ion processes are presented in the following the four sections. Mechanical Modificati ons to Induce Surface and Subsurface Properties The surface structure of an imp lant is very important. Many of these methods have been applied to modifying the surface p roperties of Mg bio-alloys.

ceramics. 4. During this process physiochemical changes take place in the sub-surface of the substrate. but also found that an interfusion layer had formed between the Ti coating and the Mg substrate. Subsequent testing in simulated body flu id at 37 ± 1℃ revealed that the corrosion resistance of ion treated AZ91 alloy was improved significantly. In a similar study by Fang et al. metal alloys. which was predominantly composed of TiO2 with a smaller amount of MgO. The results revealed that after ion implantation. This highlights the weakness of thermally sprayed ceramic coatings which have rough surfaces. but in the case of Mg the substrate temperature must be kept below 180 o C for material stability reasons. Ceramic coatings such hydroxyapatite (HAP). a post heat treatment process was carried out 450℃. which effectively reduced any protective properties offered by the coating. The resulting micro meter size droplets are accelerated in the gas stream. This technique can also be used to improve the surface properties of an Mg alloy substrate by melting a metallic coating and the underlin ing sub-surface. 150]. The ionized part icles penetrate the surface and become embedded in the sub-surface of the substrate. The chemical vapour deposition process has also been used to produce a variety of coating processes that can create a protective coating or modify the existing Mg alloy surface. the deposition of diamond like carbon (DLC) films on metallic imp lants can improve the surface properties of the imp lant. Wan et al. The material is then heated to a molten or semi mo lten state within a gas stream.2. 4. the results found that the ion-imp lanted substrates had a lower corrosion resistance than the untreated substrates[157].2. During the deposition of a solid material fro m the vapour phase onto a (usually) heated substrate a chemical reaction over the surface takes place. The results not only revealed a substantial improvement in corrosion resistance.9 wt % NaCl solution[158]. and ZrO2 have also been successfully applied to Ti alloys to improve their corrosion resistance. surface chemistry and wear resistance. The subsequent corrosion studies have revealed that the binary-alloyed surface coating were capable of increasing the corrosion resistance of the various Mg alloys[151-153]. thus making it biocompatible with the surrounding body tissues[154]. Ion Imp lantation and Plating Ion imp lantation consists of bombarding the surface of a substrate with ionized particles. The study also revealed that galvanic corrosion occurred between the surface of the Mg alloy and the coating layer. The surface region of the alloy can be melted to create a meta-stable solid solution. used this technique to plate a pure Mg substrate with Ti ions and then subsequently studied its corrosion behaviour in a 0. to deposit an Al layer on an AZ91D substrate[160]. This is then followed by rapidly cooling the substrate. roughness. The PVD process has successfully deposited binary alloys such as Mg-Ti. thermally sprayed TiO2 onto an Mg alloy (AM60) revealed that the subsequent coating showed no improve in its corrosion resistance compared to the untreated Mg alloy when they were both immersed in Hanks’ solution[162]. To date there have been relatively few studies carried out that have used ion imp lantation to enhance the surface properties of Mg alloys. 4. Al2 O3 .. The lower substrate temperature of Mg also influences the adhesive and corrosion resistance properties of the coating[149.2. Subsequent analysis of the results suggests that Zn was an unsuitable metal for ion imp lantation with Mg-Ca alloys for b io medical applicat ions. Mg-Zr and Mg-Mn along with other less biocompatible and to xic alloys. materials such as metals.Gérrard Eddy Jai Poinern et al. The study revealed that a compact surface oxide layer was formed. The surface o xide layer fo rmed during corrosion testing in simulated body fluid enhanced the Mg-Ca alloys corrosion resistance. However. To ensure adhesion of the coating to the substrate.4. However. examined a Mg-Ca alloy before and after Zn ion implantation. During the rapid melting process both the coating and sub-surface mix before re-solidifying during subsequent cooling to form a new surface alloy which coats the bulk of the substrate. The ionized particles soon neutralize in the interstitial positions within the grain structure forming a solid solution. A recent study by Liu et al. The disadvantage of using an Al coating on the AZ91D substrate for a possible bio medical implant applicat ion is the negative effect of Al3+ ions being released into the surrounding tissues during subsequent corrosion. Zhang et al. For examp le. Furthermore. high porosity and poor adhesion properties[163].2. Thermal Spray Coatings During th is coating process. Ion plating is a technique that deposits noble metal ions onto a less noble metal substrate to form a dense and 228 well-adhered layer. TiO2 . which chemically modifies the surface properties. poly mers and composites are feed (powder or wire form) into a gun. Laser Surface Melting. the Zn had improved the surface hardness and elastic modulus of the alloy. in a study by Zeng et al. the corrosion behaviour of a new med ical grade Mg-Ca alloy was examined before and after Zn ion imp lantation[156].: Biomedical M agnesium Alloys: A Review of M aterial Properties. which is directed towards the surface of the substrate[159]. This technique was successfully used by Zhang et al.3. wear resistance and biocompatibility[161]. There was significant diffusion of Al and Mg around the interface of the coating. examined the corrosion behaviour of surgical AZ91 after it was subjected to Ti ion imp lantation[155]. if the appropriate alloying metals are . wh ich results in the refinement of the surface microstructure. wh ich enhanced both the corrosion resistance and anti-wear properties of the coating. Alloying and Cladding The high-density energy of a laser beam can be effectively used to modify the surface region of Mg alloys. while the bulk properties of the substrate remain unchanged. The plating layers improve surface properties such as topography. This results in changes to the sub-surface of the substrate. Surface M odifications and Potential as a Biodegradable Orthopaedic Implant 400 and 550 o C.

but it did significantly slow down the degradation rate[171].3. with each element being used individually to form a surface treatment solution. with the excess phosphate ions being released into the surrounding environment. In . most metals are mo re electrochemically noble than Mg. Fro m an industrial point of view. imp roved surface properties of a Mg alloy (AZ91) have been achieved with the dispersion of hard metallic part icles such as TiC and SiC in the molten pool generated by laser melting[166. phosphate/permanganate. have investigated the behaviour of a phosphate treatment on an Mg alloy (Mg-Mn-Zn) that was subsequently immerged in a simulated body solution (SBF). 4. However. 2(6): 218-240 incorporated into this surface modificat ion technique it is possible to significantly imp rove surface properties such as corrosion resistance[164. While a stannate treatment developed by Gonzalez-Nunez et al. the electrons for reduction are supplied fro m an external source and the resulting metallic ions are deposited on to the surface of the substrate. The study revealed that the second conversion layer had improved corrosion resistance compared to the first. The first solution contained CeCl3 which formed a conversion layer consisting of Mg (OH)2 . laser cladding of an Al-Si alloy onto a number of Mg alloys such as AS41. there are several different types of conversion coatings such as chromate. but unfortunately. Unfortunately. The conversion coating acts as protective barrier that isolates the substrate from the surrounding environment and prevents the corrosion. rare earth. In this technique a metal salt is reduced in solution to its metallic form.3. An alternative treatment to chromate conversion coatings are: 1) phosphate. 169]. And an in vivo study carried out by Witte et al. electroplating is a highly effect ive technique for coating Mg and its alloys with metallic coatings such as nickel. 4. However. which was incapable of withstanding minor mechanical damage. All three of these conversion treatments have comparable corrosion resistant properties to those of chromate t reatments. was able to deposit a 2 to 3 µm thick layer of MgSnO3 on an Mg alloy (ZC71). these metals are also harmful to human t issues. In a similar study by Gao et al. 167]. Xu et al. 2) phosphate-permanganate. Magnesium fluoride (MgF2 ) conversion coatings on Mg alloys have produced mixed results in providing corrosion protection. indicating that more studies are needed to indeed gauge the effectiveness of this process for in vivo applications. 4. Many of the processes used to produce conversion coatings involve the use of toxic materials that are detrimental to hu man health. While in a similar study Hassel et al. both coating provided limited corrosion resistance due to their thin thickness and soft structure. using Mn 3 (PO4 )2 was ab le to produce a resilient surface coating on a Mg alloy (AZ31D) that was self healing in saline solutions[172]. that is used in chromate coatings. continuous. found that a conversion layer of MgF2 formed on an Mg alloy (ZM 21) could provide reasonable corrosion resistance[175]. The coating was adherent. Electrochemical Deposition of Metallic Coatings The corrosion resistance of Mg and its alloys can be increased by an electroplating technique. and 3) stannate coatings. CeO3 and MgO. Such imperfections will expose the underlin ing substrate and result in the format ion of s mall localized areas of corrosion. the surface properties were not significantly improved[168. which make them h ighly unsuitable for biomed ical applicat ions.2H2 O] was formed on the surface of the substrate.3. The released phosphate ions were also found to neutralize the alkalizat ion effect produced by the corrosion process. During the treatment process a biocompatible brushite layer[CaHPO4 . Furthermore.9 wt % NaCl solution[174]. both the toxico logy and metabolic pathways within the human body of RE elements such as Ce and Y are still unclear and need to be fully investigated before they can be used in bio medical applications. which can cause serious problems if there are any imperfect ions in the deposited layer.2. 165].229 American Journal of Biomedical Engineering 2012. the feasibility of forming RE conversion layers on pure Mg to improve corrosion resistance was examined[177]. AZ91 and W E54 have also been attempted.3.1. Chemical Conversion Coatings Chemical conversion coatings are formed by chemically treating the surface of Mg and Mg alloys to produce a thin outer coating of metal o xides. Subsequent immersion in SBF revealed that the brushite layer transformed into a coating of HAP. Industrially. Unfortunately. reported that an MgF2 conversion layer formed on an Mg alloy (AZ31) provided marg inal corrosion resistance in a 0. the presence of hexavalent chromiu m (Cr6+). Degradation studies carried out by Zeng et al. revealed that a conversion layer thickness between 150 and 200 µm formed on the surface of a RE based Mg alloy (LAE442) was able to reduce the degradation rate and reduce the release of alloying elements[176]. stannate and hydrides. And a phosphate-permanganate process developed by Han et al. Also. Y2 O3 and MgO. and crystalline which produced a passivating effect on the substrate surface[173]. The two RE elements under investigation were Ce and Y. These coatings have good mechanical properties and provide effective corrosion protection. The treatment process did not prevent corrosion. The corrosion sites form h ighly corrosive pits that tunnel down into the Mg substrate and seriously weaken the substrate[141]. ch ro me and alu min iu m coatings[142]. phosphates or other compounds that are chemically bonded to the surface[170].3.. Fo r examp le. no degradation rate data was reported. while the second solution contained Y(NO3 )2 which formed a conversion layer consisting of Mg (OH)2 . Wet Chemical Processes 4. Fo r example. Calciu m Phosphate Surface Coatings A more bioco mpatible form of conversion coating can be derived fro m a variety of calciu m phosphate compounds.

the microstructure of the Mg-Al alloy changes as the Al atoms in the alloy diffuse towards the grain boundaries and subsequently precipitate out of solution to fo rm the β phase. used an electro-deposition technique to produce three types of coating namely. Alkali Heat Treat ments Heat treat ment can be a beneficial way of improving the microstructure and enhance the surface properties of Mg and Mg alloys. During heat treatment (solution treat ment at 413 o C for 24 h followed by aging at 216℃ for intervals of 1 h.2H2 O) surface coating. 191]. a calciu m phosphate compound with a mo lar ratio of 1. The processing parameters that influence oxide layer formation include: 1) the type. which has been widely used as a bone substitute and replacement in several biomed ical applicat ions[178-180]. These parameters can also .4H2 O and Na2 HPO4 . Anodization The anodization of magnesium is an electro-chemical process that changes the surface chemistry of the metal.. And as a consequence of the diffusion process (Aging). In addition. The porous layer can d isplay a variety of different structures and properties which are dependent on the composition. 18 8]. The study also found that the brushite coating was able to improve the surface biocompatibility of Mg alloy substrate. SBF solutions with and without chloride ions were used to study the influence of chloride ions on the corrosion behaviour of treated Mg samples.: Biomedical M agnesium Alloys: A Review of M aterial Properties. HAP[Ca (PO4 )6 (OH)2 ]. It is also due to these positive biolog ical responses within the human body that has made calciu m phosphate coating an attractive option for potentially reducing the biodegradation rate of Mg orthopaedic imp lants. HAP and fluorapatite (FHA ). The DCPD layer was effective in providing protection for the Mg substrate during the first 21 days of immersion in a simu lated body fluid. Furthermore. which involved immersing a Mg substrate into a solution containing Ca and P[Ca (NO3 )2 and Na2 HPO4 ] to create a di-calciu m phosphate di-hydrate (DCPD) surface layer[194]. ele ctro. DCPD. 4.Gérrard Eddy Jai Poinern et al. the surface of the untreated samples displayed deep and uniform corrosion. investigated the influence of low magnetic fields during a one-step dipping technique [195]. 5.18 6]. The corrosion behaviour and cytotoxicity of alkali heat-treated pure Mg samples immersed in simulated body fluid (SBF) were investigated by Li et al. A similar calciu m-phosphate coating was produced by Wang et al. In an alternative method. Surface M odifications and Potential as a Biodegradable Orthopaedic Implant particular.858 was detected on the surface of the samp les. 2) current density. the corrosion behaviour of a heat-treated Mg-Al alloy (AZ63) immersed in a SBF solution for 14 days was investigated[198]. In addition. which tended to have a neutralizing effect on the alkalizat ion process[192]. It is these advantages that make HAP and TCP (tri-calciu m phosphate) compounds attractive for coating metallic orthopaedic implants. These properties are very important because bone tissue constantly undergoes remodelling. In a similar study by Liu et al. Recently. acid ic phosphate ions were released into solution. and 3) it offers good osteoconductivity and osteoinductivity capabilit ies[181. (osteoblasts and osteoclasts respectively). the study found that samples microstructure significantly influenced the overall corrosion morphology..4. the layer formed was porous and did not prevent corrosion in a simulated body fluid. The samples for treat ment were p laced into a super saturated NaHCO3 -MgCO3 solution and then heat-treated. wh ich in turn reduced the degradation rate[195]. Deposition of both DCPD and HAP phases under the influence of magnetic fields lead to crystal orientation during the formation of the phases. Several techniques have been used to deposit calciu m phosphate coatings onto Mg substrates. and 3) the applied anodization voltage.5h and 12 h). However. after 14 days of immersion in the SBF flu ids. hydrothermal [189] and wet chemical methods[190. 182]. fo llo wed by a less dense porous oxide layer. b io-mimet ic co atings[1 84.5. the degradation rate was significantly reduced and provided the Mg alloy substrate with reasonable protection against the corrosive effects of the simulated body flu id. temperature and concentration of electrolyte. There are three major advantages in using HAP in hard tissue engineering applications: 1) it has good biocompatibility and bioactivity properties with respect to bone cells and other body tissues. Unfortunately. v ia oxidation.3. The study found the FHA coating had long-term stability and remained intact even after 1 month of immersion in a simulated body fluid and provided effective corrosion resistance to the Mg alloy[196]. 230 Song et al. While the subsequent cytotoxicity testing revealed no signs of morphological changes in the cells and no inhibitory effect of the surface treatments on cell growth could be detected. For examp le. the concentration of Al atoms remain ing in the matrix (α phase) decreases and results in the matrix having a reduced corrosion rate. since the brushite coating transformed into a HAP phase with time. to produce a stable anodic o xide layer. A ll the treated samples showed a significant imp rovement in corrosion resistance in both SBF (Cl-) and SBF solutions compared to the untreated Mg samples. has investigated using an immersion technique that involves soaking an Mg-Mn-Zn alloy in an alkaline solution to form a b rushite (CaHPO4 . a process in which bone tissue is simultaneously replaced and removed by the bone cells. The technique also produced coatings with enhanced corrosion resistance.12H2 O. The structure of this layer is characterized by a thin barrier layer at the metal-o xide interface. Yanovska et al. The involved dipping a Mg substrate into an aqueous solution containing Ca (NO3 )2 . both HAP and TCP coatings promote bone formation which enhances bonding between the imp lant and the surrounding tissues. Xu et al. substrate micro-structure and processing parameters[142]. 4.3. In this application. while the surface of the treated samples had only shallow pitting[198].de position[1 87. Also during this transformation. the surface treatment enhanced the bioactivity of the Mg-Mn-Zn alloy and pro moted bone format ion[193]. 2) it has a slow biodegradability in situ. these range fro m anodization[183].[197].

selecting the correct polymer coating is crucial in determin ing the biocompatibility of the implant and also provides a wider range of design options that can be used to improve the surface properties of the original imp lant surface. the (MAO) technique can produce high quality coatings with superior adhesion. investigated untreated and MAO treated substrates immersed in different composition based solutions composed of NaCl and NaHCO3[204]. wear resistance and strength. Song et al. Industrially. physically and mechanical customized to suit a specific application. since the sub-surface of the metal substrate is also oxidized[202]. 2(6): 218-240 significantly influence the resulting corrosion behaviour of the substrate[199]. Zn and Zr and their alloys. However. 4. research efforts have focused on searching for biocompatib le surface treatments and process that are non toxic. indicating that the degradation had been delayed[205. Pol ymer Coatings Many implantable bio medical devices and imp lants are coated with a thin adherent poly meric material that effectively isolates the device fro m the flu idic environ ment of the body. since controlling the dissolution rate allows matching of the degradation rate of the imp lant with the growth o f new replacement bone tissue. The coating should also be capable of being sterilised and be sufficiently durable to perform its protective function under the expected conditions of the particular application[208]. a successful polymer coating must adhere to the Mg imp lant and be strong and flexib le enough to withstand the normal movement of the implant. The interface between implant surface and body environment is critical in soliciting the appropriate immunological response. Bio medical coatings can be divided into two primary categories: 1) short term. The decreasing wear resistance was caused by wear debris. To achieve the bio-functional requirements and protection. Ti. For examp le. have studied the effects of controlled calciu m phosphate (Ca-P) precipitation on pure Mg substrates by anodization and then thermally treating the substrates in an autoclave[200]. antimicrobial. After thermal treatment. During this time no hydrogen evolution was detected. Before coating. the subsequent immersion studies in Hanks’ solution revealed that the Ca-P coated substrates had very litt le corrosion[201]. adhesion resistance. the mass loss from the untreated substrates during wear tests was 1. This process should produce a clean. improved lubricity.. Mg. Chen et al. being able to select and fine-tune the various properties has enabled polymeric materials to be used in a wide range of coating applications such as protection. Unfortunately. whose size and density is dependent on the selection of the appropriate processing parameters. since both bioactive materials are known to induce osteoinduction and promote new bone tissue growth[201]. Immersion testing revealed that the untreated substrates loss 15 times mo re mass due to corrosion than the MAO treated substrates. In a recent study examin ing the comb ined effects of corrosion and wear on an Mg Alloy (AZ91). The anodization process can also produce an oxide layer consisting of pores. Ta. porous oxide layers are usually coloured and then sealed or form part of a pre-treat ment process prior to painting or coating. For examp le. The study revealed that the MAO coating did improve the corrosion resistance of the Mg alloy. And by selecting the appropriate process parameters. Many of the industrial coating and surface treatments used on anodized Mg alloy components to reduce corrosion are toxic to the human body. wh ich consisted of abrasive particles produced by the breakdown of the MAO coating. The advantage of this technique comes fro m the Ca and P elements being deposited on the substrate. has demonstrated that the oxide layer produced during the anodizat ion of a pure Mg substrate was capable of providing an effect ive barrier to corrosion for 1 month in Hanks’ solution..231 American Journal of Biomedical Engineering 2012. corrosion resistance. In a corrosion and wear study by Zhang et al. dry and contaminant free surface capable o f provid ing the maximu m possible . the wear resistance of the treated substrate tended to decrease with t ime. W. performance and therapeutic effectiveness. Then both treated and untreated substrates were immersed in the Hanks’ solution to determine the effectiveness of the MAO coating in reducing the corrosion rate[203]. die cast Mg alloy (AZ91D) substrates were treated with a MAO coating. selecting a poly mer coating wh ich slowly biodegrades can potentially delay the corrosion of an Mg implant and maintain its mechanical integrity over a longer timeframe. an appropriate pre-treat ment process is required to effectively clean the surface of the Mg imp lant. Both anodization and MAO o xide coating can effect ively reduce the corrosion rate of Mg and Mg alloys by producing a strong resilient o xide layer that provides an effective protective barrier between the metal substrate and the fluid environment. Therefore.4. This technique can be used to deposit ceramic coatings on valve metals such as Al. there is no current data available describing the combined effects of corrosive and wear on MAO treated Mg alloys in Hanks solution. Poly mer coatings are frequently used to modify the surface properties of biomed ical imp lants to improve their bioco mpatibility. The advantage of polymer coatings is that they can be chemically. micro -hardness. For example. In addition. Micro-arc o xidation (MAO) is an electrochemical process which uses a high anodic voltage and high current density to create an intense micro-arc (plas ma) near the metal surface to induce o xidation. Hiro moto et al. The o xide layer formed during this process is substantially thicker than conventional anodization. And as a result. 206]. The tests clearly indicated that the MAO surface treatment was effect ive in imp roving both the corrosion and wear resistance of the Mg alloy. which include d isposable or single patient use. and 2) long term applicat ion of prosthetic implants and reusable laboratory equipment[207]. Thus.5 times greater than those of the MAO treated substrates. ultrasonic imaging and blood compatible coatings for drug delivery[209]. This is an important factor for a biodegradable imp lant.

with superior physiochemical and mechanical properties has the potential to enhance the performance of Mg alloy imp lants by improving both their corrosion and wear resistance. alloying elements such as Al and Li can be used to improve the corrosion resistance of an alloy. However. Both these issues are critical for any material being considered for a b io medical application within the hu man body. In a similar study. Conclusions Mg and Mg based alloys are ext remely biocompatib le and have similar mechanical properties to natural bone. Poly meric coatings have the potential to modify the surface properties of an Mg based implant and significantly improve the implants usability. since there are no toxic solvent wastes produced. the development of new b ioactive surface modifications and coatings. is a polymer coating that has been used to protect implanted sensors and other bio medical devices[210]. The first type of surface modification discussed used conventional mechanical processes such as machining and rolling to enhance both surface and sub-surface properties. This makes them an attractive material for the manufacture of biodegradable. was able to show that producing different surface modifications on chitosan coatings applied to Mg alloy substrates were able to influence the biodegradability of the coating[212]. PLGA. such as the addition of alloying elements and surface modification techniques were discussed. dependable. However. In the case of ion imp lantation. While a conversion coating technique using a calcium phosphate compound produced a coating that not only reduced the corrosion rate. but also improved the biocompatibility and promoted bone format ion at the surface of the Mg alloy. the practical application of Mg based alloys faces the serious challenge of overcoming the rapid corrosion rates that occur within the physiological environment of the body. For examp le. The second type of surface modification discussed examined the types of physical and chemical surface treat ments that could deposit a metallic or ceramic coating or produce a surface conversion coating. The coating process and associated coating parameters can influence the resulting microstructure and morphology of the polymer coating. To overcome the effects of b iological corrosion. corrosion protection of the Mg substrate was dependent the degradation of the PLGA. a nu mber of treat ment methods designed to reduce the corrosion rate. Mg needs a suitable surface primer or b inding agent to improve the adhesion between the poly mer coating and the imp lant surface. Subsequent corrosion testing in Hanks solution revealed that the PLGA could provide an effective coating and protect the underlining Mg substrate. protein adsorption on the implant surface and the influence of the surrounding tissues was discussed. the coating was unable to provide an adequate protective barrier[211]. The silane coupling agent was found to improve the adhesion between the poly (lactic acid) and the substrate. chemical and mechanical responses that can be fine-tuned to solicit and enhance specific biochemical responses within the body environment. Xu et al. concentration of ions. The combination of new Mg alloys and evolving surface . Similarly. And in a bone replacement application. Therefore. but the release of their ions in the body can create undesirable health problems. The types of biological corrosion occurring within the body environ ment and the influence of body fluid pH. Water based coating techniques have the advantages of eliminating or reducing solvent effects on the substrate and are more environ mental friendly. the technique gave mixed corrosion resistance values when Zn was used to treat an Mg-Ca alloy. In addition. Parylene (poly (p-xy lylene). Surface M odifications and Potential as a Biodegradable Orthopaedic Implant adhesive strength between the polymer and imp lant surface. And despite having the potential to function as an osteoconductive and biodegradable substitute in load bearing applicat ions. The corrosion resistance and biocompatibility of the various surface modifications were discussed. durability and performance. a poly mer with good blood compatibility was also coated onto a pure Mg substrate using the same process. Unfortunately. an aqueous solution or fro m the vapour phase. primed a pure Mg substrate using a silane coupling agent before using dip coating technology to coat the substrate with degradable poly (lactic acid)[211]. Recently. Poly meric materials used in coating an implant have the potential to be specifically designed to provide physical. with the capability to replace many currently used orthopaedic materials such as biodegradable biopolymers. The presence of entrapped air and mo isture on the surface could lead to degassing and the format ion of holes in the coating during the curing process. mult i-functional coatings with controllable degradation rates that can be used to prolong the mechanical effectiveness of Mg based implants. careful selection of the appropriate alloying elements and the resulting corrosion by-products were discussed in this article. The biological consequences of adding alloying elements to reduce the corrosion rate was explored and the need for careful selection was d iscussed. Huang et al. The quality and chemical structure of these coatings combine to provide an effective barrier to the body environment and also enhance the protective properties of the coating. Furthermore. A poly mer coating can be applied to an Mg implant using a solvent. Whilst the use of poly meric coatings to protect imp lanted sensors and biomedical devices is well established. 232 5.: Biomedical M agnesium Alloys: A Review of M aterial Properties. a significant research effort is still needed to find poly meric materials that can produce thin. For example. primers composed of metallic ions. components of binding agents and almost all organic solvents found in paints and similar surface preparations are to xic or detrimental to the hu man body and therefore cannot be used in bio medical applicat ions. This explains why coatings with similar co mpositions can have different surface properties[210].Gérrard Eddy Jai Poinern et al. further studies are needed to examine the viability of using a polymeric material with suitable biodegradable properties to extend the operational life of a Mg alloy implant. Poly mer coating produced by vapour-deposition can produce both uniform and defect-free coatings.

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