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Magnesium matrix composites for biomedical applications: A review
Vijay Kumar Bommala, Mallarapu Gopi Krishna∗, Ch Tirumala Rao
Department of Mechanical Engineering, Acharya Nagarjuna University, Guntur-522510, Andhra Pradesh, India
Received 19 April 2018; accepted 13 November 2018
Available online 26 December 2018
Abstract
In recent years, a new wave of bioactive, biocompatibility and biodegradable metallic materials were developed for orthopedic applications.
Pure Magnesium, Magnesium alloys, Magnesium alloy-based composites are extensive material to the biomedical applications, by virtue of its
high biocompatibility and reasonable strength. Pure magnesium, Magnesium alloys can corrode too fast during the physiological conditions
and loses their properties before bone heal. The new era for the development of magnesium-based composites can satisfy the orthopedic
applications. Magnesium-based composites, as bio-materials, can produce adjustable mechanical properties like Ultimate tensile strength,
ductility, elastic modulus, and corrosion resistance in the physiological conditions. In the Mg based composites, the matrix materials are
biomedical magnesium alloys base like Mg–Ca, Mg–Al, Mg–Zn, and Mg–REE alloy and The reinforcements are based on hydroxyapatite
(HAP), calcium polyphosphate (CPP), and β-tricalcium phosphate (β-TCP) particles. This comprehensive review is focused on different
grades of biodegradable magnesium matrix composites including their mechanical properties and corrosion resistance.
© 2018 Published by Elsevier B.V. on behalf of Chongqing University.
This is an open access article under the CC BY-NC-ND license. (http://creativecommons.org/licenses/by-nc-nd/4.0/)
Peer review under responsibility of Chongqing University
https://doi.org/10.1016/j.jma.2018.11.001
2213-9567/© 2018 Published by Elsevier B.V. on behalf of Chongqing University. This is an open access article under the CC BY-NC-ND license.
(http://creativecommons.org/licenses/by-nc-nd/4.0/) Peer review under responsibility of Chongqing University
V.K. Bommala, M.G. Krishna and C.T. Rao / Journal of Magnesium and Alloys 7 (2019) 72–79 73
Table 1
The comparison of mechanical properties of Mg composites to bone and other metals [5].
exhibits the properties like tensile strength, yield strength and from the aqueous medium, then the following reaction occurs
Young’s modulus, as well as corrosion resistance by choos- [17,18]:
ing the suitable reinforcement [2]. The aim of this paper
Zn+H2 O → Zn (OH )2 +H2
will be discussing biocompatible, biodegradable metal ma-
trix composite particularly Magnesium matrix composites for Zinc ions will be removed by the magnesium metal from
orthopedic applications. The composite contains at least two aqueous solution [19,20]:
components which include matrix and reinforcement. In the
Mg + Zn2+ → Zn + Mg2+
biodegradable composites, all elements should be biodegrad-
able and non-toxic to the human body condition. As observed from the above reactions, the rapid corro-
Magnesium is the lightest metal which is having the den- sion rate of magnesium metal produces hydrogen gas with an
sity of 1.74–2.0 g/cm3 , which is 33% lighter than aluminium, aqueous solution; because of this hydrogen evaluation usage
77% lighter than steel. The magnesium material has a high of magnesium alloys as implants are undesirable. To over-
strength-to-weight ratio and also density is very similar to come this problem slow rate of corrosion of magnesium alloy
bone density (1.84 g/cm3 ). Magnesium (Mg) alloys and its is more advisable.
composites have been considered as potential alternatives and
used as conventional implant materials because of their attrac- 1.2. Applications
tive biodegradation and mechanical properties [3–5]. Table. 1
shows the mechanical properties of Magnesium materials to The capability of magnesium-based metals has various
the bone and other metals. The degradation rate is extremely numbers of biomedical applications due to its high degrada-
high in physiological condition; it may lead to deterioration tion rate. Past research and current studies are paying atten-
of mechanical integrity of implant before complete healing tion to biodegradable biomaterials contact with cellular mech-
of fractured bone tissue and also releases a large amount of anisms, and how they are biologically influenced by the cor-
hydrogen gases which delays the healing of fractured bone tis- rosion byproducts [15,21]. Present studies explore how re-
sue. Due to these major issues pure magnesium, magnesium inforcement elements manipulate the corrosion behavior of
alloys, and magnesium composites have been developed for biodegradable orthopedic applications [22]. For orthopedic
bio applications. Magnesium alloys mostly used in biomedical applications, magnesium metal has been reached to increase
applications are Mg–Sn, Mg–Ca, Mg–Zn, Mg–Si, Mg–Sr, and bone strength and interfacial potency when implanted [24].
Mg–Zr, which are non-toxic in a physiological environment. Magnesium metals can be used for various types of fascina-
Along with this magnesium matrix, composites exhibit appre- tion devices for orthopedic surgeries, such as plates, screws,
ciable mechanical strength and corrosion resistance. The se- and fasteners. Current studies have shown that the implanta-
lection of reinforcement materials is calcium phosphate-based tion of a magnesium device shows nominal changes to blood
ceramics [6–10], calcium polyphosphate particles (CPP) [11], composition within a 6-month study post-implantation with-
hydroxyapatite (HAP) [12] and Tricalcium phosphate (ß-TCP) out causing damage to excretory organs like the liver or the
[13]. kidneys [23].
Alloys of Magnesium metal undergo deterioration by var- Metallic metals have been radically growing in biomedical
ious Redox reactions, which are accessed by the alloying applications proposed for development of orthopedic implants
elements. Practically the decay of magnesium in aqueous (hip replacement, joint replacement, prosthesis etc.) and tem-
medium turns out magnesium hydroxide and hydrogen gas. porary implants (wires, rods, pins, plates, screws etc.) [24].
The overall reaction is as follows [14,16]: The Magnesium material as biodegradable implants in vivo
and vitro conditions was already used more than a century
Mg+H2 O → Mg (OH )2 +H2
[25]. Magnesium composites had excellent biocompatibility
Generally, the metal zinc is used as an alloying agent, as compared to other metallic metal composites. Magnesium
because it shows the capability to dislocate hydrogen ions is the fourth most abundant element present in the human
74 V.K. Bommala, M.G. Krishna and C.T. Rao / Journal of Magnesium and Alloys 7 (2019) 72–79
Table 2
Implant metals applications, advantages, and disadvantages [28,31–35].
body and it acts as an essential nutrient for human’s life erties as well as degradation performance. Selections of alloy-
[26–30]. Magnesium composites are valuable material over ing elements were playing a vital role in biodegradable Mg
the other implant materials viz. Stainless steel, Co–Cr, and Ti- alloys, to enhance the mechanical properties and exhibit the
tanium alloys are outlined in Table 2 [28,31–35]. The metallic biocompatibility in the biological environment. The adding of
response of commercially available AZ91D magnesium alloy alloying elements in pure magnesium may improve grain re-
was investigated in vivo and vitro conditions and proposed to finement and strengthen the solid solution. The mainly used
use as a matrix in magnesium composites for orthopedic ap- alloy elements in magnesium and their effect on mechanical
plications [36]. Magnesium material has high corrosion rate properties were presented in Table 3 [37,38]. To step up the
and it releases of Hydrogen (H2 ) gas, which was existed in biocompatibility of Mg alloys in the biological environment
few studies in the middle of last century. However, the most which was based on strengthening ability, toxicity and degra-
of the researchers were focused on Mg composites in the dation rate were shown in Fig. 2.
early 2000s, along with corrosion rate in Mg materials. The Biocompatibility is the key factor for selection of degrad-
modern techniques were developed to control the corrosion able metals and its alloys in a biological environment. The
rate of Mg material at the same time it can heal the frac- implant materials either pure or alloys should be non-toxic
ture tissue without the need for secondary surgery to remove and easily degrade and dissolved into the surrounding tissues
the implanted material. The most of the researchers focus [39]. Alloying elements can be classified as toxic, allergic and
on biodegradable Mg-based materials is developing to design nutrient-based elements which are present in the human body
the implants for orthopedic applications as well cardiovascu- [40–42].
lar stents. The composite contains at least two components
which include matrix and reinforcement. The uncertain toxi- 1) Toxic: Ba, Pb, Be, Th, Cd.
city may develop it will be coming out by the urinary system 2) Allergic: Al, Ce, Cr, Co, Cu, La, Ni, Pr, V,
for the purpose of reducing the itches or any other damage 3) Nutrients: Ca, Mn, Sn, Sr, Zn.
occurred on the human body.
For the above condition, an extreme concern should be 3.1. Presence of Mg in human body
taken for selecting the biological reinforcements to magne-
sium composites. These magnesium composites may exhibit Magnesium is solitary macro mineral presented in the hu-
the biomechanical properties as well as corrosion rate in the man body environment. In generally a human body required
biological condition. 320–420 mg of magnesium minerals were needed in a day.
These magnesium minerals found in a human body 65% at
3. The process to enhance the mechanical properties and bones and teeth, the remaining 35% was presented in blood,
corrosion rate body fluids, organs and other tissues. Magnesium had a den-
sity of 1.74–1.8 g/cm3 , which was very lightest metallic ma-
Pure Magnesium having very high degradation rate in the terial as compared to other metals. It’s having excellent me-
biological environment which causes the implant metal can chanical properties and biocompatibility. Density and elas-
degrade before heals the tissue. Intended for this cause Mg- tic modulus of pure magnesium (41–45 GPA) is nearer to
based alloys were developed to increase the mechanical prop- the cortical bone (3–20 GPA) [43,44]. The other implant
V.K. Bommala, M.G. Krishna and C.T. Rao / Journal of Magnesium and Alloys 7 (2019) 72–79 75
Table 3
Effects of alloy elements in biocompatible Mg alloys [37,38].
material has the density as well as elastic modules is high can be classified as biodegradable pure metals, alloys and
as compared to the cortical bones, due to this mismatch may metal matrix composite (MMC’s). The Metal matrix com-
lead the implant carrying problems (load acting) and causes posite as biodegradable materials is having good mechanical
trauma defending of the bone. With this biological incom- properties (ultimate tensile strength, Young’s modulus, and
patibility, the medical issues were raised like early implant yield strength) as well as corrosion resistance by choosing
loosening, damage to the healing process and chronic inflam- the suitable composite. The composite contains at least two
mation [45]. Magnesium-based implants were similar to bone components which include matrix and reinforcement. In the
density, so there were no medical issues as compared to other biodegradable composites, all elements should be biodegrad-
metallic material [46]. The extensive applications of Mg and able and non-toxic in the human body environment.
its alloys were constrained by their degradation rate and suc- Selection of Matrix may play the very important role in
cessive losses in mechanical properties at pH levels (7.4–7.6) biological implants, as well as reinforcement. The signifi-
on chloride environment. Also, rapid formation of hydrogen cant magnesium compositions were currently being explored.
gas bubbles could be a negative effect on Mg-based implants Those were developed in various stages and every alloy has
[39]. been verified for different applications. Pure magnesium and
Mg-based alloys possess excellent tensile strength, stiffness other elements like Zn, Mn, Al, Ca, Li, Zr, Y, and (RE)
which are nearer to human bones. This gives more interest to [47–51] are used as degradable biomaterials. By using pure
utilize as biodegradable materials in orthopedic applications. magnesium in the biological environment, there is a great oc-
Next advancement of Mg alloys is surface treatment, which currence of Corrosion in Mg as well as H2 gas, which was
reduces the degradation rate of implant material until healing existed in few studies, Zinc has an excellent property which
the fractured tissue. Once the coat is degraded in the physio- suppresses the hydrogen gas developed in the physiological
logical environment the alloy was going to degrade drastically condition. The metallic response of commercially available
before healing the tissue, this is impacts on coated biological AZ91D magnesium alloy was investigated in vivo and vitro
implant materials. conditions and proposed to use as a matrix in magnesium
The main focus of the review is to enhance the mechanical composites for clinical applications [36]. The SEM image of
as well as corrosion property for orthopedic implant materi- commercially available AZ91D is given Fig. 5.
als. A new ere for this is developing of magnesium com- Composites made of bioinert and bioactive ceramics pro-
posite. In this composite nutritional elements were used as duced to achieve two important features; those are biocom-
reinforcement to the strengthening of properties. Selection of patibility and mechanical strength which are very similar to
reinforcement plays a very significant role in the composite cortical bone. There is a specific focus on material properties
which may possess self-resorbable nature to heal the tissue. of biodegradable composites and chemical reaction towards
Mg composites were developing to improve the mechanical formation of fractured bone tissue. Ceramic materials are in-
properties, degradation rate in the biological environment. vestigated to use as biomaterial implants. Ceramics which are
well advised for bio applications and these are called as bio-
4. Biodegradable Mg based composites ceramics. These bioceramics again classified into biocompat-
ible, bioactive, and biodegradable materials. Nowadays cal-
Composite as the name implies, the composite contains at cium phosphate-based ceramics are used as reinforcement in
least two components which include matrix and reinforce- magnesium composites to heal the fractured tissues and ex-
ment. In biodegradable composites, all components within hibits outstanding performance in toxicity and immunological
the composite must be biocompatible, biodegradable and non- reactions. The bioceramics materials properties were given in
toxic to the physiological condition. Biodegradable materials Table 4. The selection of reinforcement materials is calcium
76 V.K. Bommala, M.G. Krishna and C.T. Rao / Journal of Magnesium and Alloys 7 (2019) 72–79
Table 4
The properties of bioceramics [52].
Fig. 3. Microstructure of composites: (a) Mg, (b) Mg–10% HAP, (c) ZM61–0% HAP, and (d) ZM61–5% HAP [72].
(PM) method followed by a hot extrusion process and stud- Khanra et al. [71] provided a comparative study on Mg–
ied mechanical, micro structural properties. The XRD study HAP and ZM61–HAP composites using various amounts of
confirms that small peaks occurred in HAP particles. Hap it- chemically sterilized HAP powder (0, 5, 10, and 15 wt.%).
self shows a poor load carrying capacity which will limit the They prepared the composites by an extrusion process. The
applications. microstructure of fabricated composites shows that by adding
Gu et al. [66] developed the Mg/HAP composite consist of HAP constituent, the grain size decreases (Fig. 3). The
10, 20 and 30 wt % of HAP by PM technique and studied its HAP particles (black) in the Mg composite in case of Mg–10
microstructure, mechanical properties, corrosion, and cytotox- HAP are visible. The SEM micrographs of Mg–10% HAP
icity. Some agglomeration of the HAP particulates is observed consists of agglomerated HAP particles. The SEM micro-
at regular intervals at the Mg/20%HAP composite, where graphs also reveal that decrease in grain size between Mg and
more no of agglomeration can be seen for the Mg/30HAP Mg–10% HAP. With the addition of HAP, the tensile strength
composite, this may reduce the properties of the composite. of the Mg–HAP composites decreases. As observed that per-
Witte et al. [67] prepared and studied mechanical, corrosive centage of elongation decreases also increase in brittleness
and cytotoxicity properties of an MMC based on AZ91 (as the of the Mg–HAP composites. The compressive strength of the
matrix) and HAP particles as reinforcements. They adjust the composite is increased by the addition of HAP. According to
properties of Mg MMC by varying the particle percentages Xu et al. [72], the Mg–15% HAP and Mg–0% HAP com-
and size. The MMC consist of 20 wt. % of HAP powder (size posites exhibits high compressive strength, yield strength and
44 mm), 80 wt.% of AZ91 powder(size 33 mm). The compos- decreases tensile strength by the addition of HAP, where the
ite prepared in PM technique and comparison of properties, compressive yield strength increases by adding HAP particles.
Chen et al. [68] measured the compressive strength of the
porous HAP, AZ91, and AZ91/HAP composite. They found
that AZ91 possesses the superlative strength and ductility as 4.3. Magnesium–tricalcium phosphate (TCP) matrix
compared with the porous HAP and AZ91/HAP composite. composites
However, porous HAP shows very low strength and ductil-
ity that cannot bear any external forces. It has been reported β-TCP has excellent biocompatibility, bioactivity and
that the adding of HAP particles greater than 10 wt.%, the bioabsorbable properties in physiological conditions. The Tri-
yield strength and ultimate tensile strength can be affected calcium phosphate is naturally occurred mineral and has a
through the greater agglomerations of HAP particles and also chemical formula of (Ca3 (PO4)2). Tricalcium phosphate
the formation of pores and defects [69]. possesses high dissolution rate as compared to HAP, which
helps to achieve complete degradation of implant material af-
78 V.K. Bommala, M.G. Krishna and C.T. Rao / Journal of Magnesium and Alloys 7 (2019) 72–79
Fig. 4. (a) SEM micrographs of β-TCP. (b) XRD pattern of β-TCP [73].
5. Conclusions
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