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General Review

Preparation Strategies for Mg-alloys for Biodegradable Orthopaedic

Implants and Other Biomedical Applications: A Review
G. Chandra ∗ , A. Pandey
Department of Mechanical Engineering, Maulana Azad National Institute of Technology, Bhopal, Madhya Pradesh, 462003, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• Mg-alloy Implants likely to minimize/elim-

inate secondary surgeries in orthopaedics.
• Appropriate design of biodegradable im-
plant is of critical importance.
• Density function theory can be employed
to predict elastic properties of alloys.
• Surface modifications help delay the pro-
cess of biodegradation.

a r t i c l e i n f o a b s t r a c t

Article history: Biodegradable materials offer many advantages over the conventionally used non-biodegradable bioma-
Received 28 February 2020 terials. A number of biodegradable material-based (BMB) alloys have been developed for biomedical
Received in revised form 1 June 2020 applications. Such alloys are increasingly used for manufacturing orthopaedic implants. The elimination
Accepted 11 June 2020
of secondary surgery depends on the efficacy of the BMB implant which needs to fulfill two essential
Available online xxxx
requirements. While such an implant has to be strong enough to provide adequate support to the dam-
Keywords: aged structure in skeleton, it should also be capable of maintaining just the right balance between rate
Biodegradable of healing of the damaged structure and rate of degradation of the implant. The complexities involved
Biomedical in striking a balance between these two apparently conflicting requirements makes it imperative to op-
Biomaterials timize the design and preparation strategy of the BMB alloy. Many biodegradable metals, ceramics and
Orthopaedic polymers have been investigated for this application and the Magnesium (Mg)-based alloys have been
Implants found to be amongst the most suited ones. This review focuses on preparation techniques employed in
development of Mg – alloys for biodegradable orthopaedic implants (fracture fixation implants). The pro-
cess can essentially be split into: material optimization, processing techniques, and surface modifications.
© 2020 AGBM. Published by Elsevier Masson SAS. All rights reserved.

1. Introduction different cases in fracture surgeries. The biological motivation for

The design of BMB implants is quite involved. It almost al-
ways requires identifying a set of relevant properties that need to
be idealized/optimized to make the implant adequately suited for
* Corresponding author.
E-mail address: girishcd.3003@gmail.com (G. Chandra).
choosing biodegradable implants over non-degradable metallic im-
plants has its genesis in issues arising out of stress shielding, metal
ion release, secondary infection, etc. The long healing time and
non-degradability of the implant necessitates a secondary surgery
operation to remove or replace the implant after healing [1–3].
Some drawbacks of metallic implant materials are shown in Ta-
ble 1. Out of the various metals tested for this purpose, Mg and
its alloys have shown great potential and emerged as strong con-

https://doi.org/10.1016/j.irbm.2020.06.003
1959-0318/© 2020 AGBM. Published by Elsevier Masson SAS. All rights reserved.
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Table 1
Major drawbacks of some metallic implant materials.
Element Characteristic Value
Stainless Steel/Fe - Elastic Modulus 190–200 GPa
Alloys
Density ∼7.9 g/cm3
Degradation 0.1–0.5 mm/year
Ti - Alloys Elastic Modulus 113 GPa
Degradation - Negligible
Pure Mg Elastic Modulus 43 GPa
Degradation - Very High
Hydrogen >1 mL H2 /cm2 /day
Evolution
3
Density 1.74 g/cm
Cortical and Density 1.5 - 2.0 g/cm3
Cancellous bone
Elastic modulus 22.4-132.32 MPa and 7.7 to
21.8 GPa respectively
tenders for use in developing biodegradable metal implants [4–7].
Mg is a low-density material (1.8 g/cm3 ). Its remarkable strength-
to-weight ratio, compressive yield strength, and elastic modulus
are comparable to the natural bone and makes it a preferred choice
over commonly used metallic implants materials [8,9]. Mg, in its
pure form, is not capable of serving as an ideal implant material
because not only it degrades quickly during the process of healing,
it also oxidizes rapidly. However, it can be an ideal biodegradable
material if alloyed with some bio-active alloying elements.
Some elements like Calcium (Ca), Zinc (Zn), and Strontium (Sr)
are found important alloying elements for Mg-based material for
orthopaedic applications. Zn is found mainly in muscles and bones
and helps improve the yield stress in implant, reduces H2 gas evo-
lution during bio-corrosion due to Mg, and also helps avoid the
adverse effect of iron and nickel impurities that might be found in
Mg [10]. Sr can enhance strength and corrosion resistance by refin-
ing the grain size. It provides a passive layer on Mg alloys which
can improve the human bone mass and osteoblast formation. Ca
is a vital bone element and potentially essential for maintaining
bone health [1,11–13]. Mg alloys have set a new benchmark in or-
thopaedic implant materials due to its high corrosion resistance,
especially in In-vitro (electrolytic and aqueous environments). In
In-vivo, non-toxic hydroxide is harmlessly excreted due to soluble
formation in urine that can make it useful for biomaterial applica-
tions [14].
Biodegradable material has to stay in the body for reasonably
long durations and should ideally dissolve completely upon ful-
filling the intended design objectives. But it must maintain its
mechanical integrity for a minimum of 12 to 18 weeks during frac-
tured bone tissue healing process. Mg-based alloys are biodegrad-
able materials that offer extra advantages over Fe-based, Ca-based,
Sr-based, and Zn-based alloys [1,2,8,15–17]. During the healing
periods, biodegradable implant materials exhibit unpredictable be-
haviour due to continuous degradation with varying degradation
rates in the complex physiological environment which is one of
the major challenges. Biodegradable implant may lose its strength
quite early because of localized corrosion behavior that is depen-
dent on pitting, corrosion fatigue, etc.
The mechanical loading factors and associated biodegradation
process make it rather complex to develop better alloys and im-
prove the structural design. An implant, like other medical devices,
have to be stiff and offer considerable resistance to cracking/frac-
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Drawbacks Details Ref.
Very High May give rise to stress shielding. The [22–24]
heavy implant may cause bone
distortion.
Very high
compared to Bone
Very Low May require secondary surgery.
High Stress shielding occurs due to brittle [22,25]
behavior
Secondary surgery needed.
(almost zero)
Low Lower elastic modulus of Mg proves [22,26–28]
advantageous in stress shielding.
May go through complete
degradation before bone healing.
High The released H2 gas accumulates at
the surrounding soft tissues.
Low Nearly equivalent to cortical and
cancellous bone.
Low - [3,29,30]
Low -
ture. The design of the implant plays its own role in controlling the
degradation rate. In orthopaedic applications, implant devices are
subjected to acute dynamic loadings during normal physical activ-
ities and get exposed to physiologically - stressed environments.
This may result in stress corrosion cracking and corrosion fatigue
[3,14,9,18]. The intrinsic maximum alloy stress of or threshold
stress of stress corrosion cracking are the main agents usually re-
sponsible for early failure of the device [3,14].
An ideal biodegradable implant must have low rates of degra-
dation to provide appropriate mechanical support until the com-
pletion of the healing process. A regenerated tissue is likely to
start providing strength to the fractured bone but this process
has a close connection with the mechanical integrity and degrada-
tion behavior of the biodegradable implant. Delay in degradation
of the metallic Mg-alloys by using surface modification offers sig-
nificant benefit over a non-delayed degradation process (like pure
Mg). However, sometimes immediate degradation can also provide
satisfactory healing outcomes [19]. An important parameter for a
biodegradable implant is its biocompatibility which can be con-
trolled by using nutrients, bioinert elements, etc. [1]. Structure of
medical device is another important parameter for controlling the
overall cycle of healing process.
A biodegradable implant goes through typical healing process
stages including inflammation, granulation, and remodeling, be-
fore its complete degradation. Localized corrosion and stress cor-
rosion cracking interfere and delay the healing processes locally
[20,21]. This review essentially focuses on identifying key prepa-
ration points and chart a path for developing Mg-alloys for or-
thopaedic implants. Fig. 1 is a flow chart representation of all three
critical material development stages involved.
2. Evolution of orthopaedic implants
Stainless steel and pure titanium are well - explored and fre-
quently discussed as metallic biomaterials for implants since 1940
[31]. However, they started getting widely used in fracture surgery
of damaged tissue/bone from 1993 [32]. An acute need of exten-
sive research was later felt to explore new alloys/materials to avoid
secondary surgery due to allergy, bacterial reaction, stress shielding
effect in the bone due to higher density, or the incomplete degra-
dation of the implant even after complete healing of the tissue.
Biodegradable metallic materials and their alloys are now increas-
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Fig. 1. Flow Chart of Critical Material Development Stages.
ingly used in fracture surgery for development of implant devices
like pins, bone plates, screws, etc., that will degrade simultane-
ously with accompanying loss of mechanical integrity and tissue
healing [33,34].
The evolution of Mg and its alloys as biomedical implant ma-
terials in In-vivo applications is largely due to their good degra-
dation, biocompatibility, strength, and light weight. Mg2+ and its
alloying elements like Zn and Ca carry essential nutrients that con-
tribute to the biological regeneration of damaged tissue in the hu-
man body. Mg, as resorbable ligature, was first used in the form of
wire to stop bleeding from blood vessels in 1878 [35]. Biodegrad-
able materials like Pure Mg or Mg - alloys (AZ91 and AZ31) have
shown their benefits in terms of improved biological properties
over the previously used non-degradable implant materials like
Stainless Steel, Co-Cr alloys, and Ti – alloys for clinical applications
[36]. For Mg - alloys, rapid corrosion associated with the release
of H2 gas with accompanying loss of mechanical strength has been
observed. It has also been reported that its degradation and me-
chanical dynamics must be controlled over the healing cycle. Due
to many distinct advantages of Mg-alloys, new generation medical
devices like biodegradable vascular stents have also emerged, along
with orthopedic plates, screws, fixator pins, etc. These are fast be-
coming the finest examples in usage of biodegradable materials
for usage other than orthopaedic applications; the common feature
being their disappearing ability after serving the purpose [37,38].
For achieving ideal time line in controlling the primary parameters,
an adequate strategy is needed for preparing the material to avoid
the requirement of implant removal by secondary surgery. The sec-
ondary parameters of biodegradable implant are also evolving in
the design for orthopaedic applications. The biodegradable metallic
alloys, especially Mg-alloys with adequate alloying elements, have
the ability to replace the non-degradable metallic alloys, specifi-
cally for the purpose of developing orthopaedic/fracture fixation
implants for orthopaedic application mentioned in Table 2 that
also lists the advantages and disadvantages of some metallic bio-
material alloys used in orthopaedic implants [1].
3. Material optimization of Mg-alloys for biodegradable
orthopaedic implant applications
Material optimization, as employed in biodegradable orthopae-
dic implants design, aims to control and balance performance
– affecting factors like number of alloying elements/the alloying
system, alloying elements’ compositions and microstructure, func-
tional characteristics, mechanical and biological behaviour and cor-
rosion/biodegradation characteristics.
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3.1. Biological behaviour of Mg-alloys
The primary motive of biomaterials/biodegradable materials is
to become compatible with physiological environment they have
to serve in (In-vivo/In-vitro). Biodegradable, non-toxic nutrient el-
ements can be synthesized and allowed to participate in many
enzymatic reactions and cofactors or regulators within the human
body. Mg and some alloying elements like Zn, Ca, etc., have been
found to be involved in more than 50% of the cellular activities
like replication, transcription, translation process, stabilization of
plasma membrane, etc. Most of the biodegradable metal elements,
sequestered in bone, act as reservoir for quick change in levels of
serum. Some of them are contained in soft tissues and repossessed
in levels of serum. Mg2+ ion content in bone mineral is around
six molar percentage but it decreases during re-generation of bone
[43,44]. The blood serum level, parts in human blood and parts
in human bone for Mg are about 0.73–1.06 mM, 900 mmol/L and
1.7 mg/g, respectively. Total amount of Mg usually present in the
human body is 25 g, out of which about 30%–40% is present in
muscles and soft tissues, although its daily requirement in adults
is only up to 0.7 g (∼0.5 g in male and ∼0.4 g in females) [45,46].
Though the concentration of Mg2+ depends on aging, it is ob-
served that Mg2+ is in higher concentration in cartilage and im-
mature bone tissues. Moreover, the presence of Mg in bone com-
position affects the osteoblast cells and increases the elasticity of
bone. The bone formation process stimulates healing during degra-
dation of implant by releasing Mg2+ ion. Mg, in pure form, exhibits
high rate of formation of hydrogen gas cavity which may decrease
the survival time in in-vivo. Higher amounts of hydrogen gas start
swelling in the periphery of implant site near damaged position of
the bone by filling the loose compartments and then dispersing
subcutaneously to other areas. It leads to improvement in cor-
rosion performance of biodegradable Mg-alloy and consequently
decreases the risk of gas accumulation. It also improves the me-
chanical properties, corrosion resistance, and other characteristics
that need to be optimized [14,47].
3.2. Alloying elements, alloy systems and element compositions for
Mg-alloys
Appropriate design for biodegradable orthopaedic implant ap-
plications involves selecting the alloying elements, alloy system
and element compositions for development of Mg-alloys. The ad-
vantages (biological and mechanical) and disadvantages of some of
the commonly employed elements are listed in Table 3 that may
serve as a useful aid in selecting the alloying elements.
The selection of alloying elements in Mg-alloys should be based
on their non-toxicity, solubility, absorbability, and dissolvability by
the adjacent tissues as nutrients to help in healing while allow-
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Table 2
Metallic materials and their alloys: advantages and disadvantages.
Material Advantages Disadvantages Ref.
Stainless Steel Biocompatibility High Elastic Modulus [1,39]
(Not Degradable) Easy Availability Insufficient Wear Resistance
Cheap Allergic Behaviour in Physiological Conditions
Excellent Fabrication Stress Shielding Effect (SSE) in Bone
Toughness

Co-Cr Alloys Biocompatibility Expensive [40]

(Not Degradable) Fatigue and Wear Resistance Poor Machinability
Resistance to Corrosion SSE
High Strength High ElasticModulus
Toxic in Physiological Environment due to ions released
by Co, Cr and Ni
Ti-Alloys Biocompatibility Expensive [41]
(Not Degradable) Resistance to Corrosion Low Wear Resistance
Light Weight Low Bending Ductility

Mg-based Alloys Biocompatibility H2 evolution during Biodegradation [22,42]

(Degradable) Biodegradability Inadequate Corrosion Resistance
Bioabsorbability
Light Weight

Zn-based Alloys Biocompatibility Low Mechanical Strength [1]

(Degradable) Biodegradability Less Soluble with Mg, Ca, Sr and Fe
Bioabsorbability Low Ductility
Ideal Corrosion Rate

Fe-based Alloys Long-term Biocompatibility Low Degradation Rate [1]

(Degradable) Bioabsorbability
High Strength

Ca-based Alloys Biocompatibility Low Degradation Rate [1]

(Degradable) High Strength

Sr-based Alloys Biocompatibility Slow Degradation Rate [1]

(Degradable) Good Compression Very Fine Micro Structure
Properties

ing excretion of the excess amounts [8]. Toxic elements (in red),
allergic elements (in orange) and nutrient elements (in green) indi-
cating solubility limits of different alloying elements for Mg-alloys
have been shown in Fig. 2 (the toxicity of remaining elements is
not known) [1,50,56–58]. These solubility limits may serve as the
indicators for deciding the compositions for alloying elements.
For better optimization of Mg-alloys, many potential alloy sys-
tems such as binary, ternary, quaternary, and more than four el-
ements are discussed here which may be helpful in appropriate
design of material for biodegradable orthopaedic implants.
Binary Mg-Ca alloys with different Ca contents (wt. % of 1 to 3)
have been taken as two phases in fabrication, pure Mg and Mg2 Ca.
It is observed that tensile properties can be controlled by Ca con-
tent. The implantation in rabbit femoral shafts for up to 3 months
indicates that the Mg-1Ca alloy pins gradually degrades in In-vivo
within 90 days whereas a newly formed bone is clearly seen in
the 3rd month of implantation [59]. The mechanical properties of
Mg/Ca composite with 1, 5 and 10 wt.% of Ca have been compared
with Mg-1Ca alloy and it is observed that the UTS and elonga-
tion of this composite decreases with increasing Ca content [60].
The observation concludes with the recommendation of Mg-1Ca
alloy as an orthopaedic biodegradable material [59,60]. Many re-
search findings have shown improved bio-absorbable properties of
binary Mg - based alloys. All in all, 9 different types of alloying
elements (Mn, Si, Sn, Al, Ag, In, Y, Zn and Zr) have been identi-
fied individually with different weight % of alloying elements. It
is observed that improvement in strength is due to Al, Si, Sn, Zn
and Zr whereas decrease in corrosion rate is due to Al, In, Mn,
Zn or Zr, in both SBF and the Hank’s solution. However, some el-
ements like Si and Y have shown negative effect on the corrosion
behavior. In cytocompatibility observation, Mg–1Al, Mg–1Sn and
Mg–1Zn alloy have shown no considerable reduction in cell via-
bility to fibroblasts, although Mg–1Al, Mg–1Si, Mg–1Zn, Mg–1Sn,
Mg–1Y and Mg–1Zr alloy showed no considerable effects on tox-
icity to osteoblasts [50]. An example for binary Mg - alloys with
different alloying elements has been shown in Fig. 3. The mechani-
cal properties and corrosion characteristics of some of these binary
Mg-alloys are listed in Table 4.
In ternary alloy system in Mg-5Znalloy, Sr has been taken as
the 3rd element and minor Sr addition of 0, 0.2, 0.6 and 1.0 (wt.
%) have been used. It is observed that Sr refines the grain in all
compositions but the best composition of Sr is 0.2% (Mg-5Zn-
0.2Sr) that exhibits significantly improved mechanical properties
with UTS and elongation of 233 MPa and 15% respectively. It is
also observed that there is an adequate corrosion resistance in
In-vitro (0.9%NaCl and Hank’s solution) [11]. Similarly, Mg-Zn-Ca
alloys were developed with Ca as a third element and found to
have improved superior biocompatibility. It was observed that im-
provement in mechanical properties happened via additional age
hardening for 2–5 hours and corrosion also got reduced to half of
the predefined rate [61]. As ternary, Mg – alloys (as-cast and ex-
truded), Mg–4.0Zn–0.2Ca shows improvement in mechanical prop-
erties; the tensile yield strength, ultimate tensile strength, and
elongation values being 240 MPa, 297 MPa and 21.3%, respectively.
After 30-days in SBF solution, good biocompatibility and decreased
degradation rate are observed, with YTS, UTS, and elongation of
160 MPa, 220 MPa and 8.5%, respectively. These values may be
adequate to support the fractured bone [62]. The mechanical prop-
erties and corrosion characteristics of some of these ternary Mg-
alloys are listed in Table 4.
In the quaternary alloys system, Mg72-x Zn23 Ca5 Pdx , with x
ranging from 0 to 6 %, shows Pd free ternary Mg72 Zn23 Ca5 alloy in
amorphous state, but the addition of Pd lowers the glass-forming
ability due to formation of crystalline phases. This quaternary alloy
system also shows that increased Pd content results in increased
hardness and young’s modulus (2.71 GPa for x = 0, to 3.9 GPa and
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Table 3
Biological advantages, mechanical advantages and disadvantages of some commonly used elements.
Element Biological Advantages
Mg 7th Macro mineral for human body;
65% of Mg is found in bones;
promotes bone formation during
healing
Zn 85% of Zn is found in muscles and
bones; Reduces the hydrogen gas
evolution; decreases the degradation
rate; Helps to overcome the harmful
corrosive effects of impurities found
in Mg-alloys
Sr Favors the growth of osteoblasts and
prevents bone resorption; Improves
bone mass and reduces the chance of
micro fractures. Enhances corrosion
resistance
Ca 99.5% of Ca is found in bones;
Improves bioactivity and corrosion
resistance
Mn Helps in assisting metabolic activity;
Prevents osteoporosis and decreases
rate of debilitating disease
Sn Encourage the synthesis of proteins
and nucleic acids; Improve corrosion
resistance
Fe Necessary for proper function of
enzymes and oxygen transport.
Zr Low toxicity; improves corrosion
resistance.
Si Corrosion resistance; non-toxic.
Li Low-toxicity.
Al - Improves UTS
REE Anti-carcinogenic; Corrosion
resistance.
Mechanical Advantages Overall Disadvantages Ref.
Outstanding strength to weight ratio, High degradation rate; Hydrogen gas [1,5,8]
33% and 77% lighter than Al and evolution; undesirable in pure form
Steel, respectively; improves damping
capacity.
Improves the strength and ageing - [1,7,48,49]
strengthening effect; up to 5% by
weight can be used for better
mechanical properties.
Results in grain refinement; - [1]
Improvement in strength and
Reduction in elongation with up to 3
% by weight.
Results in grain refinement; Improves - [1,5,48,49]
strength and creep resistance
Results in grain refinement and - [1,50,51]
improved tensile strength
Improves both tensile and - [50]
Compressive strength
- Higher amounts may be harmful; [1,51]
Very slow degradation
Improves tensile strength, ductility - [6,1]
and elongation; High specific
damping capacity; Powerful grain
refiner
Significant improvement in - [50,52]
mechanical properties
Ultra-light weight; Improvement in monotonically accelerate the [53,54]
plasticity corrosion rate
Probability of occurrence of [50,1,54,55]
neurological disorders such as
Alzheimer, Dementia and Senile
Dementia diseases
Improves creep properties; - [1]
strengthening ability

for x = 6). At x = 2, the wear resistance becomes maximum due
to the formation of high-strength phases. It does not show dead
cells even after culturing for 27 hours in a mouse pre-osteoclasts
and delays the bio-degradability of this alloy due to addition of
Pd [63]. Mg–Zn–Ca–Sr alloy, are treated as bulk modulus glass
(BMGs) due to good glass-forming ability, significantly improved
mechanical properties, good corrosion performance, and reduced
hydrogen evolution with minor Sr additions. The fracture strength
and specific strength are above 827 MPa and 2.8 × 105 Nm/Kg, re-
spectively, which is higher than Sr-free ternary Mg–Zn–Ca BMGs
[64]. The Mg-Zn-Zr-Sr (Mg-3.2Zn-0.8Zr-0.3Sr) alloy, made by cast-
ing using magnetic agitation, is homogenized at 300◦ C for 2 h and
goes through hot extrusion at 300◦ C with extrusion ratio of 1:56.
This improves the mechanical properties as shown in Table 4. By
immersion tests and cytocompatibility tests (In-vitro), the Mg-Zn-
Zr-Sr alloy is found to have good corrosion resistance and helps in
proliferation of cell [65]. The mechanical properties and corrosion
characteristics of some of these quaternary Mg-alloys are listed in
Table 4.
More than four elements, e.g. as cast Mg-4.2Zn-1.7RE-0.8Zr-
0.2Ca(wt.%) alloy with Sr, contains increased fluidity (122.8%) as
compared to the quaternary alloy system and refined grains with
reduction in oxides formation and melt viscosity. The Mg-4.2Zn-
1.7RE-0.8Zr-0.2Ca-0.2Sr alloy exhibits mechanical properties with
UTS,YTS and elongation of 144.1 MPa, 114.4 MPa and 4.9%, respec-
tively [66]. Mg-3.0Gd-2.7Zn-0.4Zr-0.1Mn (GZKM-1) alloy contain-
ing traces of Gd and Zn shows improved mechanical properties.
However, little amount of Zr and Mn results in increased corro-
sion resistance due to refined grains. The best mechanical property
values of UTS, YTS, and e% of 341.5 MPa, 315.2 MPa and 21.3%, re-
spectively, are obtained with cast, hot extruded, and heat-treated
material [67]. The mechanical properties and corrosion character-
istics of some of these Mg-alloys are listed in Table 4.
Density functional theory (DFT) can be used to arrive at the
alloy systems in Mg - based or Fe - based alloy system, as well
as composition of alloying element. DFT has been used to investi-
gate the influence of biocompatible elements of Mg and Fe crystal
lattice alloying elements and their effect on general elastic prop-
erties. Some studies of Mg - alloy with binary alloy system of
elements like Zn, Ca, Li, Ag, Sr, and Zr, as well as ternary and
quaternary Mg-based alloys, have been carried out and indicated
improved ductility of alloys, especially alloying of Mg with Zn,
Ca, and high percentage of Li. DFT is immensely useful in deter-
mining the best alloying elements and their respective proportions
with the objective of improving the ductility of Mg-based and Fe-
based bioresorbable alloys for cardiovascular, Broncho-tracheal and
orthopaedic applications [68].
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Fig. 2. Solubility limits of some alloying elements in Mg. (For interpretation of the colors in the figure(s), the reader is referred to the web version of this article.)

Fig. 3. Maximum elongation, UTS and degradation rates of Mg-alloys with adequate binary alloying elements (Zn, Ca, Sr and Y) by wt. % [1].

3.3. Microstructure of Mg-alloys
Microstructure of Mg-alloys plays a vital role in the design of
Mg-alloys and is briefly discussed here.
3.3.1. Porous structure
Porous microstructure of biodegradable implant can help in or-
thopaedic applications because it has better bone regeneration and
degradation capabilities. It allows the circulation of body fluid in
bone tissue, and hence contributes to its growth. Apart from this,
it prevents loosening of the implant [69]. A porous structure can be
created by some manufacturing techniques like powder metallurgy,
additive manufacturing, negative salt-pattern molding process, etc.
Very finely milled and uniformly distributed spacer powder parti-
cles of different elements can build porous microstructure. Further
pressure is applied to a specified mold shape followed by sintering
to engage intermediate bond. The porosity and pore size can be ad-
justed by the type of content and its particle size to adopt spacer
particles for pulverized pressed shape of metal, ceramic or mixed
powders with detachable spacer particles (i.e. Carbamide) [70,71].
Porous structure obtained vide laser additive manufacturing (LAM)
of Mg-Ca alloys exhibits the effect on porosity as shown in Fig. 4.
The porosity of a LAMed Mg-Ca alloy mainly depends on three fac-
tors: energy density, pulse width, and frequency of the laser input,
and the porosity of porous Mg-Ca alloy decreases gradually with
the increase in laser energy input [72].
Many research findings indicate that the mechanical proper-
ties and corrosion resistance get reduced in Mg-based porous al-
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Table 4
Compositions and Corresponding Mechanical Properties of Biomaterials and Bone (Red, green, blue and grey are shown binary, ternary, quaternary and more the four elements
systems respectively for Mg-alloys) [112–116,118,119]. (For interpretation of the colors in the table(s), the reader is referred to the web version of this article.)
Tissue/Implant/ Density US YS e (%) E (GPa) HV Corrosion Ref
Alloys (at. %/wt.%) (g/cm3 ) (T/C) (T/C) properties
(MPa) (MPa) (CV/CC/CR)
Bone 1.8-2.1 110-130 104-121 0.7-3 15-25 - - [29]
Pure Mg 1.74-2.0 90-190 65-100 2-10 41-45 - 0.011 mg.cm−2 .h−1 [8]
Pure Zn 5.4 33 - 16 9.1 18 −0.85V/138 × [112]
10−6 A.cm2 /
2.71 mm/year
Mg-1Ca - 71.38 40 1.87 - - 320 mV/1.63- [59]
12.75 mm/yr
Mg-1Zn - 134 25.5 18.2 - - [49]
Mg-1Sn - 194 79 20 - -
Mg-2Sr - 213.3 147.3 3.15 - - 300 mV/ [113]
0.87 mm/yr
Mg-1Mn - 86.3 28.5 7.5 - - [49]
AZ31 1.78 263 185 15-23 45 - 0.0065 mg.cm−2 .h−1 [114,8]
AZ91 1.81 230 (T)/160 (C) 45 0.0028 mg.cm−2 .h−1 [8]
Stainless Steel 7.9 490 190 40 200 - - [23]
(SS316L)
Titanium alloys 4.43 950 880 14 113.8 - – [25]
(Ti-6Al-4V)
(Ti-6Al-7Nb) 4.52 900 800 10 105 - -
Chromium 7.8 450-960 240 - 450 50 195-230 - - [115]
cobalt alloys
(CoCr20Ni15Mo7)
Mg-2Zn-0.5Sr - 142 62 - - 8.9 - [116]
Mg-4Zn-0.5Sr - 169 104 - - 3 -
Mg-6Zn-0.5Sr - 200 128 - - 3.6 -
Mg-5Zn - 212 120 10 - 52 −0.56 V/ [11]
33.80 μA cm−2
Mg-5Zn-0.2Sr - 233 117 15 - 56 −0.51 V/
22.40 μA cm−2
Mg-5Zn-0.6Sr - 215 115 13 - 59 −0.53 V/
31.62 μA cm−2
Mg-5Zn-1.0Sr - 194 107 9 - 65 −0.54 V/
26.61 μA cm−2
Mg–4.0Zn–0.2Ca - 297 240 21.3 45 −1.67 V/ [62]
243 μA cm−2 /
1.98 mm/yr
Mg-1.2Zn-0.5Ca - 116.1-126.5 57.2-63.4 3.07-3.33 - 44.5-53.1 −1.83 V/ [61]
(as-cast) 695 μAcm−2 /
8.2 mm/yr
Mg-1.2Zn-0.5Ca - 142.2-159.2 77.2-91.4 4.66-5.14 - 56.4-64.6 −1.81 V/
(Heat treated) 420 μAcm−2 /
4.8 mm/yr
Mg72 Zn23 Ca5 2.84 - - - 50.38 - −1.15 V/ [63]
1.7 mAcm−2
Mg70 Zn23 Ca5 Pd2 3.01 - - - 64.2 - −1.04 V/
2.1 mA cm−2
Mg66 Zn23 Ca5 Pd6 3.40 - - - 72.98 - −0.93 V/
2.7 mA cm−2
Mg66 Zn30 Ca4 Sr0 2.940 ± 0.003 - - - 48.8 ± 0.1 2.45 ± 0.01 −1.15 V/ [64]
10 μAcm−2
Mg66 Zn30 Ca3.5 Sr0.5 2.952 ± 0.004 - - - 48.5 ± 0.2 2.49 ± 0.01 −1.15 V/
10 μAcm−2
Mg66 Zn30 Ca3 Sr1 2.964 ± 0.005 - - - 49.1 ± 0.2 2.51 ± 0.02 −1.15 V/
10 μAcm−2
Mg66 Zn30 Ca2.5 Sr2.5 2.980 ± 0.004 - - - 49.4 ± 0.2 2.51 ± 0.02 −1.15 V/
10 μAcm−2
Mg-3.2Zn-0.3Sr - 278.002 ± 5.352 187.324 ± 4.015 19.8 ± 3.6% - - 24.92 mm/yr [65]
Mg-3.2Zn-0.8Zr - 306.052 ± 4.588 227.509 ± 5.009 20 ± 2% - - 17.05 mm/yr
Mg-3.2Zn-0.8Zr-0.3Sr - 376.400 ± 7.526 322.363 ± 4.547 16 ± 1% - - 24.2 mm/yr
Mg-1.0Ca-0.5Sr - 307.4±1.8 304.3±2.2 10.4±2.2 - - - [117]
(Extrusion Temperature
275 ◦ C)
Mg-1.0Ca-0.5Sr - 234.9±1.2 202.7±2.4 18.3±3.4 - - -
(Extrusion Temperature
340 ◦ C)
Mg-1.0Ca-0.5Sr - 215.1±0.9 157.2±2.3 18.7±2.7 - - -
(Extrusion Temperature
400 ◦ C)
Mg–Zn–Y–Nd - 242 170 20.9 - - −1.753 V/ [118]
139 μAcm−2
Mg–1.5Y–1.2Zn–0.44Zr - 236 178 28 - - −1.667 V/ [119]
75 μAcm−2
(continued on next page)
JID:IRBM AID:619 /REV
8 G. Chandra, A. Pandey / IRBM ••• (••••) •••–•••
Table 4 (Continued)
Tissue/Implant/ Density US YS
Alloys (at. %/wt.%) (g/cm3 ) (T/C) (T/C)
(MPa) (MPa)
Mg30 -Fe70 (673K) 5.25 - 1120
Mg30 -Fe70 (723K) 5.262 - 1130
Mg30 -Fe70 (773K) 5.321 - 1380
Mg30 -Fe70 (823K) 5.209 - 1100
Mg-4.2Zn-1.7RE- - 144.1 114.4
0.8Zr-0.2Ca-0.2 Sr
Fig. 4. Porosity variation curves of different processing parameters. (a) energy density, (b) pulse width, (c) frequency [72].
loys due to adopted increased porosity, pore size, and thickness
of porous layer [73–75]. For making a porous structure in as-cast
Mg-Al alloys, electrochemical de-alloying process may be used via
neutral aqueous 0.6M NaCl solution, to form coarse as well as
fine pores. A single-sized porous structure can be made by an
annealing–electrochemical de-alloying approach [76].
3.3.2. Composite structure
For composite microstructure biodegradable implant, a matrix
is required to perform as a base element and reinforcement ad-
ditives (different from matrix element) like metal particles, poly-
mers, ceramics, etc., are incorporated in it [77]. This can be used
to control the mechanical and corrosion properties, which are ad-
justed as per the desired requirement. Appropriate reinforcement
material selection may lead to improved specific stiffness, abrasion
resistance, specific strength, creep resistance, thermal conductiv-
ity and dimensional stability, and the ability to perform better in
organic or physiological fluids environments. A group of biodegrad-
able materials (like Zn, Ca, hydroxyapatite (HA), etc.) used as rein-
forcement in orthopaedic applications has shown similar charac-
teristics as the mineral required for bone. Composite structure of
Mg/Ca binary with 1, 3 and 5 wt. % of Ca has been found to exhibit
significantly improved mechanical and biological properties [60].
Many types of composites like ceramic matrix composites, poly-
mer matrix composites, and metal matrix composites (MMCs), are
available but MMCs are the most commonly used composites for
orthopaedic applications. MMCs play a very important role in con-
trolling the mechanical and degradation properties of biodegrad-
able material - based alloys, through factors like content type, dis-
tribution, shape, size, and orientation of the reinforcements. Many
compositions of calcium phosphate (CPP)-based ceramic [78–83],
bioactive glass [77], magnesium oxide [84], calcium particles [60],
and many more oxides formed with bioactive materials as re-
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e (%) E (GPa) HV Corrosion Ref
properties
(CV/CC/CR)
- - 398.1 - [120]
- - 422.7 -
- - 424.3 -
- - 298.8 -
4.9 - - - [66]
inforcements have been used to prepare Mg - based MMCs. On
the other hand, biodegradable polymers like polylactic acid (PLA),
polylactic co-glycolic acid (PLGA), as well as PLA/phosphate com-
posites, can also be used as reinforcement biomaterials [85,86].
Mainly two methods are used to make MMCs, namely - powder-
metallurgy and stir casting. Matrix of Mg-3Zn-0.2Ca alloy, with
reinforcement MgO as spherically shaped, nanoparticles, in (0.1,
0.2, 0.3, 0.5 wt.%) using high shear melt solidification, solution
treatment, and hot extrusion, shows significant increase in yield
stress (T/C), ultimate stress (T/C), and corrosion resistance [84].
The HA micro particle can also serve as reinforcement but has a
deficient load carrying capacity which makes its application re-
stricted, although it has significantly better biological properties
[87]. Biodegradable Mg-3Zn alloys matrix with dried 5 wt.% of
HA is reinforced as a functional bioactive and osteogenic ceramic,
and causes an improvement in the corrosion resistance by ∼72%.
It also improves the YCS of biodegradable Mg alloy by∼23% [88].
Hot extrudedAZ91D alloy with HA (reinforcement) also shows good
corrosion resistance and leads to re-iteration of the porous mi-
crostructure to promote bone cell adhesion and proliferation due
to HA fiber [89]. PM is used as a traditional pressing-sintering
technique to prepare the MMC alloys. It also accounts for better
operation and ease of preparation of composite to obtain homo-
geneous and uniform distribution of reinforcement, like - ceramic,
metal oxide, and polymer in matrix [90,91,80]. Biodegradable pure
Mg with 20 wt.% of ZnO in the form of nanoparticles, made by PM,
is reported to improve the UTS and surface hardness, although cor-
rosion rate and elongation decreases in Mg matrix [91]. AZ91/FA
MMCs, fluorapatite (FA) nanoparticles, etc., affect the mechanical
properties when FA nanoparticles increase up to 20% with UCS of
the AZ91/FA and accompanying reduction in degradation rates [80].
Biodegradable Mg/MgF2 with continuous network of MgF2 re-
inforcement using SPS (Spark Plasma Sintering) to form a particle
JID:IRBM AID:619 /REV
G. Chandra, A. Pandey / IRBM ••• (••••) •••–•••
interface thickness of 3.5 μm, results in improvement in mechan-
ical properties and corrosion resistance by ∼70% (0.7 mm-y−1 ),
compared to pure Mg [92]. A Biodegradable Mg-2Zn/PLA compos-
ite rod made by hot press and self-reinforcement effect of PLA
after hot drawn process, leads to improvement in grain orienta-
tion, crystallinity, and melting temperature, as well as strengthen,
toughness, and interfacial bonding strength by MAO- treated Mg-
2Zn wires [93]. Mg-6%Zn alloy matrix and β -Ca3 (PO4 )2 reinforced
particles have been used to make homogeneous distributed com-
posites by PM followed by hot extrusion and aging treatment. This
resulted in improved bio-safety, corrosion resistance, and mechan-
ical properties [94]. CPP particles (<750 nm) up to 5 wt.% have
been used to improve the mechanical properties (YTS of 319.5%
and elongation of 30.5%) for ZK60/CPP MMCs [95,79]. Stirring cast-
ing method has also been used but only sparingly to develop
MMCs, where it can be seen that 1 wt.% nano - HA particles addi-
tion in Mg–Zn–Zr alloy is appropriate [96].
3.3.3. Ultrafine-grained structure
Ultrafine-grained structure (nano-crystalline microstructure)
can play a key role in providing mechanical stability to the
biodegradable implant. It may be obtained in an ultrafine state
in BMB alloys by severe plastic deformation (high-pressure torsion
(HPT)) [97], equal channel angular pressing (ECAP) [98], accumu-
lative roll-bonding [99], etc. Cyclic extrusion - compression (CEC)
and accumulative channel-die compression [100] can improve the
mechanical strength by ultra-refining the grains in any material
or alloy in accordance with the Hall-Petch relationship. They also
serve to reduce the biodegradation rate in In-vivo and In-vitro
mechanisms [101]. Mg–3Ca alloys of grain size 200–500 μm have
been made by rapid rate of cooling and solidification [56]. Fast so-
lidification of Mg–Zn–Ca alloy has been reported to result in very
fine microstructure and considerable improvement in corrosion re-
sistance as compared to as-cast Mg–3Ca alloy [48]. Mg–2Zn–0.5Ca
composite with 1 wt.% of β -tri-CPP reinforcement made using high
solidification rate followed by ECAP. It is shown to have very high
hardness and corrosion resistance due to ultra-refined grains [102].
Very fine grains have been obtained in as-cast pure Mg by friction
stir processing (FSP) using 3 simultaneous passes and good me-
chanical, and biodegradation properties in the nugget zone have
been observed [95]. Mg–Nd–Zn–Zr alloy made by CEC have very
fine grains which can also be compared with its extruded version
in terms of improvement in UTS ∼300 MPa, 71% increased YTS
and increased elongation (154% increase) [103].
Using HPT has been very useful in ultra-refined grain structure
of Mg–Zn–Ca alloy towards enhancement of corrosion resistance
compared with its extruded version [61]. AZ31 alloy as ECAPed
with back pressure is shown to have considerable enhancement in
UTS of ∼380–420 MPa and elongation of ∼27–35% [104]. As-cast
WE43 billet after heat-treated (solution treated) at 525◦ C for 16 h,
quenched for rapid cooling in water, and 8 passes - processed by
ECAP, resulted in ultra-refined grains and substantial precipitation.
It also showed average grain size of ∼340 nm, highest density of
Mg5 RE precipitates (size of ∼150 nm), and YCS of 427 ± 10 MPa
[105]. Some other considerably improved factors like fatigue and
degradation performance are found enhanced inAZ31/ECAPed as
compared to its hot-rolled version [106]. For Mg – alloys, it is
reported that after incomplete degradation, if ultrafine-grained or
nano-crystalline structures are found on pits with superficial depth
in microstructure, then it’s a different version e.g. extruded or hot-
rolled [103,61,107]. Rapid solidified Mg- RS66 ribbon with recipro-
cal extrusion has also shown ultra-refined grain (size of ∼1.3 μm)
[107,108]. Ultra-refined Mg alloys have the capability to achieve
improved mechanical properties up to a UTS value of 400 MPa,
elongation of 23.5% and also reasonable corrosion behavior in In-
vivo mode [109].
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3.3.4. Amorphous (Glassy) structure
Mg–Zn–Ca–Sr master alloy is characterized as a biodegradable
BMG due to ultimate glass formation ability. It has improved cor-
rosion performance and is deficient in hydrogen evolution. It is
also observed to have better mechanical properties and compat-
ibility with cell culture to fulfill the criterion of biodegradable
materials [64]. Biodegradable Mg–Zn–Ca BMGs, when compared
to traditional Mg alloys, have an extraordinary strength but inef-
ficient plasticity of ∼2–4%. It was also shown that Mg66 Zn30 Ca4
BMGs have very high UCS of∼716–854 MPa compared with re-
crystalline AZ91D alloys of UCS ∼400 MPa. Mg67 Zn28 Ca5 BMGs
reportedly have very high UTS of ∼675–894 MPa compared with
crystalline WE43 alloy with UTS of ∼270 MPa [110]. Master alloys
of as-cast Mg66 Zn30 Ca4−x Srx with variable value of x (wt.%) from
0 to 1.5 have excellent glass forming ability by minor Sr addition
compared with its Sr - free version, and exhibit enhanced fracture
strength of ∼827 MPa with specific strength of 2.5 × 105 Nm/Kg
[64]. The specific advantage of these Mg-based BMGs has been
found in minimized galvanic corrosion effect due to its single-
phase structure and chemical homogeneity. A good correlation is
observed regarding H2 evolution and bubble-less gas cavities in In-
vitro test of Mg95−x Znx Ca5 BMGs compared with Mg60 Zn35 Ca5 in
In-vivo.
3.4. Mechanical and biodegradation/corrosion characteristics and
behaviour
The contributions made by the base element and alloying el-
ements are truly important for orthopaedic application as they
influence mechanical, biological, and biodegradation properties, as
shown in Table 3. Apart from this, a secondary important parame-
ter is the manufacturing method for all such enhancements. Some
of the impurities present in alloys can react with the base or
alloying elements to form secondary phases and deteriorate the
mechanical integrity [111,1]. Table 4 illustrates the details of some
common pre-defined biocompatible and BMB alloys that can be
used for orthopaedic applications.
Biodegradable materials must have optimum biodegradation
rates for design and manufacture of successful biodegradable im-
plants. Biodegradation rates are found variable at different im-
plantation sites in the human body due to difference in blood
flow. Many researchers have reported that biodegradable materi-
als, especially Mg-alloys, do not have uniform biodegradation rates
throughout the life cycle of healing process. Biodegradation rate is
basically a rate of corrosion reaction that occurs within a phys-
iological environment either in In-vivo or in In-vitro mode. The
biodegradation rate in In-vitro mode can be determined by either
of the two commonly used techniques, namely - the electrochem-
ical test and immersion test. In electrochemical corrosion test, the
common reactions occur in such a manner that electrolyte (that
produces oxides), hydroxides, hydrogen gas, or other compounds
are evolved in physiological environment. For Mg, the expected re-
actions are as below [1,121]:
Mg→ Mg2+ + 2e− (anodic dissolution reaction of Mg metal)
2H2 O + 2e− → H2 + 2OH− (cathodic reduction reaction)
M2+ + 2OH− → Mg(OH)2 (corrosion product layer formation in
Mg metal surface)
There exist many different, unbalanced, influencing factors like
inorganic ions (influenced by presence of Cl− , etc.), buffering sys-
tems (influenced by pH values), organic molecules (influenced by
absorption of proteins), dissolved oxygen (influenced by oxygen
concentration in electrolyte), and stress (influenced by load bear-
ing capacity). In Mg-alloys, with different alloying elements and
respective compositions, the rate of reactivity of each element may
JID:IRBM AID:619 /REV
10 G. Chandra, A. Pandey / IRBM ••• (••••) •••–•••
be different according to alloying system contaminants. Some of
these alloys’ corrosion properties have also been listed in Table 4
as corrosion characteristics in electrochemistry [1,28].
All alloying elements and/or other metallic impurities in Mg -
alloys work as local cathode, and may provide extra advancements
by improving all desired characteristics. The base element (Mg)
works as anode, due to intermetallic phases. All these intermediate
phases interact with each other in mainly two aspects during gal-
vanic corrosion. The first one is due to individual electrochemical
potential difference of the cathodic and the anodic sites, whereas
the other one is due to different kinetics existing on the same. In
Mg-alloys, compatible alloying elements with higher over-potential
are better than lower over-potential due to lower hydrogen - evo-
lution reaction. Similarly, over-potential difference may also occur
due to hydrogen reaction for surfaces modified via various sur-
face modification methods, due to pigmentation of different impu-
rity particles, oxides, etc. These reactions can directly affect/alter
the existing uniform corrosion and load bearing capacity due to
continuous mechanical loading and its microstructure reshaping.
This makes life prediction of BMB/Mg-alloys quite difficult due to
non-uniform dissolution than for layer-by-layer removal (Biodegra-
dation) on material surfaces during continuous corrosion. Overall,
these non-uniformities in corrosion/biodegradable rates make it
very difficult to accurately predict the degradation of biodegrad-
able implant [1,28,45].
Apart from this, BMB implant must have a unique design for
better support and minimum degradation to stand up to complete
healing in physiological environment (PE). This is an important fac-
tor that deserves careful scrutiny and optimization in orthopaedic
applications. The biodegradable alloy degrades over the healing
time span of the damaged bone in contact with body fluids. It is
necessary to know the rates of mass/volume loss and evaluation of
strength over the implantation or immersion time in In-vivo and
In-vitro test. The biodegradation scenario in In-vivo orthopaedic
applications has always been very complex than in glass exper-
iments (In-vitro). The hydrodynamic environment i.e. cell, blood
culture, etc., and modes of transfer of nutrients could be different
on different implantation sites [122,123,28]. The fine, concentrated,
and continuous distribution of secondary and intermetallic phase
have been found to play an efficient role in enhancement of cor-
rosion resistance in internal galvanic corrosion [124]. Some of the
low solubility limits alloying elements in biodegradable material
- based alloys, like Mg-alloys, Zn-alloys, etc., act as cathode and
have been observed under dynamic condition (In-vivo) to induce
corrosion that generates higher corrosion rates than those in static
condition (In-vitro).
To conclude, adequate alloying elements (or alloy system), ap-
propriate composition, and microstructure play their own signif-
icant roles in material design optimization. The solubility limits,
DFT and functional characteristics, are certainly of help in selecting
adequate Mg-alloys but the desired/requisite microstructure can
only be obtained by controlling the alloying elements and process-
ing techniques.
4. General processing techniques for Mg-alloys
All critical properties of biodegradable implant materials are
primarily based on base-element and alloying elements but they
do get affected by the processing methods to ensure desired qual-
ity for the orthopaedic implant. For BMB alloys, pre-processing
techniques are divided into solid state and liquid state techniques.
The solid-state processing synthesis technique involves blending
the form powders for desired compaction, distribution and spec-
ified composition, and further sintering the material below its
solidus or recrystallization temperature. The liquid-state process-
ing, on the other hand, involves superheating in a furnace to melt
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above or close to the melting point of base material and prepare
the mould for its transfer and solidification. Traditionally, addi-
tive manufacturing techniques have incorporated this feature in
biodegradable material preparation for orthopaedic applications.
After pre-processing, mechanical properties can be further con-
trolled by post-processing techniques like heat treatment, hot/cold
working process, etc. [125–127].
4.1. Pre-processing techniques
After the material’s optimization, the pre-processing techniques
are used to fabricate and shape the alloys. Some major pre-
processing techniques used for BMB alloys are discussed herein.
4.1.1. Liquid state (casting)
Liquid state casting is the most commonly used technique to
prepare alloys. However, biodegradable Mg-alloys are easily oxi-
dized during melting. To avoid oxidation, inert gases like argon,
etc., or vacuum can be used to provide a protective environ-
ment. Successful execution of this process depends on selection
of microstructure, number of alloying elements, their composi-
tions, temperature, time for melting, etc. Relatively recent research
work has shown that biodegradable Mg-alloys composites have
adjustable degradation rates and mechanical properties [27]. To
develop new composites for BMB alloys with various alloying el-
ements and systems, this can be a promising route to meet the
demand of appropriate quality in casting for biodegradable im-
plants [128,129].
4.1.2. Solid state {powder metallurgy (PM)}
PM is especially used for highly porous, dense, brittle structures
that are employed in different applications. This process consists of
smallest possible refining by repeated fracturing and re-welding.
This is accomplished by sintering and compacting to obtain the
finest microstructure alloying of powder particles for better qual-
ity and applications [14]. PM can ensure the integrity of composite
structure and porosity. Usually two PM techniques, namely: the
pressure - assisted sintering and cold compaction are used [130].
An example of green compacts is WE43 powder, which is com-
pacted by hot vacuum press in cylindrical pattern at 425 MPa and
350◦ C for 1 h. Recrystallized structure of WE43-PM has slightly
finer grain size (majority of grains lying in the range 1–2 μm), im-
proved mechanical properties, corrosion resistance, and homoge-
nously dispersed secondary phases compared to as-cast extruded
WE43-IM [131]. There are many influencing factors that affect the
final quality of the implant obtained through PM. For powder for-
mation, ball-milling is commonly used with variable parameters
like ball-to-powder ratio, milling time and turning speed. For com-
pacting and sintering, operating pressure, preventive atmosphere,
and temperature must be taken into due consideration. Achiev-
ing the finest possible grains is an efficient method to compact
two or more metallic materials grains. The hexagonal structure
of biodegradable Mg-alloys and their limited slip systems makes
it rather difficult to produce deformation due to the poor ductil-
ity existing. Ultra-fine grained structure made by PM can provide
very high strength, high strain rates, and super plasticity at low
temperatures and high pressures [132,3]. Biodegradable Mg-Fe al-
loy powders using SPS techniques at sintering temperature 773 K
with compacting at high pressure (600 MPa) and simultaneous
10 minutes of holding time can provide reduced biodegradation
rates with ultra-high strength (1380 MPa), high hardness and den-
sification [120]. Overall, PM has the ability to ensure uniform and
homogeneous distribution of particles for any alloying technique.
Some significant tensile properties of Mg-1Ca obtained with dif-
ferent techniques are shown in Fig. 5.
JID:IRBM AID:619 /REV
G. Chandra, A. Pandey / IRBM ••• (••••) •••–•••
Fig. 5. Comparison of Tensile Properties for Mg-1Ca obtained through Different Processing Techniques [59,60].
4.1.3. Additive manufacturing (AM)
Traditionally, AM has been frequently used in various types of
manufacturing industries (mainly in biomedical, construction and
prototyping) as it consumes less time and material. 3D printing
is one of the conventional and most widely used AM techniques.
It is widely used for fabricating a complex structural geometry
which is otherwise very tough to manufacture through casting and
powder metallurgy. 3D printing/AM offers various advantages like
less waste, less cost, less time, design flexibility, etc. Any specific
3D design can be obtained from 3D CT - scanned geometry or
a computationally designed model. 3D printing/AM is especially
useful in biomedical engineering to make 3D organs, tissues or
any internal body parts as part of the preliminary planning for
surgery [133,134]. 3D printing/AM can also be used to analyze
the biodegradable material - implant design by making internal
real time structure which is so useful for the manufacturer to
adequately conceptualize the final product for orthopaedic appli-
cations for all implantation site regions, different types of bones,
fracture types, age groups, and vastly differing human body sizes
[135]. Biomedical applications using AM have great potential in
making it possible to evolve patient-specific and customized or-
thotics to prostheses from biomedical implants to drug dosage and
hearing aids [136,137].
Another important and commonly used AM technique is fused
deposition modeling (for hot continuous filament of a thermoplas-
tic polymer). The challenge in 3D printing of composite parts is
to develop fiber-reinforced composites with desired fiber orienta-
tion, bonding between the fiber and matrix, and void formation.
Some other methods have also been used such as selective laser
sintering, selective laser melting (energy directly used to prepare
any structure by fine metal powders), etc. There are many limi-
tations for selection of materials in 3D printing in order to meet
the demands imposed by metals, alloys and composites. Currently,
ceramics and polymers are used in stents and scaffolds for tissue
engineering [138,139].
4.2. Post-processing (secondary) techniques
Such processing techniques are basically used to achieve the
requisite mechanical properties and corrosion characteristics by
adequately modifying the microstructure. This happens with ac-
companying improvement in intermediate phases or refinement
between elements with the help of different hot and cold work-
ing processes. Some of these techniques are discussed in brief for
biodegradable Mg-alloys.
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11
4.2.1. Extrusion
Extrusion is the most efficient method used to improve the
mechanical properties and microstructure. Of late extrusion has
been used in BMB alloys to control mechanical and biodegrada-
tion properties with the help of controlling factors like working
temperature, extrusion rates and extrusion ratio [59,125]. Billet of
Mg-1Ca-0.5Sr has been extruded with extrusion ratio of 25:1 to
impart a high degree of deformation by a large driving force for
microstructure refinement and mechanical properties. Yielding and
flow behavior mainly depends on extrusion temperature wherein
maximum UTS of 304 MPa has been obtained with the lowest ex-
trusion temperature of 548 K [117]. An extruded Mg-3.0Gd-2.7Zn-
0.4Zr-0.1Mn (GZKM-1) alloy, with extrusion ratio of 8:1 at 350◦ C
using ram speed of 4 mm/s, has been observed to have enhanced
mechanical properties as compared to as cast and heat-treated
version [140]. The reasons behind all such improvements in hot
or cold extrusion are transformation of microstructure in eutectic
compounds and directional distribution along the extruded por-
tion. These multiscale microstructure formations may be helpful in
improving the corrosion resistance due to grain boundary strength-
ening and precipitation strengthening effects [67,44,141]. One ex-
ample has been shown in Fig. 6 that shows how the mechanical
properties of GZKM-1 alloys change due to post - processing tech-
niques [140].
4.2.2. Rolling
This is the second most effective method that results in con-
siderable improvement in mechanical properties, surface hardness
and refined-microstructure. An example of this is two - stage
rolling for LX41 alloy aimed at spontaneous characteristics through
grain refinement at the first stage of rolling at 350◦ C for about 50%
working. Further refined grains are obtained at the second stage
of rolling carried out at 200◦ C, about 12% above the recrystalliza-
tion temperature [142]. Mg-3Zn alloy in as - cast, heat-treated,
and right-angled state, bi-directionally rolled at 310◦ C by two high
with 10 passes, exhibits dynamic recrystallization of new grains
with increase in grain boundary area and grain refinement up to
83% at reduced thickness of 57%. It is also observed that the re-
fined grains result in enhanced UTS and YS values that are about
77% and 65% more, respectively, and with 264% improved ductility
represented via toughness [88].
4.2.3. Heat treatment
Heat treatment is mainly used to recrystallize grains and ensure
intermetallic precipitation to enhance the mechanical properties of
JID:IRBM AID:619 /REV
12 G. Chandra, A. Pandey / IRBM ••• (••••) •••–•••
Fig. 6. Mechanical Properties of GZKM-1 Alloys with Post-processing Techniques [140].
biodegradable material - implant alloys using different tempera-
tures and time durations for respective specified alloys. Heat treat-
ment process mainly involves annealing, homogenization, solution
quenching, and age hardening treatment [7]. As a post-processing
method, heat treatment can also result in improvement in bio-
corrosion behaviour and mechanical treatment characteristics as in
case of Mg-Zn-Ca alloys [143,144]. In as-cast, homogenized Mg-Sr
alloys at 450◦ C for 12 h and quenched in water, enhanced duc-
tility and corrosion resistance are observed but the strength is
reduced. Aging treatment at 160◦ C with periods of 30–300h fol-
lowed by water quenching shows enhanced strength, marginally
reduced corrosion resistance and ductility [132].
4.2.4. Other hot/cold working processes
Other techniques are also available and used to refine grain
size and improve mechanical properties. Some of these are forg-
ing, drawing, and other conventional thermo - mechanical pro-
cessing techniques. Few others are high pressure torsion, multi-
directional forging, twist extrusion, accumulative, equal-channel
angular pressing, roll bonding, repetitive corrugation, straightening
compression and cyclic extrusion [145,146].
Pre - processing techniques, though quite efficient, fail in
achieving all desired characteristics qualitatively and/or quanti-
tatively. Post - processing techniques fill this void and, in their
own way, constitute a truly important class of secondary opera-
tions. They have the ability to affect the functional capability by
changing every minor variable, controlling parameters like applied
pressures, temperature, etc. They serve the purpose of refining the
micro-structure adequately and play an important role in control-
ling the biodegradation rates and mechanical properties that are
so critically important for a biodegradable - material implant.
5. Surface modification techniques for Mg– alloys
To delay degradation in PE, surface modification is the most
effective tertiary way that enhances biocompatibility, controls cor-
rosion properties, and ensures adequate degradation rates for
any BMB implant. For Mg-alloys, in particular, fluoride treatment,
Micro-arc oxidation (MAO), dip-coating, and electrodeposition can
help in resisting excessive corrosion by providing protective, anti
– corrosion layers which can boost its functional capabilities too
[147]. There are many techniques that have been proposed for
better surface finish and quality, such as, MAO [148], sol - gel
deposition [149], etc. It is quite important to delay the biodegra-
dation process of biodegradable implant after implantation in the
[m5G; v1.287; Prn:30/06/2020; 12:20] P.12 (1-21)
human body and simultaneously avoid the synergetic effect of bac-
terial, cell and bloody culture.
5.1. Surface coatings
The physical and chemical properties of coatings regulate the
cell behavior to determine their bio-compatibility. To alter and ad-
just the degradation rates of BMB alloys, the surface coating is
employed that acts as a barrier between external biological envi-
ronment and implant material substrate. The addition of a coating
on outer surface of the implant is required to protect from some
metal ions creeping into the human physiological culture [43].
5.1.1. Deposition coatings
Deposition in outer surface layer of any biodegradable metal
surface solution to enhance osteointegration in In-vivo culture
and In-vitro (hemocompatibility, cytocompatibility, etc.) provides
protection from exposure to oxidation [150,151]. An organic coat-
ing can be applied by various techniques like powder coat-
ing, e-coating, sol–gel coating, and plasma polymerization. In a
hybrid coating system, organic coating is used mainly on the
top. The component used in organic coatings is a resin - like
acrylicpolyurethane, vinyl, polyvinyl butyral, epoxy and baked phe-
nolic compound containing zinc chromate or strontium chromate.
Polymers are organic components that are essentially based on the
solution of organic solvent, monomeric metal or metalloid alka-
loid precursor in alcohol [152]. Polymers do serve as a protective
coating (a layer separating two materials) or as a substrate for
the medical device [153,154]. Polymeric implant materials based
on polylactic acid (PLA), polyglycolic acid (PGA), etc., and their
co-polymers are available for bone fracture repair applications.
Polymers have good biocompatibility and biodegradability but the
accompanying inadequate mechanical performance acts as a bar-
rier for a bone with low load bearing capacity [155].
In an organic coating, sol-gel formation plays a major role in
processes condensation, hydrolysis and polymerization of mono-
mers. The monomer particles and their chains create polymer
structures by improvement in particle growth and agglomeration,
and occurrence of formed network throughout the liquid medium
exhibits better gel formation by increase in viscosity [156]. Syn-
thetic aliphatic polyesters, such as PLA, poly-lactic-co-glycolic acid
(PLGA), polycaprolactone, polyethyleneimine, etc., have been used
in biomedical applications [157]. In polymeric deposit coatings, it
is observed that non-toxic biodegradable elements have the abil-
ity to provide enhanced mechanical properties and corrosion re-
JID:IRBM AID:619 /REV
G. Chandra, A. Pandey / IRBM ••• (••••) •••–•••
sistance; and also stay compatible in osteo-inductive and osteo-
genic environments [158]. The natural polymer is observed as ex-
traordinarily biocompatible in comparison to sol-gel and synthetic
polyesters due to their biomimetic nature [159].
It is also observed that natural polymer-based coatings has-
ten the regeneration of tissues to enhance the intermediate in-
teractions between biodegradable implant and cell/tissue matrix
environment. Overall, polymers can be used for hydrogel scaffold
synthesis and housing drugs delivery [138,160,161]. In inorganic
coatings, CPP coating on BMB alloys shows better compatibility
with cell culture, bone inductivity and toxicity. Apart from this,
it can promote wear resistance between bone tissue interface and
partially avoids bio-corrosion too [162,163]. CPP - coated metallic
biodegradable implants exhibit a combination of improved me-
chanical strength and better biological properties. They also play
a significant role due to superior initial rate of osseointegration to
promote clinical fixation process and promotes the shortening of
healing duration in comparison to uncoated implants [154]. Most
of the natural minerals are in the form of calcium apatite where
HA has the ability to increase osteoblast response by promoting
osteointegration [164,165]. Di-CPP dihydrate is the most easily de-
posited coating which has enhanced bio-corrosion resistance when
used on Mg-alloys [166,167].
Amorphous CPP has better osteoconductive properties than HA
in In-vivo and higher biodegradability than tri-CPP, although it
lacks in long-range and periodic atomic scale order of crystalline
CPP [168]. Amorphous CPP is generally produced by pulsed laser
deposition or plasma spraying at high temperature and energy
[169]. Tri-CPP is generally used in orthopaedics and maxillo-facial
surgery where α -Tri-CPP constituent is used in hydraulic bone ce-
ments whereas β -Tri-CPP constituent is used in bio-ceramics and
composites. However, it may be deficient in resisting biodegrada-
tion rates compared with HA in-vivo [170,171]. AZ31 alloy with
β -Tri-CPP coating has been observed to have improved surface
compatibility with cell culture, osteo-conductivity and osteogen-
esis with better corrosion resistance than its uncoated version
[172,173]. It is usually combined with HA in the formation of
CPP mixture with optimal degradation and improvement in bone
growth rates [174]. There are various methods to develop CPP coat-
ings in deposition mode on biodegradable metals implants like
sol–gel (spin coating, dip coating, etc.), biomimetic precipitation,
plasma spraying, electrophoretic, ion beam dynamic mixing depo-
sition, electrochemical deposition, etc. [175].
Addition of metallic coating offers electromagnetic shielding
due to small electrical resistance while showing improved corro-
sion resistance and surface mechanical damage resistance [176].
Many deposition techniques such as physical vapor deposition (ba-
sically used in metal deposition), sputtering and plating have also
been used for coatings in BMB metallic alloys. They also provide
high hardness and wear resistance which may improve its corro-
sion resistance [177]. Hybrid coating is a combination of two or
more coatings that mainly includes ceramics, polymers or metals.
It serves to provide desired properties in a better manner than
a single coating [178]. HA has extraordinary biocompatibility and
bioactivity and can also be used as a second or third constituent
coat on BMB alloys [179]. Chitosan, on the other hand, has also
been shown to have considerable biocompatibility, corrosion be-
havior, non-toxic and adsorption properties, but not better than
HA [180]. Using high velocity oxy-fuel, MgO and HA powder coat-
ings on Mg-1Ca-1Zn alloy, the amount of H2 release may decrease
in the initial stage of corrosion of the biodegradable Mg-alloys. HA
coating can reduce H2 evolution up to 84% as observed in immer-
sion in In-vitro for 29 h [179].
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13
5.1.2. Reactive coatings
Reactive coatings in biodegradable implants are of two types;
fluoride coating and metal oxide coating. Fluoride coating can de-
velop a protective layer due to its non-toxicity, chemical inertness,
and easy preparation techniques [181]. Magnesium fluoride (MgF2 )
is used to improve intermediate corrosion resistance and bioactiv-
ity, which can result in beneficial growth of potentially essential
nutrients for growth in dental and skeletal due to stimulation
of osteoblast proliferation and new mineral deposition. In MgF2
treatment, improvement in osseointegration and corrosion resis-
tance have been observed during inflammatory phase of healing
[182–184]. Its treatment mainly proceeds in two stages. The first
one is chemically produced MgF2 whereas the other one is flu-
oride salt or a hydrofluoricacid contained solution. The fluoride
- treated Mg-Ca-Zn-Co alloys have improved corrosion resistance
and desired mechanical properties for biomedical applications in
Mg–alloys [185]. Fluoride-coated AZ31B has been immersed in hy-
drofluoric SBF solution for 45 days for different time durations, and
observed to have improved corrosion resistance and mechanical in-
tegrity than the uncoated alloy version [186]. Fluoride - coated
AZ31 alloy has also shown enhanced corrosion resistance and
growth of osteoblastic cells in biological validation [187]. Two-step
fluoride coated (10–20 μm thickness) biodegradable Mg-Ca alloy
has shown enhanced mechanical properties, corrosion resistance,
and good compatibility with vascular cells culture [188]. Apart
from this, metal oxide coatings generally developed by micro-arc
oxidation (MAO) have been conventionally applied to provide ox-
ide - protected layer of their own in biodegradable metallic al-
loys [189,166]. MAO is an effective way to detract corrosion of
biodegradable Mg-alloys and also shows good wear resistance to
sustain better stability, improved hardness, and control of H2 evo-
lution [190,191]. In MAO, high voltage generated discharge with
plasma-assisted anodic oxidation can react as localized plasma
which causes sintering, followed by surface melting, oxidation and
re-solidification to densify grown oxides [162,192]. There are three
layers that have been reported in MAO - coated AZ31 alloy, where
thickened, rough porous structure is found in outer layer, dense
compact found in inner layer and intermediate thin layer is found
between the inner layer and AZ31 Mg alloy substrate [193]. Factors
affecting the MAO coatings properties in biodegradable implant
alloys are voltage, current density, pulse frequency, duty cycle,
treatment time, electrolyte solution, and other additives like NaF
and Na3 PO4 . Although post treatments could be performed like or-
ganic, inorganic sealing, and sometimes ion implantation can also
be used over the MAO [193].
Cu – containing, MAO - coated, extruded Mg-2Zn-1Gd-0.5Zr al-
loys have been observed to have enhanced corrosion resistance,
insignificant difference in cell viability and anti-bacterial character-
istics (up to 96%) [190]. There are many combinations used with
MAO to incorporate with titanium dioxide, hydroxyapatite, elec-
trophoretic deposition, etc., to enhance corrosion resistance and to
ensure antibacterial properties [191]. In reactive coatings, tanta-
lum (Ta) has the ability to form a self-passivating surface oxide
layer (Ta2 O5 ) and observed as biocompatible, osteogenesis, bio-
safety in In-vivo. Ta2 O5 is one of the best formed insulating films
for anticorrosion resistance and shows rapid attachment with bone
and soft tissues. Ta contains films on biodegradableZK60 alloy
to improve the corrosion resistance and cytocompatibility, which
contains favorable surface for proliferation, cell attachment and
spreading [194,195]. Ta (High purity) nitride films are deposited
onto the Mg-Y-RE (WE43) alloy by DC reactive magnetron sputter-
ing system with a pressure of 6.0 × 104 Pascals. The power used
for deposition is 100 W for 3 h without substrate heating. WE43
Mg-alloy with deposited TaN film also shows reduction in corro-
sion [196].
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14 G. Chandra, A. Pandey / IRBM ••• (••••) •••–•••
5.2. Ion implantation
Ion beam processing/ion implantation is a process of injecting
ions into the surface layer of substrate via bombardment, with-
out detrimentally affecting the substrate. It gives high adhesive
strength between the high degree controllable modified layer and
substrate to maintain quality of the modified layer. Ion implan-
tation is used to control degradation rates, surface strength, and
biocompatibility to modify the surface properties. Generally, micro-
electronic processing has been used during the favorite bulk char-
acteristics [178,197]. Some elements like Zn, Ti, Fe, Al, N, Ta, Zr, Cr,
Y have been ion-implanted into the BMB Mg – alloys [198,31,199].
Fe and Zn has been used to influence mechanical properties and
ensure better corrosion behavior to ensure delay in degradation
and perform surface modification using ion implantation on ZK60
alloy [200]. As-extruded Mg-1Ca alloy using the compound coat-
ing machine coated Zn II&D with MEVVA ion source at voltage
8 keV and current 25 mA for 60 min during implantation, shows
increased corrosion potential and current density. It is comparable
with coated Mg-1Ca alloy and exhibits improved cytocompatibil-
ity of Mg-1Ca by Zn ions with better cell adhesion and growth
in cell culture. Ion implantation Mg-Ca alloy with Zn immersed in
SBF for 18h is followed by a test in electrochemical polarization
and morphological examination. This test exhibits improvement in
surface hardness, modulus and corrosion resistance [201]. GZ91K
alloys have been ion - implanted using metal ion implanter with
following parameter values: dose of 1×1016 ions/cm2 in Sn ca-
thodic arc source, accelerating voltage of 50 kV, and base pressure
of 2×103 Pa. Its modified layer, composed of SnO2 and MgO, re-
sulted in almost double the hardness value and modulus of elastic-
ity than Mg - alloy substrate. It also improves corrosion resistance
and abrasion resistance [199].
5.3. Laser surface modification
Laser surface modification (LSM) is an anti-corrosion technol-
ogy for BMB alloys where the surface melting during laser irradi-
ation provides significantly improved surface properties (viz., cor-
rosion resistance and wear resistance) in comparison to other sur-
face modification techniques such as chemical conversion, anodic
oxidation, micro-arc oxidation, organic coating, thermal spraying,
etc. Significant advantages of LSM are low cost, lack of contam-
inants, high surface integrity and high quality surface [202,203].
LSM-treated Mg alloys and AZ91D with dissolved surface inter-
metallic secondary phases provide better corrosion resistance and
finer grain boundaries with precipitates that favor anchoring and
retention of the Mg(OH)2 film [202,204]. Mg-6Gd-0.6Ca alloys with
continuous wave fiber laser spot irradiation modify the surface
with the power density 2.04 × 106 W/cm2 and scanning speed 70
mm/s in 50% overlapped beam striking twice in the same direction.
This results in changed solidified thick layer (360 μm) microstruc-
ture to alpha-Mg phase, and no beta-phase grains are observed to
be precipitated in grain boundaries. Laser surface melting has also
shown good adhesion property, spreading performance, and pro-
liferation capacity [205]. Laser melting controls the surface wetta-
bility, structure, homogeneity, and changes the surface topography
of the polymer surface layer, thereby influencing the degradation
behavior of the biodegradable alloy substrate [206].
5.4. Surface nano-crystallization
Surface modification of bulk material on nano-scale basis
greatly enhances the surface properties, wherein the grain size can
be reduced without changing the chemical composition [207]. For
the synergistic effect between high surface energy and topography,
[m5G; v1.287; Prn:30/06/2020; 12:20] P.14 (1-21)
Osteoblasts are necessary on nano-scale, μ-scale and submicron-
scale structural features with Ti substrate. In the case of biodegrad-
able alloys, there are many ways to enhance surface hardness and
induce nano crystallization on nano-scale, such as - surface me-
chanical attrition treatment (SMAT) [188,208], laser shock peening
(LSP) [209,210], and high-velocity oxygen-fuel flame supersonic
microparticle bombardment [211]. Surface self-nano crystallization
induced by severe plastic deformation is also an effective technique
for grain refinement on conventional bulk material on a nano -
scale [207].
SMAT can produce a very hard layer with nanocrystalline struc-
ture by repetitive multidirectional impact of flying balls [187].
SMAT has been applied on LA36 with vibration frequency of
20 kHz. The average grain size was quickly refined by about 80
nm on the top surface and the hardness gradually decreased with
the increase of depth; the maximum hardness reaching 1.6 GPa
due to the presence of the nanostructured layer and high den-
sity of dislocations [188]. SMAT has been applied in commercially
available rolled AZ31 at vibrating frequency of 20 kHz for 10 sec
on each side and results in nano-size refined grains with im-
proved surface microhardness. Tensile fracture of nano-structured
AZ31 Mg alloy may exhibit fine/coarse grains and deformation lo-
calization. The strain concentration is effectively suppressed and
alleviated in fine grain microstructure of gradient; the plasticity
mainly depending on the matrix [212]. In SMAT-induced disloca-
tion, precipitation strengthening effect offers another possibility to
improve aging precipitation in Mg-RE alloy [213]. For many metals,
LSP is a promising surface nano-crystallization method, where en-
hancement in the corrosion resistance and wear resistance occurs
with improvement in surface hardness, UTS and fatigue strength
[214,210]. LSP with intensity 2 GW/cm2 , overlap ratio 75% and
beam size 1 nm, has been used in AZ31B alloy. It resulted in
improvement in surface hardness, wear resistance and fatigue per-
formance due to plastic deformation in outer surface layer made
up of sub-grains and twins [209]. It is believed that the biodegra-
dation performance of surface nano-crystallized BMB implant is
influenced by various factors such as the micro-strain, density, re-
fined grains and secondary phases dissolution.
In short, surface modifications do play an important role in
that they considerably improve corrosion resistance performance
by various techniques, such as fluoride treatment, MAO, etc., and
thus may be useful in biodegradable orthopaedic implant develop-
ment. It may be an optional step in preparation of a biodegradable
fracture fixation implant for orthopaedic applications because ade-
quate material optimization and achieving desired functional char-
acteristics may not be possible without it.
6. Preparation strategies for an ideal BMB/Mg-alloy implant
Pure form of biodegradable Mg, like many other metals, has in-
adequate mechanical strength, corrosion resistance and other prop-
erties for orthopaedic application [47]. Preparation of an ideal BMB
alloy requires identification of the targeted parameters or control-
ling parameters. The major parameters for an ideal implant are
long – term biocompatibility, optimal mechanical properties, and
adequate biodegradation rates. All these parameters primarily de-
pend on material optimization wherein base material and selection
of proper alloying elements, selection of alloying systems (binary,
ternary, quaternary, and so on), and respective compositions and
microstructures (porous, composite, amorphous, etc.) play an im-
portant role. Base Mg element with some nutrients mentioned in
Table 3 can result in getting rid of some of the limitations of the
biodegradable implant. It may minimize the impact of higher rate
of implant degradation and early loss of strength of the implant;
and may also improve the regeneration of biological tissue(s) by
use of nutrients, via primary design optimization of BMB alloys.
JID:IRBM AID:619 /REV
G. Chandra, A. Pandey / IRBM ••• (••••) •••–•••
Fig. 7. Ideal Cycle for a Biodegradable – material Implant showing various stages involved.
The secondary methods that are employed to optimize the
properties are the processing techniques. There are various pre-
processing techniques, such as casting, powder metallurgy and
additive manufacturing under different processing conditions.
Further, the post-processing operations like heat treatment and
hot/cold working processes, do play a significant role too. Mg-Fe
alloy made by the spark plasma sintering technique has ultra-high
strength. It enhances the strength of the biodegradable implant
by improving the stiffness and reduces the probability of breakage
before complete healing.
The tertiary method having the objective of optimizing the
properties is surface modification. Many techniques have been
used in biomedical applications for achieving optimal surface prop-
erties. Some of these techniques also improve the corrosion resis-
tance for existing PE using hybrid coating. They help in avoiding
high decay rate of implant during inflammation and callus growth;
and atmospheric reactions leading to osteolysis to balance the nec-
essary strength and biocompatibility. The use of biodegradable Mg
- alloys may result in elimination of secondary surgery.
An overview of the ideal cycle for a biodegradable - material
implant, depicting all stages from preparation to complete dis-
appearance, is represented by Fig. 7. For an ideal biodegradable
implant that is designed and employed to serve as an internal fix-
ation device, the mechanical properties should be the best possible
and corrosion rates have to be the lowest possible to allow the
BMB implant stand its ground till the completion of healing pro-
cess, followed by eventual degradation [215,216].
This work is an attempt to elaborate all aspects and facets in-
volved in the design of biodegradable materials for orthopaedic
applications. Various biodegradable materials have been employed
and developed with the best possible mechanical properties by
resorting to different processing techniques. Conscious efforts
have been made to ensure the minimum possible biodegradation
rates/corrosion rates in actual PEs through various processing and
surface modification techniques. The ultimate objective is to attain
the highest possible mechanical strength with conforming biocom-
patibility and biodegradability. The biodegradation rate must be
adequate or controllable due to the complex time management
during different phases of the healing process. The task becomes
more involved due to different age groups of patients, their spe-
cific response to injury, different implantation sites, and differing
biodegradation rates. Biocompatibility, desired mechanical proper-
ties, and controllable biodegradation rates have to be there in a
perfect mix to ensure a successful design of the BMB implant.
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15
7. Conclusion
To completely eliminate secondary surgery, preparation of BMB
alloy plays a major part in the scheme of things. Preparation of
biodegradable alloys for optimized property parameters mainly de-
pends on three preparation steps that are listed below:
(1) Material optimization is the most important and primary
perspective of biodegradable materials for material design. Selec-
tion of base elements and number of alloy elements for the prepa-
ration of an alloy system is the key to emergence of a success-
ful implant. This is essentially based on analyzed biocompatibility,
biodegradability, absorptivity in PE, and solubility limit of each al-
loying element in connection with the respective base elements.
Further, the proportions of all elements can be defined in accor-
dance with the density function theory and microstructure type,
so as to ensure optimization of mechanical properties.
(2) Processing techniques provide another major perspective
in the design and manufacturing of BMB alloys. Selection of
pre-processing techniques has a definite linkage with microstruc-
ture and mechanical properties. Post-processing techniques, on the
other hand, are quality optimization techniques that are executed
with the objective of attaining an improved microstructure, as also
better mechanical and biodegradation properties.
(3) The last important aspect of this design process is surface
modification. The main objective is to achieve requisite surface
quality that influences the biodegradation rate for orthopaedic ap-
plications.
These three are the critically important steps that help achieve
ideal quality of alloys for orthopaedic applications. This strategy,
coupled with validated experimental results pertaining to biologi-
cal, mechanical, and bio-corrosion behaviour of different BMB al-
loys, will be of significant aid in evolving an effective structural
design for a BMB implant for orthopaedic applications.
Human and animal rights
The authors declare that the work described has not involved
experimentation on humans or animals.
Funding
This work did not receive any grant from funding agencies in
the public, commercial, or not-for-profit sectors.
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16 G. Chandra, A. Pandey / IRBM ••• (••••) •••–•••

(continued)
Author contributions
Symbols Stand for
GPa Giga Pascals
All authors attest that they meet the current International Com- Li Lithium
mittee of Medical Journal Editors (ICMJE) criteria for Authorship. Mg Magnesium
Mn Manganese
MPa Mega Pascals
Declaration of competing interest
Pd Palladium
Si Silicon
The authors declare that they have no known competing finan- Sn Tin
cial or personal relationships that could be viewed as influencing Sr Strontium
the work reported in this paper. Ti Titanium
Y Yttrium
The authors declare that the current research work does not Zn Zinc
involve any conflict of interest in any manner whatsoever. They ZnO Zinc oxide
are thankful to Maulana Azad National Institute of Technology Zr Zirconium
(MANIT), Bhopal (INDIA), for the facilities extended.
References
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