Journal of Alloys and Compounds 714 (2017) 636e667

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Review

Biomedical materials and techniques to improve the tribological,

mechanical and biomedical properties of orthopedic implants e A
review article
Mahmoud Z. Ibrahim a, b, Ahmed A.D. Sarhan c, d, *, Farazila Yusuf a, **, M. Hamdi a
a
Centre of Advanced Manufacturing and Material Processing, Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603,
Kuala Lumpur, Malaysia
b
Department of Mechanical Engineering, Faculty of Engineering, Ain Shams University, Cairo, 11517, Egypt
c
Mechanical Engineering Department, King Fahd University of Petroleum and Minerals, Dhahran, 31261, Saudi Arabia
d
Department of Mechanical Engineering, Faculty of Engineering, Assiut University, Assiut, 71516, Egypt

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

Article history: Recently, there has been an increasing trend in researches focusing on improving the performance of the
Received 28 January 2017 biomedical implants. The clinicians used metallic implants to treat bone imperfections and fractures. The
Received in revised form commonly used metals (Stainless steel, Ti-alloys and Co-alloy) failed to prove long-term durability and
18 April 2017
did not build sufficient bond with human bone. Since the invention of bioactive materials, which can
Accepted 21 April 2017
generate chemical bond with bones, the researchers proposed combining the superior mechanical
Available online 23 April 2017
properties of metals and bioactivity of bioactive materials. This can be achieved by cladding bioactive
material on metallic substrate. Different techniques, like thermal spraying, electron magnetron sput-
Keywords:
Biocompatible metals
tering, laser cladding, etc., were proposed to successfully deposit bioactive materials on metallic sub-
Bulk Metallic Glass alloys strates. In this article, we will discuss the potential of available metallic alloys and bioactive materials in
Bioactivity biomedical implants including different techniques used in depositing bioactive materials on metallic
Coating techniques implants.
Bioglass © 2017 Elsevier B.V. All rights reserved.
Hydroxyapatite

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 637
2. Metallic alloys in biomedical implants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
2.1. Stainless steel alloys (SS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
2.1.1. 316L stainless steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
2.1.2. Ni-free, high concentration stainless steel (ASTM F2229) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
2.1.3. Mechanical and biocompatibility properties of SS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
2.2. Cobalt alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640
2.2.1. Biocompatibility of Co-based alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640
2.2.2. Mechanical properties of Co-based alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641
2.3. Titanium alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641
2.3.1. Biocompatibility of Ti-alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641
2.3.2. Mechanical properties of Ti-alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
3. Metal based amorphous alloys (Bulk Metallic Glass) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 643
3.1. Fe-based BMG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 643

* Corresponding author. Mechanical Engineering Department, King Fahd Uni-

versity of Petroleum and Minerals, Dhahran, 31261, Saudi Arabia.
** Corresponding author.
E-mail addresses: ahsarhan@kfupm.edu.sa (A.A.D. Sarhan), farazila@um.edu.my
(F. Yusuf).

http://dx.doi.org/10.1016/j.jallcom.2017.04.231
0925-8388/© 2017 Elsevier B.V. All rights reserved.
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667 637

3.1.1. Mechanical properties of Fe-based BMG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644

3.1.2. Biocompatibility of Fe-based BMG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
3.2. Ti-based BMGs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645
3.2.1. Mechanical properties of Ti-based BMGs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645
3.2.2. Biocompatibility of Ti-based BMGs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 646
3.3. Zr-based BMGs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647
3.3.1. Mechanical properties of Zr-based BMG alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647
3.3.2. Biocompatibility of Zr-based BMG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 648
4. Bioceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 649
4.1. Bioinert and biodegradable ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 649
4.2. Bioactive materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 650
4.2.1. Hydroxyapatite (HA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 650
4.2.2. Bioactive glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651
5. Techniques to improve the performance of biomedical implants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 653
5.1. Physical vapor deposition (PVD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 654
5.2. Sol-gel technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 656
5.2.1. Hydroxyapatite coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 656
5.2.2. Bioglass coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 656
5.3. Plasma spraying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657
5.3.1. Hydroxyapatite coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657
5.3.2. Bioglass coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 658
5.4. Laser cladding technology (LCT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659
5.4.1. Hydroxyapatite coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
5.4.2. Bioglass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661
5.4.3. New approaches of cladding bioactive material on metallic implants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
5.5. Plasma electrolytic oxidation (PEO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
5.5.1. PEO coatings derived HA coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664
7. Research gap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665

1. Introduction induce poor bioactivity which means that metals do not form
chemical bond with living tissues. By the 1930's, polymers were
The development of medical implants is of great importance to used in biomedical applications, but were limited in load bearing
treat bone fractures and deficiencies. The need for implants applications for their lower mechanical properties than metals. In
increased dramatically in the past 5 years (the number of revision 1970, Larry Hench introduced bioactive glass [6], Fig. 1 shows the
hip surgery increased by 26% and is predicted to reach 137% in development of implants materials in the last century [7].
2030) [1]. This increasing need lead to more focus on developing Bioactive materials are active to form chemical bond with hu-
more durable implants. Until now, there is no record of successful man bones. Bioactive materials are blend of oxides (SiO2, CaO, MgO,
long-term implantation of metallic device in human body. In the P2O5, etc.) which stimulates the composition of bones. Bioactive
past, the used materials were silver and gold which are believed as glass, wollastonite, and Hydroxyapatite (HA, Ca5(PO4)3(OH)) are
bioinert materials, but they are expensive and exhibit poor me- commonly used in implants because of its excellent bioactivity [8].
chanical properties. After Lister introduced his aseptic surgical Usually the most important elements in bioactive materials are Ca
technique, the metallic alloys have been developed to be used in and P and the ratio Ca/P should be controlled (Ca/P ratio in bones is
medical implants [2]. The metallic alloys find wider applications in 1.67). These bioactive materials faced limitations in medical ap-
medical implants than pure metals due to their enhanced me- plications especially load-bearing implants because they are brittle
chanical properties and tribological properties besides good and weak [9]. These materials have very low fracture toughness
biocompatibility. The first implant alloy developed for human was (usually < 1 MPa m1/2) compared to cortical bones (2e10 MPa m1/2)
“Sherman Vanadium Steel” [3]. This alloy failed to last for long time [10]. In the other applications which no load or small loads are
due to rapid corrosion in human body. induced, the bioactive materials proved excellent treatment results,
In 1920's, the stainless steel alloy (18-8 SS) was introduced as an example the middle ear bones replacement [11].
which, at this time, considered a superior corrosion resistant alloy Recently, new trend has been developed to combine the supe-
compared to available alloys [4]. After that time, researchers rior properties of metals (especially the excellent fracture tough-
focused on developing high corrosion materials to be used in ness) and the properties of bioactive materials (bioactivity and
medical application. Later, 316L SS, Cobalt alloys and Titanium al- biocompatibility). Numerous of researches focused on developing
loys introduced and proved high mechanical properties as well as techniques for coating or depositing bioactive materials on metallic
good biocompatibility. Biocompatibility is a term used to describe substrates to improve the mechanical, tribological and biomedical
the behavior of material dealing with living tissue, which is non- properties of biomedical implants. These techniques of improve-
toxic, not releasing harmful elements and not causing allergic ef- ments are still under investigations and further studies are needed
fects [5]. to obtain long-term implants. The different coating techniques
Studies showed that metallic substrates release metal ions used are still under investigations and further studies are needed to
which may be considered toxic and hazardous. Also, the metals obtain long-term implants. Further studies on the adhesion
638 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667

Fig. 1. History of implants materials development [7].

strength between coating and substrate, develop multilayers to Table 1

provide different characteristics, application of new materials (as Metallic elements in human body, their functions and normal concentrations.

metallic glass), and more focused in-vivo tests on developed Metallic Function Normal
techniques. element Concentrations
In this paper, we will focus on the most common metallic alloys FE Contained in heme groups of hemoglobin and 4-5 g in body
used in biomedical implants, bioactive materials and the tech- myoglobin which are required for oxygen transport
niques developed to improve the performance of the implants. in the body. Anemia is the primary consequence of
iron deficiency. Excess iron levels can enlarge the
liver, may provoke diabetes and cardiac failure.
2. Metallic alloys in biomedical implants CU Contained in enzymes of the ferroxidase system 0.9e2.8 mg/L
which regulates iron transport in the blood and [13]
After the discovery of iron, humans used iron in food containers facilitates release from storage. A copper deficiency
can result in anemia from reduced ferroxidase
and other usages. Silver and gold were used in bone implants and
function. Excess copper levels cause liver
dental replacement. In fact, the materials dealing with living tissues malfunction and are associated with genetic
should meet the following requirement; non-toxic, high corrosion disorder Wilson's Disease
resistance, accepted by living tissues and have suitable mechanical ZN Important for reproductive function due to its role 2 g in body
properties as hardness, UTS, fatigue limit, and Young's modulus. in FSH (follicle stimulating hormone) and LH [14]
(leutinizing hormone). Required for DNA binding of
Generally, there is no total inert metal or in other words doesn't zinc finger proteins which regulate a variety of
corrode in the human body. So, the metals and their alloying ele- activities. An excess of zinc may cause anemia or
ments are evaluated according to their toxicity level and durability reduced bone formation.
in the human body. As a fact, metals exist in human body for certain MN Major component of the mitochondrial 2-4 mg/day in
antioxidant enzyme manganese superoxide body [15]
functions. Normal concentrations of different elements are listed in
dismutase. A manganese deficiency can lead to
Table 1 [2]. These elements when exceed certain levels, they improper bone formation and reproductive
become harmful. The human body is highly corrosive media, so as disorders. An excess of manganese can lead to poor
the metals corrode, hazardous metal ions released [12]. iron absorption
Usually, the metallic implants failed to prove durability and CO Contained in vitamin B12. An excess may cause 0.3e0.9 mg/L
cardiac failure. [16]
long-term due to severe bio-corrosion. Developments and im- MO Required for the excretion of nitrogen in uric acid 0.6e13.1 mg/L
provements were made to the alloys to increase their corrosion in birds. An excess can cause diarrhea and growth [17]
resistance. The corrosion of implant can be minimized as follows: reduction.
CR A cofactor in the regulation of sugar levels. 0.4e0.6 mg/L
Chromium deficiency may cause hyperglycemia [16]
1. Usage of appropriate metals.
(elevated blood sugar) and glucosuria (glucose in
2. Avoiding implantation of different types of metal in the same the urine). Elevated levels of some forms of
region. This may cause electro-chemical corrosion. chromium, such as Cr(VI), can be carcinogenic
3. Design the implant to minimize notches, pits and crevices.
4. Recognize that metal corrosion resistance is not the same all
over the body [3]. century. This feature is referred to the formation of chromium oxide
film which is stable and prevents further oxidation. In 1930's, cli-
In the next sections, we will present the most common metallic nicians used 18-8 SS as biomedical implants, but it failed to prove
alloys used in implants considering their properties, applications durability due to rapid corrosion. Further developments were car-
and limitations of use. ried out to enhance the corrosion resistance and new SS alloys were
presented.
2.1. Stainless steel alloys (SS)

Stainless steel is iron-based alloy. The alloy contains Cr, Ni, Mo, 2.1.1. 316L stainless steel
Mn, Si, Cu, and carbon. Stainless steel is featured for its high A further development of 18-8 SS has been done by adding Ni. It
corrosion resistance when first revealed in the early of 20th is found that the corrosion resistance is enhanced when Ni is added,
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667 639

Table 2 Table 3
Chemical composition of 316L SS, compositions presented are in % wt [18]. Mechanical properties of 316L SS [20].

Material Fe Cr Ni C S P Si Material UTS, MPa Yield strength, MPa Modulus of Elasticity, GPa

316L SS Balance 16.0e18.0 10.0e14.0 0.03 0.03 0.045 1.0 316L SS 1170 480 190

and this called 316 SS. After that, it was found that the carbon
causes the formation of chromium carbides which is located at the
grain boundaries leading to localized corrosion. So, decreasing the
carbon content improved the corrosion resistance of the SS, and
316L SS is introduced [2,3]. Chemical composition of 316L SS are
shown in Table 2.
For long years, 316L SS was considered for medical devices and
implants used in trauma surgeries [19], Fig. 2 shows examples for
biomedical implants made from 316L SS in (a) knee replacement
and (b) ankle replacement [2]. 316L is featured for its accepted
mechanical and tribological properties. The mechanical properties
of 316L SS is shown in Table 3. Also, the 316L has high ductility and
can be easily manufactured.
316L SS has reasonably biocompatibility and proved success in
implants. Until now, 316L SS is the most common used alloy in
medical implants due to its low cost, accepted biocompatibility and
good mechanical properties [21]. Moreover, 316L are approved by
the US FDA (Food and Drug Association). Fig. 3. Corrosion failure of SS implant [2].
The studies showed the high risk of releasing of Ni ions in hu-
man body which result from the bio-corrosion of 316L SS when
better pitting corrosion, wear and corrosion resistance than con-
implanted. For this reason, 316L SS was approved only for short-
ventional 316L SS [23]. Besides, it showed enhanced fatigue
term and temporary implants. Ni is important in 316L SS as it sta-
strength and hardness [7]. The developed alloy has great potential
bilizes the austenitic phase (austenitic SS is preferred rather than
in biomedical applications, but still need further studies to evaluate
martensitic SS in implants) [22].
its biomedical properties.
Although the proposed high corrosion resistance of 316L SS,
The developed Ni-free SS has enhanced bio-corrosion (Fig. 4),
they showed poor durability as implant in human body. Normally,
enhanced fatigue resistance, and excellent cytocompatibility near
they corrode rapidly when implanted and corrosion failures take
to commercial pure titanium (Fig. 5), [7].
place as shown in Fig. 3. So, their applications are limited in medical
devices or short-term implants [2,4]. Also, the release of Ni ions,
which included in the 316L SS alloy, may cause severe adverse ef-
2.1.3. Mechanical and biocompatibility properties of SS
fect on the human health. Further development introduced a Ni-
The nature of loads is static and dynamic. The dynamic load is
free SS alloy with enhanced properties.
more critical as the most of implants fail due to lack of fatigue
strength. Normally, the implants are directed to corrosion and
2.1.2. Ni-free, high concentration stainless steel (ASTM F2229) pitting corrosion due to the aggressive behavior of the human body
New developments were investigated to enhance the biocom- which affects the fatigue resistance.
patibility of 316L by replacing Ni with high concentration of ni- Generally, SS-alloys are reliable in terms of fatigue resistance.
trogen. Nitrogen was found to act as austenitic phase stabilizer However, the alloy showed reduced fatigue properties (by about
replacing hazardous Ni. So, Ni-free, high concentration nitrogen SS 20% of dry fatigue strength) when subjected to corrosive media
(ASTM F2229) was developed (Table 4 shows compositions (in (Fig. 6) [2]. As a fact, SS is very sensitive to fatigue failure in
wt.%) of 316L SS and ASTM F2229). The ASTM F2229 SS proved corroding environment, which increase the possibility of failure

Fig. 2. Examples of 316L SS implant in (a) knee, (b) ankle [2].

640 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667

Table 4
Composition (in wt. %) of 316L SS and Ni-free, high concentration SS (ASTM F2229).

Stainless Steel type Cr Ni Mo Mn Si Cu N C P S

316L SS (ASTM F138) 17.00e19.00 13.00e15.00 2.25e3.00 2.00 0.75 0.5 0.1 0.03 0.025 0.01
ASTM F2229 19.00e23.00 0.10 21.00e24.00 0.50e1.50 0.75 0.25 >0.90 0.08 0.03 0.01

Fig. 4. Potential/current density curve for 316L SS, ASTM F2229 SS and CP Ti [7].

Fig. 6. ASTM F2229 SS fatigue performance in air and in 0.9% NaCl solution [2].

alloy, have suitable biocompatibility, and exhibit good mechanical

properties. In addition, it is widely used and is approved from FDA
(US Food and Drug Administration) as temporary biomedical
implant material [26,27].
On the other side, SS alloys have poor bio-corrosion resistance
and pitting corrosion resistance, reduced fatigue performance in
corroding media, no bioactivity, and poor wear resistance. Even the
developed ASTM F2229 SS proved better properties (as fatigue,
wear and corrosion resistance, no Ni ion release) to replace the 316L
SS, it still lacks to make sufficient bond with bones which may
experience implant release. Further studies should be held to
ensure the bio-performance of this alloy. Also, higher nitrogen
concentrations affect the toughness of alloy [4,7].

2.2. Cobalt alloys

Fig. 5. Cell growth obtained on ASTM F2229 SS, 316L SS and CP Ti [7].
due to fatigue.
SS has poor pitting and crevice corrosion resistance because of
the chromium carbides formed on the grain boundaries [23,24]. So,
SS implants failures which were reported because of fatigue fail-
ures, was due to initiation of cracks at very poor surface finish and
crevice corrosion sites. However, the developed F2229 SS proved
better crevice corrosion resistance because of the addition of ni-
trogen, but still need more investigations [25]. (Table 5 shows
mechanical properties of 316L SS and ASTM F2229). Another point
is the inferior wear resistant of SS alloy which caused by debris
release and reduce life. So, SS alloy are limited in joint replacement
which directed to relatively wear rates [7].
As a conclusion, SS alloys are featured to be relatively cheap
In the early of 20th century, the CoCrMo alloy presented and was
employed in aircraft applications. The alloy includes Co as base
metal, Cr, Mo, W, C, and Ni as alloying elements, the role of alloying
elements is listed in Table 6. The alloy showed great corrosion and
wear resistance and excellent mechanical properties (UTS, fatigue
strength, Young's Modulus) even at elevated temperatures. The
alloying elements Cr, Mo, and Ni are responsible for the excellent
wear and corrosion resistance [2]. In 1940s, the alloy found the first
application in medical implants in dental application. After that, the
alloy was developed and utilized in orthopedics and joints Fig. 7
shows knee replacement made of CoCr alloy) because of their
excellent wear resistance and galvanic properties [19,28].
2.2.1. Biocompatibility of Co-based alloys
Although Co, Cr, and Ni are classified as high toxic elements [12],
the alloy CoCrMo showed high biocompatibility due to its high
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667
Table 5
Mechanical properties of 316L SS and ASTM F2229.
Stainless Steel type UTS, MPa Yield strength, MPa
316L SS (ASTM F138) 490e1350 190e690
ASTM F2229 931e1731 586e1551
*The fatigue strength is measured at 107 cycles.
Table 6
Roles of various alloying elements in Co-alloys.
Alloying Rule in Co-alloy
element
Cr Enhance wear and corrosion resistance
Ni Enhance corrosion resistance, increase strength and castability
Mo Enhance corrosion resistance and increase strength
C Enhance wear resistance and increase castability
W Enhance strength, but decrease corrosion fatigue strength and
corrosion resistance
Fig. 7. Knee replacement made from CoCrMo alloy.
corrosion resistance which limits the ion release of toxic elements
[29]. Co-based alloys succeeded in medical implants and consid-
ered as permanent implant replacing SS alloys, besides the superior
mechanical properties. Co-based alloys replaced 316L SS in joint
replacement as they exhibit excellent wear resistance. However, in
long term the metal-on-metal contact results in debris which
release cobalt and chromium ions in the human body causing se-
vere adverse effects [29].
Moreover, CoCrMo alloy showed low osseointegration and
exhibited no bioactivity beside the cost, which is great challenge for
Co-based alloys [19]. M. Plecko et al. investigated the osseointe-
gration of different metals. The results showed poor osseointegra-
tion, even lower than stainless steel, which brings a new limitation
for CoCr-alloys. Fig. 8 shows the fluorescence and toluidinblue dye
of bone-section after removal of screw implant. The figure shows
641
Fatigue strength in air Fatigue strength in PBS Hardness, HRC Max elongation, %
220e600 220e600 25e39 12e40
650 500 43e50 12e52
lower new cells developed at the interface in the case of CoCr
implant (the grey color represent the old bone cells and the blue
color represent the new cells formed) [19]. For this reason, further
studies should be held to evaluate the toxicity, biocompatibility and
osseointegration of the Co-alloys.
2.2.2. Mechanical properties of Co-based alloy
CoCrMo alloys are widely used in biomedical implants for their
high wear resistance and high hardness. Also, they exhibit high
mechanical strength (UTS 960 MPa), Table 7 compares the me-
chanical properties of Co-alloys and ASTM F2229, and high pol-
ishing surface quality which enhance the corrosion resistance and
minimize the pitting and crevice corrosion. They have excellent
fatigue resistance behavior (107 cycles at 610 MPa) even when
notched, and can be improved by post treatments (the fatigue
strength is increased by 100%e120%), Fig. 9 shows superior fatigue
behavior of Co-alloys over 316L SS [30]. They showed excellent
fatigue resistance when subjected to corroding media, Fig. 10 [2].
However, Co-alloys has poor fatigue strength in PBS e
100e200 MPa which is marginally unsafe compared to the loadings
for arms and legs which may reach 200 MPa e which result in
lower success rate of Co-alloys implants after 20 years [2].
As a conclusion, the main features of CoCrMo alloy are excellent
corrosion resistance, excellent wear resistance, superior mechani-
cal properties, and high fatigue resistance in air. These features
make Co-alloy excellent for biomedical applications (it occupies
about 20% of the joints replacement - hip and knee joints - market).
However, Co-alloys have low ductility, poor fatigue in PBS,
increased cost, and need expensive fabrication processes are the
main drawbacks. In addition, they are high density (9.8 gm/cm3)
alloys, and may release toxic metal particles. These drawbacks limit
the increasing use of Co-alloys in biomedical implants. One of the
other issue facing Co-alloys is the implant failure due to fretting
fatigue. However, CoCrMo alloy is still the most popular alloy used
in joints because of the excellent wear and corrosion resistance [2].
2.3. Titanium alloys
Ti alloys were first introduced as structure material in aerospace
application. Later, in 1950 Ti-alloys were employed as dentistry
implants. After that, it became of great interest to be used in bone
implants [7]. Ti is considered non-toxic, even at high doses, to the
human body [6,10,31].
Titanium is low density metal (4.8 gm/cm3) which offer superior
specific strength over other common alloys. Pure titanium can be
used, but for limited application because of their relatively insuf-
ficient mechanical and fatigue strength, however, studies showed
that titanium fatigue performance does not affected in corroding
media [32]. This makes high potential for using titanium in
biomedical applications. To enhance the mechanical properties, the
titanium is strengthened by adding alloying elements as Al, V, Nb,
Zr, Mo, etc. [32]. Ti6Al4V is one of the most common alloy used in
biomedical applications for its excellent mechanical properties.
2.3.1. Biocompatibility of Ti-alloys
Ti alloys e especially Ti6Al4V e proved excellent corrosion
642 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667

Fig. 8. Bone sections after removing screw implants (a) CoCr alloy, (b) Stainless Steel.

Table 7
Mechanical properties comparison between Co-alloys and ASTM F2229.

Material UTS, MPa Yield strength, MPa Fatigue strength in air, MPa Fatigue strength in PBS Hardness, HRC Max elongation, %

Co-alloys 650e1900 450e1610 200e950 100e200 47 12e50

ASTM F2229 931e1731 586e1551 650 500 43e50 12e52

Fig. 9. Fatigue strength of SS and Co-Cr alloys [2]. Fig. 10. Fatigue performance of Co-alloy in air and physiological solution [2].

resistance and biocompatibility. The in vitro and in vivo tests
showed that Ti element is safe for human body and possess high
osseointegration (the formation of a direct interface with bones
without intervening soft tissues), Fig. 11 shows the infusion at the
interface between host bone and Ti implant.
It is noted that Ti has excellent biocompatibility and exhibit the
highest polarization resistance, which resulted on great concern on
developing Ti-alloys, Fig. 12 shows the biocompatibility of different
metallic element [7]. It is however should be noted that Al and V are
reported to have allergic effect on the human body. So, develop-
ment of second generation of Ti alloys was proposed by replacing Al
and V with Zr, Ta, and Mo which are considered relatively safe for
human body [7,32]. Alloys Ti6Al7Nb, Ti5Al2$5Fe, Ti15Zr4Nb2Ta, etc.
were developed for biomedical applications as they are allergy-free
alloys. However, these alloys contains elements with different
specific weight and melting point causing non-homogeneity of the
casting which requires advanced manufacturing processes [7].
2.3.2. Mechanical properties of Ti-alloys
Generally, with low density and strength (500 MPa) comparable
to that of 316L SS, the most featuring property of Ti-alloy is their
superior specific strength (288 N m/kg while 63 N m/kg for SS) and
have relatively low Young's Modulus (80 GPa) which is near to the
value of cortical bones [2,32]. Table 8: Mechanical properties of
pure Ti and Ti6Al4V alloy. This reduce the effect of stress shielding
which may cause the release of implant form the bones. The Ti-
alloy proved no change in fatigue behavior in PBS (Fig. 13 shows
that the fatigue strength remains the same in air and in PBS).
However, Ti-alloy is sensitive to fretting fatigue which is about half
the plain fatigue strength [32]. This property causes the fracture of
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667 643

surface quality as its fatigue resistance is very sensitive to surface

conditions and the fatigue strength may be reduced up to 40%
when notched [2].
As a conclusion, Ti-alloy is featured for its high specific strength
compared to SS and Co-alloys, low density, high corrosion resis-
tance, and superior biocompatibility and osseointegration. How-
ever, Ti-alloy drawbacks are their relatively high cost, poor
forgeability, high sensitive fatigue strength to notches and insuffi-
cient bending strength, low hardness and low wearing resistance.
These drawbacks limit the application of Ti-alloy in long-term load
bearing implants and in joints, however, it is highly promising alloy
for other biomedical applications [32]. Until now, there is a lack of
long-term application of Ti-alloys in clinical applications due to low
wear resistance and inferior both fatigue and fretting fatigue
strength.

3. Metal based amorphous alloys (Bulk Metallic Glass)

Recently, amorphous phase alloys or Bulk Metallic Glass (BMG)

Fig. 11. Infusion at the interface between bone and Ti implant [2].
Fig. 12. Biocompatibility and polarization resistance of metals [7].
came to concern because of their superior mechanical properties
and excellent performance in wear and corrosion behavior. BMGs
do not have crystalline structure as conventional solidified metals,
Fig. 15. BMG was first introduced in 1950's by very high cooling rate
(104e107
C/s) from the vapor or liquid state. At this time the ap-
plications were limited because of limited sizes obtained [33].
Certain studies succeeded to obtain amorphous phase at lower
cooling rate through using certain levels of alloying elements e
depending on the size of the atoms used e enabling producing
much bigger sizes (up to few centimeters) [34]. Recently, it is
proved to obtain amorphous alloys by using different techniques as
ion implantation, electrodeposition or mechanical alloying [35].
Fig. 16 shows the development in BMG systems and the improve-
ments in obtained sizes [36].
The amorphous systems can be categorized as ferrous and non-
ferrous alloy systems. The ferrous alloy system (Fe-Si-B-Nb, Co-Fe-
Si-B-Nb, Ni-Si-B-Ta, etc.) are featured for their high magnetic
properties which can be employed in transformers and other
electromagnet equipment. The non-ferrous alloy systems are
employed in different applications like sport, electronics, medical
and foundry equipment.
Recently, the BMGs have high potential to be applied in
biomedical applications. They can be categorized as biodegradable,
like Mg, Ca, and Zn based BMGs, and non-biodegradable BMGs, like
Fe, Ti, and Zr, based BMGs [39]. It was found that BMGs have
excellent biocompatibility properties as high strength, high wear
resistance and superior corrosion resistance. Hence, Fe, Ti, Zr based
BMGs are potential candidatures for replacing the crystalline
stainless steel, Ti, and Co alloys.

3.1. Fe-based BMG

Ti implants, for example, at the neck of THR in Fig. 14.
On the other side, titanium is very poor in wear resistance, poor
The Fe-based BMG are considered low in cost, which make it
hardness and exhibits low tensile ductility and low bending
attractive in different applications, besides their good glass-
strength which made Ti-alloys fail to prove long-term implant
forming ability. Usually, the developed Fe-based BMG are used in
especially in THR (Fig. 14 shows fracture of Ti implant due to fret-
transformers cores, inductors, etc. for their good magnetic prop-
ting fatigue) [2]. The implants made of titanium should have high
erties. Considering the biomedical applications, these magnetic

Table 8
Mechanical properties of pure Ti and Ti6Al4V alloy.

Material UTS, MPa Yield strength, MPa Fatigue strength in aira, MPa Fatigue strength in PBS Hardness, Max elongation, %

Pure Ti 241e550 172e480 120e275 100e200 70-100 HRB 15e24

Ti6Al4V 896 827 250e300 250 30-39 HRC 10
a
Fatigue life is measured at 107 cycles.
644 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667
Fig. 13. Fretting fatigue and plain fatigue of (a) TiNbTaZr alloy, (b) Ti6Al4V alloy [32].
Fig. 14. Fracture of Ti-implant.
properties are undesirable because it affects the clinical diagnoses
using Magnetic Resonance Investigation (MRI). V. Ponnambalam
et al. presented non-ferromagnetic at room temperature Fe-based
BMG which may be applied in biomedical implants [40].
3.1.1. Mechanical properties of Fe-based BMG
The Fe-based BMGs exhibited excellent mechanical properties.
They have high ultimate tensile strength, yield strength, and high
Fig. 15. SEM of (a) Zr-based BMG [37], (b) 304 SS [38].
hardness. X.J Gu et al. evaluated the mechanical properties of non-
ferromagnetic Fe-based BMG. The results revealed that the
constitution of the alloy affects its strength as well as their elasticity
and plasticity [41]. The authors studied 23 different Fe-based BMG
alloys and the results obtained are summarized in Table 9
compared with ASTM F2229 SS and CoCr alloy. The mechanical
properties of Fe-based BMG are outstanding, but it exhibited small
elongation until fracture and it is limited bulky sizes (up to 16 mm
in diameter).
An important mechanical property required in biomedical
implant is the fatigue strength. Normally, the crystalline alloys
exhibit endurance limit (maximum stress for 107 cycles) about
0.4e0.6 of their fracture strength. D.C. Qiao et al. studied the fatigue
behavior of Fe-based BMG (Fe48Cr15Mo14C15B6Er2) and found that
its fatigue strength is considerably high (682 MPa), but with lower
endurance limit/tensile strength (4.4 GPa) ratio (0.155). However,
the material failed abruptly when the endurance limit is exceeded.
Fig. 17 shows the fatigue behavior of Fe-based BMG [42].
3.1.2. Biocompatibility of Fe-based BMG
Fe-based BMGs are reported to exhibit enhanced biocompati-
bility than stainless steel due to its promising corrosion resistance
and mechanical properties, especially in body simulated solutions.
In addition, the developed non-ferromagnetic Fe-based BMG is
nickel free, which results in less hazardous effect as medical
implant. Fig. 18 shows the surface morphology of Fe-based BMG
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667 645

Fig. 16. Historical development in BMG systems and obtained sizes [36].

Table 9
Compares the mechanical properties of Fe-based BMG with ASTM F2229 and CoCr alloy.

Material Yield strength, MPa UTS, MPa Plastic strain, % Vickers Hardness, GPa

Fe-based BMG 3400e3800 3800e4400 0e0.8 8e11

ASTM F2229 SS 586e1551 931e1731 12e52 0.42e0.51
CoCr 560 960 20 0.47

Fig. 17. Compares the fatigue behavior of Fe-based BMG, Zr-based BMG, High nitrogen steel, and Al-alloy [42].

and 316L SS before and after immersion in Hank's solution.
Y.B. Wang et al. studied the performance of three different Fe-
based BMG in body simulated solution and compared with 316L
SS performance. They measured the amount of ion release and the
cell growth on the different substrates. The result showed negli-
gible ion release from the different Fe-based BMG compared to
316L SS, Fig. 19 [43].
The results showed that better biocorrosion and pitting corro-
sion resistance of Fe-based BMG than 316L SS, as well as high cell
growth which reveals the biocompatibility potential of Fe-based
BMGs. However, these BMGs needs more in vivo and in vitro
investigation before introducing to the market.
3.2. Ti-based BMGs
Titanium and its alloy are of great concern in the recent decades
to be utilized in biomedical applications due to their excellent
corrosion resistance, biocompatibility, and mechanical properties.
However, enhanced mechanical properties are required. BMG sys-
tems present better mechanical properties and corrosion resistance
behavior. Late in previous century, Ti-based BMG was presented
with enhanced mechanical and biomedical properties which can be
considered further development Ti-alloys for permanent implants.
3.2.1. Mechanical properties of Ti-based BMGs
Many researches were held to evaluate different Ti-based BMG
646 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667

Fig. 18. Surface morphology of (a) Fe-based BMG, (b) 316L SS, (c) Fe-based BMG after immersion in Hank's solution, and (d) 316L SS after 15 days immersion in Hank's solution [43].

before, fatigue strength is very important factor for biomedical

implants. It is reported that Ti-based BMGs have promising fatigue
strength reaching 1.5 GPa and the ratio of endurance limit to tensile
strength is high up to 0.8. This indicates that Ti-based BMG may not
undergo fatigue phenomena, Fig. 20 shows the S-N curve of
different BMG alloys and crystalline alloys [44].

3.2.2. Biocompatibility of Ti-based BMGs

Fig. 19. Metal ion releasing in Hank's solution for different Fe-based BMG and 316L SS
[43].
alloys. The presented Ti-based BMG has relatively low Young's
modulus (80e120 GPa), higher tensile strength (1700e2500 MPa),
and enhanced corrosion resistance, Table 10 [39]. As mentioned
Many studies investigated the corrosion behavior of Ti-based
BMGs in different types of body simulated solutions, like
phosphate-buffered solution (PBS), Hank's solution and Ringer's
solution. The studies showed higher corrosion resistance than
crystalline Ti-alloys. Ling Bai et al. investigated in vitro behavior of
Ti70Zr6Fe7Si17 and Ti64Zr5Fe6Si17Mo6Nb2 (at.%) BMG alloys. The re-
sults showed excellent biocompatibility of both alloys, moreover,
the morphology of the specimen revealed forming HA after 15 days
of immersion in SBF, Fig. 21 [45].
These results reveal the promising potential of using Ti-based
BMG in biomedical implants replacing the crystalline Ti-alloys.
However, Ti-based BMG is limited in size (up to 15 mm in diam-
eter) and needs further investigation for both in vitro and in vivo
behavior.

Table 10
Mechanical properties of Ti-based BMG and Ti6Al4V.

Material UTS, MPa Fatigue Strength, MPaa Young's Modulus, GPa Elongation, % Vickers Hardness, GPa

Ti-based BMG 1700e2500 1500 68e102 2.3 4e5

Ti6Al4V 896 250 80 10 0.30-0-39
a
The fatigue strength is evaluated at 107 cycles.
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667 647

high tensile strength, low Young's modulus, good toughness and

good corrosion resistance which in turn become promising in
biomedical implants [47].

3.3.1. Mechanical properties of Zr-based BMG alloys

Zr-based BMG showed relatively high tensile strength (up to
2 GPa), relatively low Young's modulus (about 90 GPa) [48]. In
addition, it exhibits good wear resistance, high hardness and high
specific strength [37]. It showed to have the same hardness of
GCr15 (HRC 60e63), but has higher compressive strength
(1900 MPa) and higher fracture toughness (55e59 MPa) [46],
Table 11: Mechanical properties of Zr-based BMG compared to
Ti6Al4V.
Another important property is the fatigue strength. Certain
studies revealed that Zr-based BMG alloys has fatigue limit which is
low as 6e8% of the tensile strength (120e160 MPa) compared to
conventional crystalline steel and aluminum alloys [49]. G.Y. Wang
et al. investigated the fatigue behavior of three different Zr-based
BMG alloys. The results revealed promising Zr-based BMG has fa-
tigue limits comparable with high-strength crystalline alloys,
Fig. 22 shows (a) the fatigue behavior and (b) fatigue limits versus
tensile strength of different BMG and crystalline alloys [50].

Fig. 20. S-N curve of different BMG systems [44]. Table 11

Mechanical properties of Zr-based BMG compared to Ti6Al4V.

Material UTS, Fatigue Strength, Young's Modulus, Hardness,

3.3. Zr-based BMGs MPa MPaa GPa HRC

Zr-based 2000 550 90 55e59

The Zr-based BMG has high potential since introduced in 1993 BMG
by Peker and Johnson [46] due to their promising mechanical Ti6Al4V 896 250 80 30e39
properties and biocompatibility (see Fig. 12) [47]. Zr-based BMG has a
Fatigue is evaluated at 107 cycles.

Fig. 21. SEM image of Ti-based BMG showing formation of HA after 15 days cultivation in SBF [45].
648 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667

Fig. 22. (a) Stress-Life curve of three different Zr-based BMG alloys in vacuum and in air, (b) Fatigue limit vs yield strength of BMG and Crystalline alloys [50].

3.3.2. Biocompatibility of Zr-based BMG
One of the key properties for biocompatible materials is the
corrosion resistance. Many studies investigated the corrosion
resistance of Zr-based BMG in various physiological solutions. The
results showed enhanced corrosion resistance than conventional
crystalline alloys - like stainless steel, Co- alloys and Ti-alloys [39].
This because of the passive film formed which is composed of ZrO2.
It was revealed that the addition of Yttria 1% wt. enhanced the
biocorrosion resistance of Zr-based BMG alloy [51].
Other studies investigated the biocompatibility of Zr-based BMG
both in vitro and in vivo. The findings showed superior
biocompatibility of Zr-based BMG over crystalline stainless steel,
Zr-alloys and Ti-alloys [39]. Yu Sun et al. investigated the in vitro
and in vivo biocompatibility of Ag-bearing Zr-based BMG and
compared with pure Ti and Ti6Al4V. Fig. 23 shows the developed
pits on the surface of the specimen. It is cleared that pure Ti and
Ti6Al4V alloy exhibited larger pits than that in Zr-based BMG [52].
Generally, Zr-based BMG alloys are promising materials for
biomedical applications because of their excellent mechanical and
biocompatibility properties. However, Zr-based BMG alloys prod-
ucts are limited in size, as well as, they are very brittle in tension
and show less plasticity in compression [53]. Although the fracture

Fig. 23. SEM image of (a) Zr51$9Cu23$3Ni10$5Al14.3, (b) Zr51Ti5Ni10Cu25Al9, (c) pure Ti, (d) Ti6Al4V after 15 day of immersion in Hank's solution at 37
C [52].
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667 649

cytotoxicity and high corrosion resistance [56,57]. However, the

bioceramics are brittle due to their oxide nature which limits their
application in load-bearing implants.

4.1. Bioinert and biodegradable ceramics

The bioinert ceramics have great potential in biomedical appli-

cations because of their high corrosion and wear resistance, and
non-toxicity behavior. The bioinert ceramics result in fibrous tis-
sues formation at the implant interface.
Zirconia (ZrO2), alumina (Al2O3), Tantalum oxide and other
metal oxides are examples of bioinert ceramics. Alumina is the
most common used bioceramics for their excellent tribological and
biocompatibility behavior, in addition, their high mechanical
properties [55]. The alumina has successfully utilized in knee and
hip joints prosthesis [58].
Furthermore B. Rahmati et al. showed that Tantalum oxide
(Fig. 24) has excellent biocorrosion and wear resistance (Fig. 25
shows worn (a)Ti6Al4V and (b) Tantalum oxide surfaces) besides
the mechanical properties. The Tantalum oxide is featured for low
ion release, high hardness, and excellent wettability [57,59].
On the other hand, Zirconia (ZrO2) has superior mechanical
properties exceeding alumina (Table 12 compares the properties of
alumina, zirconia and TaO) and excellent biocompatibility proper-
Fig. 24. SEM image of Tantalum oxide [60]. ties [55]. Usually, zirconia is doped with Y2O3 (Yttria Stabilized
Zirconia YSZ) to enhance the properties - YSZ has low thermal
conductivity and high thermal stability - and improve the micro-
strain can be improved from 2% to 5.5% regarding to the existence of
structure, Fig. 26 [61,62]. ZrO2 is used to increase stability and
crystalline phase within the amorphous matrix, it is still need more
hardness of HA [63].
investigation [54]. In addition, the production processes are
The biodegradable ceramics are resorbed in the human body.
expensive as it requires high purity elements and expensive con-
These materials are degraded and then replaced by the living tissue
sumables [36].
which is highly considered to treat broken bones. Mainly, biode-
gradable ceramics are certain phases of calcium phosphates which
4. Bioceramics
Table 12
Bioceramics are referred to materials that are biocompatible. Physical and mechanical properties of alumina and zirconia.
The bioceramics are bioinert, biodegradable, or bioactive. The bio-
Property Alumina Zirconia Tantalum
inert ceramics are non-toxic and does not interact with the living
(Al2O3) (ZrO2) Oxide
tissues. The biodegradable ceramics allow the living tissue to
Density, (g/cm3) 3.90e3.93 5.60e6.12 8.2
replace the implant, i.e. the biodegradable ceramic is resorbed in
Surface roughness, Ra (mm) 0.02 0.008 e
the human body. Another promising bioceramics are bioactive Hardness, (HV) 2000e2300 1300 450e535
materials as Bioglass and hydroxyapatite which are able to form Bending strength, (MPa) 400e550 1200 e
bond with hard and soft tissues [55]. The bioceramics are of strong Young's modulus, (GPa) 380 200 100
potential to be used in scaffolds and bone grafts to treat fractured Fracture toughness, K1c 5e6 15 3e10 [64]
(MPa.m1/2)
and damaged bones because of their high biocompatibility, low

Fig. 25. Worn surface of (a) Ti6Al4V, (b) Tantalum oxide [57].
650 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667

Fig. 26. SEM of sintered (a) ZrO2 [61], (b) YSZ [62].

is the main constitute of bone. The ratio Ca/P controls the solubility
of calcium-phosphate phases. The b-tri-calcium phosphate, tetra-
calcium phosphate, and CaO are the common biodegradable pha-
ses. When the surface of calcium-phosphate is directed to water
and certain level of temperature, it forms bioactive phase (hy-
droxyapatite) [55]. These biodegradable are not stable at high
temperatures which limits fabricating them into biomedical im-
plants [65].
Scaffolds e an artificial structure that provides support for
growing tissues and cells [72], Fig. 29 [73] e should be 3D-porous to
increase the surface reactivity in physiological fluids and conse-
quently, enhance the bond strength with living tissue. Beside the
chemical composition, the microstructure and morphology of the
bioactive scaffold affects the performance [73]. In this paper, we
will focus on bioactive glass and hydroxyapatite as the most com-
mon used bioactive materials.

4.2. Bioactive materials 4.2.1. Hydroxyapatite (HA)

For medical implants, it was thought that the best material is the
most inert until 1969 when L. Hench and his research team intro-
duced bioactive glass. Bioactive glass can form chemical bond with
human bones, Fig. 27 shows the mechanism of the bonding be-
tween bioactive material and bone and formation of new bone
layers [56], Fig. 28 shows SEM image of cell growth on pure Ti and
tri-calcium phosphate as bioactive material [66]. The number of
cells over tri-calcium phosphate is higher than that on pure Ti
surface. This means higher osseointegration and bioactivity of tri-
calcium phosphate compounds. These materials are composed of
soda-calcia-phospho-silicate glasses known as 45S5 Bioglass.
Bioactive glass is non-cytotoxic and has the ability to form hy-
droxyapatite (HA) layer on its surface equivalent to the composition
of living bones [67]. For this reason, wide clinical applications used
bioactive glass in dental and bone treatment. Bioactive glasses are
reported as safe for humans and proved no toxicity to the living
tissues [68].
Other materials showed bioactivity behavior like synthesized
hydroxyapatite (HA), bioactive ceramics based on borate and bo-
rosilicate, and natural wollastonite (Ca-SiO2) [69e71].
HA is a popular bioactive material used to treat damaged or
defected bones. It is non-toxic and promote bone growth which
lead to enhanced fixation of implants [22]. The main constitutes of
HA is Ca and P, and the common chemical form is
[Ca10(PO4)6(OH)2]. This chemical form is near to the bone which
contains Ca, P and water [22]. HA can be natural or synthesized. For
pure synthesized HA e which is most common as it is cheaper and
most available, the Ca/P ratio is made 1.67 (Ca/P ratio in bones is
1.65), which facilitates growth of the living bone [74].
The HA has the advantage to be biocompatible with soft tissues
e as skin, muscle, and gum - as well as hard tissues. This feature
brings HA applicable in different biomedical applications. HA de-
grades slowly in vivo, so HA can act as temporary substrate for
further development and growth of cells [75].
An important factor for successful HA scaffold or implants is the
degree of porosity. The porosity increases the surface area of porous
parts. The cells and bone tissues are grown more on porous parts
which guarantee better bonding and fixation, Fig. 30 shows the
porosity level in scaffolds in different parts of the body [56].
Another important factor that affect the resorption of HA is the
degree of crystallinity of the bioactive material interfaced with the

Fig. 27. Formation of new bone layer on HA surface [56]; (1, 2) Solubility of HA in physiological fluid, (3) equilibrium between the HA phase and physiological fluid, (4) adsorption of
proteins and other bio-organic compounds, (5, 6) Cell adhesion and growth, (7, 8) formation of new bone.
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667 651

Fig. 28. SEM image of cell growth after 11 days of cell-culture on (a) pure Ti, (b) Tri-calcium phosphates [66].

living tissues. The dissolution of bioactive material depends on the
degree of crystallinity. The higher degree of crystallinity reduces
the resorption rate of the bioactive material and offer longer life,
which is desirable in certain cases [66]. S. Overgaard et al. inves-
tigated the influence of crystallinity of HA on the bonding strength
with bones. They found that after 16 week low crystallinity of HA
(50% crystallinity) exhibited stronger bonding with bone than high
level (75% crystallinity). After 32 weeks, both crystallinity have the
same bonding strength with bones - the bonding of 75% crystal-
linity HA increased and 50% remains the same. However, the low
crystallinity induced higher degree of cell growth, Fig. 31 shows the
bone growth on 50% and 75% crystallinity HA [76]. The arrow shows
the HA layer at the interface indicating that higher bone growth
was on 50% crystallinity.
One of the challenges that faces HA utilization in load-bearing
(as hip bone, knee joint) implants is their brittleness and poor
mechanical properties, as strength, fatigue and fracture toughness,
Table 13 shows the lack in mechanical properties of HA compared
to cortical bone [77]. Another application challenge is that the
different techniques used to fabricate HA implants impose high
temperatures, which in turn, result in decomposition of HA and
form unstable phases. Consequently, researchers studied doping
HA with stabilizing oxides as Y2O3, ZrO2, alumina, SiO2, etc [56]. C.
S. Chien et al. studied Fluorapatite as substitute of HA. The pre-
sented FA showed better stability and same bioactivity as HA [10].
Hongjian Zhou et al. revealed that nanoscale HA proved better
biocompatibility, enhanced mechanical properties, and osseointe-
gration properties [75].
4.2.2. Bioactive glass
Bioactive glass (Bioglass) was first presented in 1970's by L.
Hench. Bioglass is compounds of SiO2, CaO, MgO, Na2O, K2O, and
P2O5 [79], Fig. 32 presents SEM image of Bioglass particles [80]. The
most common type is bioactive glass 45S5 which consists of 45%
SiO2, 24.5% CaO, 24.5 Na2O, and 6% P2O5 [81]. Bioglass 45S5 is
preferred as it showed high rate of bone formation on the surface
(just one week after implantation) than that for synthetic HA or
other calcium-phosphate ceramics, Fig. 33 compares the cell
growth on different bioactive materials [67].
Normally, Bioglass forms carbonated-HA when interfaced with
living cells or tissues. This layer builds firm bond with bone, Fig. 34
shows the formation of bone cells on Bioglass (1) Bioglass particles,
(2) transition layer between Bioglass and bone (3) new bone cells
formed [67], which makes Bioglass promising in biomedical ap-
plications. An important issue in fabrication Bioglass is to maintain
its glass-phase rather than crystallization, which in turn makes it

Fig. 29. (a) Scaffold specimen made from Bioglass, (b) application of scaffold to repair broken bone [73].
652 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667

Fig. 30. Different application of bioactive material in body with the corresponding porosity level [56].

Fig. 31. Photomicrograph of bone growth on (a) 50% crystallinity HA, (b) 75% crystallinity HA [76] *B ¼ bone, BM¼Bone marrow.

difficult to fabricate Bioglass by sintering [71]. Table 13

In the other hand, the application of Bioglass e which is Mechanical properties of HA and bone [78].

considered ceramics e is limited in load-bearing implants due to its Material Young's modulus, GPa UTS, MPa Fracture Toughness MPa.m1/2
brittleness and lack of mechanical properties (bending strength HA 80e120 40 0.6e1
and fatigue), Table 14 compares mechanical properties of Bioglass Cortical bone 1e20 50e150 10e12
with cortical bone [75]. Successful bioactive implants were re-
ported. The first successful clinical use of bioactive glass was in
1985 to treat damaged middle ear bones. The clinical studies treatment [67].
showed better performance than other bio-ceramics used. These As a conclusion, bioceramics are of high concern because of their
findings bring the potential use of bioactive glass in bones excellent biocompatibility, non-toxicity, wear and corrosion
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667
Fig. 32. SEM of Bioglass particles [80].
Fig. 33. Cell growth rate on different bioactive materials [67].
resistance. Also, bioactivity e which is offered by Bioglass and HA e
is a promising behavior that improve the performance of implants
and enhance fixation. However, these materials are poor in
ductility, fatigue and fracture toughness which limits their usage in
load-bearing implants. Form the experience of the authors, syn-
thetic HA nano-powder is cheaper than 45S5 Bioglass, neverthe-
less, 45S5 Bioglass exhibit better cell growth and higher stability
during fabrication as stated above.
653
Fig. 34. SEM image showing bone formation around Bioglass particles [67].
Table 14
Mechanical properties of Bioglass 45S5 compared to cortical bones [68].
Material Young's modulus, UTS, MPa Fracture Toughness,
GPa MPa.m1/2
Bioglass 45S5 35 42 0.7e1.1
Cortical bone 1e20 50e150 10e12
5. Techniques to improve the performance of biomedical
implants
Numerous researches focused on improving the performance
and durability (nowadays an average 10e15 years lifetime) of
biomedical implants [37]. In case of metals, the poor bioactivity and
the release of toxic ions in the human body are the main challenges
facing metallic implants. The poor bioactivity result in poor fixation
of implant with the bones which may need revision surgery. Also,
the rapid bio-corrosion of metals cause release of toxic elements
that has severe adverse effect on the health [59,78]. To overcome
this problem, surface treatment techniques are used to improve the
chemical, mechanical and biological properties of the surface
interfaced with the living tissues. The surface treatment is of two
main categories; altering the chemical and microstructure of the
surface, or applying coating material on the surface.
The first category includes techniques to modify the chemical
composition of the surface e as carbonization of steels e or modify
the surface microstructure, or applying both. These modifications
affect the wettability, surface charge, and hydrophobicity. These
properties showed effect on organic adsorption into the implant
surface. Generally, increasing the hydrophobicity of the surface
result in better biocompatibility [82].
S. Muley et al. evaluated the biological performance of 316L
stainless steel by developing ultra-fine grains at the surface. By
decreasing the grain size e form 30 mme0.86 mm e the hardness
was almost doubled (from 172 VHN to 300 VHN), the wear and
pitting corrosion resistance increased, and improved localized
corrosion resistance [23]. X. Zhao et al. introduced surface nano-
topographic with chemical modification. The author developed
nanotopographic layer of TiO2 doped with Nb2O3 on CP-Ti. They
realized enhancement in corrosion resistance, bonding strength
and biocompatibility [83].
Other approaches include developing composite materials
(metal-ceramic-matrix) as 45S5 Bioglass-316L fiber composite. This
approach depends on developing scaffolds using bioceramics and
654 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667
Fig. 35. PVD magnetron-sputtering setup [59].
Fig. 36. Tantalum oxide TaO coating layer developed on Ti6Al4V by PVD [60].
reinforced with 316L fibers to improve the bending strength, fa-
tigue strength, and fracture toughness [77].
The second category is coating techniques. Coating techniques
have become promising due to the combination of the superior
properties of both metals and bioactive materials. The bioactive
coating enhances the implant fixation and results in reduced me-
chanical failure (for fully HA coated implants the mechanical failure
ranges from 1% to 6.9% which is much lower than cement type
fixation) [1], prevent further ion-release form the metallic sub-
strate, and prevent formation of fibrous tissue which may result
from micro-movements of uncoated implant. Wide range of
coating techniques introduced, but till now an optimal technique
has not been developed yet [84]. The researchers presented vast
coating techniques as physical vapor deposition (PVD), plasma
spray, laser cladding and solution based methods as sol-gel and
electrochemical deposition. However, plasma spraying still the only
approved method by US-FDA for applying bioactive coatings in
biomedical application [63].
A high quality coating should exhibit sufficient adhesion
strength (50 MPa approved by US-FDA) [63], high hardness of final
coat, excellent osseointegration and osseoconduction properties,
reduced cracks among the coating, and free of inclusions. Another
important feature is the degree of crystallinity which affect the
solubility of the bioactive coating in the human body [63]. Recently,
the research work is directed towards developing thin and uniform
bioactive coatings to reduce the fragments and debris produced
[85]. In this paper, we will focus on the coating techniques used to
improve the performance of biomedical implants.
5.1. Physical vapor deposition (PVD)
PVD techniques are based on vaporizing materials from the
source material e called target e to be deposited on the substrate.
PVD is divided into three categories; vacuum, ion spraying and
magnetron sputtering [86]. A vacuumed chamber incubates
charged substrate and target with positive and negative charge,
respectively using DC-power supply. Then the process utilizes gas
plasma (argon, neon) which is ionized by means of electric charges.
The sputtered ions hit the target causing evaporation, and free-
atoms are ejected from the surface which is deposited on the
substrate. Usually, magnets are used to accelerate the formation of
coatings [86]. Fig. 35 shows PVD magnetron-sputtering setup
layout. It is revealed that the substrate temperature affects the
quality of produced coating [59].
Numerous researches utilized PVD to coat Ti-alloy with bio-
ceramics to enhance the biocompatibility. PVD is featured as ver-
satile technique, developing high purity and dense coatings, Fig. 36
show dense Tantalum oxide TaO coating developed by PVD. Also, it
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667 655

Fig. 37. Nanotubular array on TiTaHf alloy [90].

Fig. 38. HA coating on nanotubular TiTaHf alloy [90].

exhibits excellent adhesion strength with the substrate, and can
deposit any material (metal, alloy, or compound) on the desired
substrate [87]. Another important advantage that PVD operates at
relatively low temperatures which leads to lower degradation of
the coating and substrate [88]. B. Rahmati et al. investigated the
post heat treatment to enhance the adhesion strength of previously
developed Tantalum oxide coating on Ti6Al4V using PVD
magnetron-sputtering technique. They concluded that higher
treatment temperature (500
C) enhance the adhesion strength
because of better penetration of Tantalum oxide into the substrate
[60]. So, this technique can deposit bioceramics on metallic
substrates.
WU Zhen-jun et al. presented biocomposite coating (HA/Al2O3)
on cp-Ti. The authors employed PVD to deposit Al on Ti, followed by
anodization process to develop Al2O3, and finally using electrode-
position to deposit HA coating. The results revealed that enhanced
adhesion strength obtained (21.3 MPa), and improved biocompat-
ibility [89]. Jeong et al. prepared HA coating on nanotubular TiTaHf
alloy, Fig. 37 shows the morphology of nanotubular array devel-
oped, using PVD. The authors presented great potential for HA
deposited on nanotubular surface as it will induce better bioactivity
and cell adhesion. This may result from the nano-features of the
coating on the surface, Fig. 38 shows the nano-feature of HA layer in
favor of nanotubular array previously developed on the surface
[90]. E. Mohseni et al. utilized PVD technique to develop multilayer
coating (Ti/TiN/HA) on Ti6Al4V. They studied the process parame-
ters on the adhesion strength, coefficient of friction, and surface
roughness. The results showed enhanced adhesion strength by
44.57% and surface roughness by 10.52% [91].
PVD is successful to develop bioactive coatings on metallic
substrate. Although PVD produces high dense, high purity and
excellent adhesion strength, PVD technique exhibits disadvantages
as expensive and time consuming process, and low crystalline
coating which leads to rapid dissolution of HA coating in the human
body [63]. Further studies needed to investigate the effect of PVD
parameters on the porosity and crystallinity of developed bioactive
coatings.
Brohede, U. et al. used PVD technique to develop gradient
crystalline TiO2 coating on pure Ti substrate, Fig. 39 shows the
developed coating. They evaluated the in-vitro bioactivity of the
developed and found that HA layer was formed on the crystalline
TiO2 coating after immersion in PBS for one week at 40
C, Fig. 40
shows formed HA layer on TiO2. The scratch test showed that
adhesion strength between the coating and the substrate was
greater than 1 GPa [92].
Many researches focused on PVD to deposit HA on metallic
substrate. However, to the extent knowledge of the authors, no
work was published concerning the deposition of Bioglass on
metallic substrate, which represent research gap in this area.
656 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667
Fig. 39. TEM image of the TiO2 coating on pure Ti [92].
Fig. 40. Formed HA layer on TiO2 after one week immersion at 40
C [92].
5.2. Sol-gel technique
The sol-gel technique is based on mixing different organic
precursors (that contains SiO2, CaO, P2O5) in aqueous medium to
prepare the “sol”, then the mixture is polycondensated to form
“gel” which can be further used for coating. The gel is deposited on
the substrate and subjected to sintering to form the final coating
layer [93]. The sintering temperature is considerably low (about
500
C) which is lower than other techniques used [63].
Sol-gel technique is simple technique which able to coat com-
plex geometry because of the gel state, produce high purity and
homogeneity coating, and provide excellent adhesion, as well as,
good corrosion resistance coating [94]. This technique can be used
to coat metallic substrates with bioactive materials.
5.2.1. Hydroxyapatite coating
Hydroxyapatite is sensitive to the high temperature and may
decomposes, so sol-gel technique is considered suitable for pro-
cessing and depositing HA as the sintering temperature is relatively
low. Number of research works employed sol-gel technique for
coating Ti-substrate with thin layer of HA [95] or functional graded
material (FGM) to improve the biocompatibility [96].
A. Stoch et al. deposited HA on Ti6Al4V using sol-gel technique.
Fig. 41. SEM morphology of sol-gel HA coating after immersion in PBS for 19 days [97].
The authors added animal gelatin to the sol to enhance the for-
mation of amorphous phase of HA and studied the pH effect of sol
on the final coating. The result showed the most favorable pH was
6.5e7.8 and the gelatin improved the stability of sol. The developed
HA coatings showed excellent in-vitro bioactivity which reflects the
success of the proposed technique, Fig. 41 shows the resulted
morphology after immersion in PBS for 19 days [97].
P. Choudhury et al. proposed pure HA and composite HA and
ZrO2 coatings on Ti by sol-gel. They concluded that pre-passivation
of Ti substrate increase the roughness which in turn enhance the
bonding strength of the coating. In addition, the composite coating
of HA and ZrO2 exhibited higher bonding strength. However, the
coatings are found to be worn by abrasion and delamination [98].
Not many researches focused on coating SS alloys with HA using
sol-gel technique. Dean-Mo Liu et al. investigated different sinter-
ing temperature levels effect on the coating properties of SS. The
results showed that at temperature greater than 400
C produce
better crystallinity, higher bonding strength (up to 44 MPa), and
nano pores, Fig. 42. However, the developed coating exhibited
surface micro-cracks and non-uniform thickness [99].
5.2.2. Bioglass coating
There is few researches considered Bioglass coatings using sol-
gel techniques. S. Pourhashem and A. Afshar prepared 45S5 Bio-
glass coating on 316L SS by sol-gel technique. The obtained coatings
were crack-free, Fig. 43, have good crystalline structure and
exhibited improved corrosion resistance. The results showed
bioactivity behavior and HA formation was realized on the surface
[100]. N. Shankhwar et al. developed new magnetic Bioglass by
adding iron oxide using sol-gel technique. The developed magne-
tite glass showed enhanced magnetic properties and in-vitro
behavior [101].
The sol-gel technique is featured as simple coating technique.
Also, it is suitable for complex shapes as the gel-nature can fill gaps,
exhibits relatively low sintering temperature, and produce thin
layers of coating. In the other hand, sol-gel has limitations as
cracking, low wear resistance, and high permeability. The sol-gel
technique is sensitive to the substrate material as the difference
in thermal properties between the coating and the substrate which
cause delamination of coating and hence, process failure [94].
Hence, further research is needed to overcome major drawbacks as
poor adhesion strength, cracking, and low degree of crystallinity.
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667 657

5.3. Plasma spraying

Plasma spraying is the most common method deployed for

coating Ti with HA and the only approved e by US FDA e technique
for biomedical application. The process involves melting material
powder using high temperature plasma gas (up to 15000
C). The
molten powder is sprayed over the surface and the coating is
developed. Fig. 44 shows the principle of plasma spraying tech-
nique [63].
Plasm spraying is low cost technique and has rapid deposition
rate as well as reduced thermal degradation than other thermal
techniques. However, plasma spraying still lacks to offer high
adhesion strength, cracks [102] and may induce microstructure
changes in the developed coating [63].

5.3.1. Hydroxyapatite coating

Recently, many researchers focused on coating metallic sub-
Fig. 42. Nano pores at the surface of HA layer [99].
strate with HA using Plasma spraying technique as it is approved by
FDA. Kulpetchdara et al. employed plasma thermal spraying in
coating SS substrate with nanostructured HA for hip joint implant.
The authors used commercial and synthesized nano-sized HA, and
compared the resulting microstructure (Fig. 45), hardness and
bioactivity. The nanostructured HA exhibits higher hardness (VHN
2.15 GPa compared to VHN 1.06 GPa for commercial HA), higher
degree of crystallinity, and excellent osseoconductive which can
replace the conventional HA in prosthetic applications [103].
The bonding strength of plasma sprayed HA coating with
Ti6Al4V is a weak point. M.J. Filiaggi et al. proposed post heat
treatment of plasma sprayed HA coatings. The results showed
dramatically increase in mechanical properties e bonding strength
up to 40 MPa and fracture toughness reaching 3 MPa m1/2. How-
ever, the chemical composition of the coating was changed which
affected the bioactivity of HA coating [104].
Manoj Mittal et al. investigated the corrosion behavior of HA
coated 316L SS and Ti, and compared the results with the uncoated
ones. The authors used plasma spray to deposit HA on SS and Ti
substrate. The results showed that certain decomposition of HA
took place, as well as micro-cracks on the surface, and porosities,
Fig. 46 shows the induced micro-cracks and porosities in HA
coating on SS and Ti. The electrochemical test showed enhanced
corrosion resistance of coated samples. In addition, the HA coated
Ti showed better results than HA coated 316L SS which reveal the
Fig. 43. SEM of Bioglass coating on 316L SS.
effect of the substrate material [105]. Y. Wang et al. studied HA

Fig. 44. Plasma spray method [63].

658 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667

Fig. 45. SEM of plasma sprayed (a) commercial HA coating, (b) synthesized nano-sized HA coating [103].

Fig. 46. Micro-cracks and porosities included in HA coating on (a) 316L SS, (b) Ti [105].

coatings on Ti using micro-plasma spraying. The results showed

improved crystallography and higher crystallinity than atmo-
spheric plasma spraying. The in-vitro tests showed higher HA sta-
bility in Hank's solution for 14 day [106]. V. Shamray et al. proposed
preheated substrate to promote the HA coating using plasma spray.
The authors noticed that the composition and structure of the final
coating has been affected. The surface of coating appears to have
flattened splats which is formed from molten particles as shown in
Fig. 47 [107].
Generally, plasma spraying is an effective technique for depos-
iting HA on metallic substrate, but exhibit poor crystallinity reduce
the lifetime of the coated implants which needs further in-
vestigations and improvements [102].

5.3.2. Bioglass coating

Although the studies reported excellent biocompatibility and
bioactivity behavior of Bioglass, few researches considered Bioglass
coating using plasma spraying technique. This is because of the
poor adhesion of Bioglass to the substrate. This can be solved by Fig. 47. SEM of HA coating on preheated Ti to 300
C.
increasing the surface roughness of the substrate, developing Bio-
glass/metallic composite, introduce interlayer as bond coat and in
situ plasma spraying. The in-situ plasma spraying involves pre- obtain the powder. However, these techniques need more investi-
paring suspension containing the raw materials of Bioglass which is gation to validate the bioactivity of the resulting coatings [108].
dry sprayed, pressed and sintered. The sintered material is milled to L. Altomare et al. used high velocity suspension flame spraying
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667
Fig. 48. Apatite formation on Bioglass surface after immersion in SBF for 1 week [109].
Fig. 49. SEM image of the coating layers on Ti (A) Ti-substrate, (B) 60Al2O3 40TiO2
interlayer, (C) Bioglass layer [110].
Fig. 50. Laser cladding process using (a) by gravity [117], (b) injected powder [118], (c) preplaced powder [119].
659
to deposit Bioglass e dispersed in aqueous-isopropanol mixture -
on grade Ti. The authors deposited multilayer of Bioglass to obtain
denser and thicker layers. The results showed full-glassy structure
of the coating and excellent in vitro bioactivity behavior, Fig. 48
shows formed apatite on crystalline Bioglass coating [109].
In another approach, G. Goller et al. utilized 60Al2O3 40TiO2 as
interlayer in plasma spraying Bioglass on Ti, Fig. 49 shows the
interlayer and Bioglass layer deposited on Ti-substrate. The
resulting bond strength increased three-times (on average
27.18 MPa) compared to the bonding strength obtained without
interlayer (on average 8.56 MPa). The tests revealed no reaction
took place at the interface [110].
5.4. Laser cladding technology (LCT)
Laser is a promising technique in various applications. Recently,
laser was successfully employed in welding dissimilar materials
[38], surface melting and treatment [111], metal additive
manufacturing [112] and prototyping [113], and coating processes
[114]. Laser techniques found wide applications in different in-
dustries; aerospace, marine, oil and gas, and biomedical
applications.
Laser cladding technique was developed to deposit coating
material on substrate using laser energy. The coating material is
usually in powder form which may be preplaced [115] over the
substrate surface or injected under pressure [65] or gravity [116].
Laser beam melts the powder e the process involves rapid heating
and cooling e and creates melt pool without melting the substrate.
As the laser scans the surface, the pool solidifies building a firm and
dense coating on the surface. Fig. 50 illustrates methods used in
laser cladding.
Laser cladding (LCT) is a promising technique because it pro-
duces full-dense coatings with outstanding properties [120], forms
strong metallurgical bond between substrate and coating [121],
able to deposit ceramics or metals on metallic substrate [122], and
leads to reduced heat affected zone (HAZ), Fig. 51 shows different
zone induced at cladding area [119]. Also, it provides controlled
shape of the coating, flexible process, controlled degree of dilution,
low surface roughness with high deposition rate, and requires
minimum surface preparations [123].
LCT offers metallurgical bonding between coating and substrate,
as well as, excellent full-dense coating layer. Different works
investigated coating Ti-alloys and SS e as the most common alloys
used in implants e with different bioactive materials as HA and
Bioglass to enhance the corrosion resistance, besides the bioactivity
behavior.
660 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667

5.4.1. Hydroxyapatite coating

Fig. 51. Cross-section of single laser cladded bead showing substrate, HAZ, and clad-
ded bead [119].
Fig. 52. Coated Ti with FG CNT/HA composite [74].
Many studies done to enhance the microstructure of the coating
and improve the bonding strength. These improvements were
attained by developing functionally graded carbon nano-tubes
(CNT) with HA composite coating. The coating consisted of three
layers: bottom layer (5% CNT), intermediate layer (3% CNT), and top
layer (pure HA), Fig. 52 shows the coating layers and it is noted no
existence of separation between layers. X. Pei et al. found that CNT
increased the crystallinity of HA coating and bonding strength from
14.6 to 29 MPa, besides the excellent bioactivity as shown in Fig. 53
[74].
Y. Yang proved that addition of SiO2 to HA enhance the crys-
tallinity, reduce cracking and exhibited better wettability than pure
HA. The HA doped with SiO2 coating showed 14.5% increase in bone
in-growth, Fig. 54 compares the SiO2-HA coating with pure HA [70].
The application of self-fluxing alloys e alloys containing Al and Si e
result in sound and crack-free coatings. The Al and Si oxidize during
laser cladding process, float at the surface, and protect the coating.
These self-fluxing additions minimize the oxidation of the sub-
strate and the clad which may affect the bioactivity of the implant
[124].
Not many studies focused on coating SS with bioactive materials
using laser cladding technique. Q. Wei studied the selective laser
melting of SS/nHA composite implant to offer uniform metallur-
gical bonding of metal and ceramics. The nano-HA powder showed
better bioactivity performance [125]. They reported that increasing
the laser scanning speed decreases the degree of cracks [126]. Fathi
et al. investigated the coating of 316L SS with pure HA, pure Ti, and
double-layer coating of Ti and HA. The double-layer showed posi-
tive improvement in corrosion resistance behavior compared to the
other specimen [127]. M. R. Mansur et al. proposed composite
coating of HA and TI6Al4V on SS. The study revealed that Ti diffused
into the substrate in the heat affected zone. At the top layer, Ca/P
ratio was 1.66 which is near to the human bone composition. They
found that the suitable energy density of laser was below 167 J/
mm2 [22].
Functionally graded materials (FMGs) approach was proposed
because the HA coating deteriorates during working period due to
poor interface bonding. This method reduces the dilution rate of HA
and reduces the cracking possibilities. M. A. Hussain proposed a
hybrid mixture of HA, 316L SS and CNT to build FGMs, Fig. 55 shows
SEM morphology of the resulting coating layer. The HA powder was
50% micro-sized and 50% nano-sized to increase the density of the
HA. The proposed coatings showed increased hardness and
enhanced mechanical properties [128].

Fig. 53. SEM image of (a) pure HA, (b) FG CNT/HA composite after 7 days of cell-culture [74].
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667
Fig. 54. SEM and EDX of (a) pure HA, (b) 25% Si-HA [70].
Fig. 55. HA/316L SS composite coating layer (white particles are 316L SS and grey color
is HA) [128].
Li H. C. et al. investigated the usage of CaO-SiO2 as coatings on
Ti6Al4V and the effect of addition of CeO2 and Y2O3. The addition of
rare earth oxides refined the microstructure, reduced the loss of
weight, and increased the bonding strength between coating and
substrate, and improved the degradability of the sample [9,69]. In
cladding process using bioactive ceramic, CaO is formed which is
considered toxic for osseoblast. To reduce the CaO content, 5 mol%
ZrO2 was added. It was noticed the formation of CaZrO3 and the CaO
phase disappears [129].
661
M. Mansur et al. proposed HA and Ti6Al4V composite coating to
obtain stable HA coating. The resulted coating showed better
adhesion as well as more stable HA. The analysis of the coating
showed Ca/P was 1.67 which is exactly the same of human bone
composition [130].
5.4.2. Bioglass
When cladding HA on metallic substrate using LCT, the high
temperature levels cause the decomposition of the HA (above
1300
C) [56]. This problem causes lower bioactivity of the devel-
oped HA coating. Bioactive glass 45S5 and S520 proved higher
stability than HA at high temperatures [11,131]. The simulated body
fluid test showed that bioactive glass S520 is more appropriate than
45S5 in laser cladding rapid prototyping [80].
Bioactive glass S520 was successfully cladded on Ti substrate
using LCT. It is noticed that preheating the substrate reduced
cracking in the coating layer and reduced the laser power. The
preheating of the substrate reduces the cooling rate which improve
the cracking resistance. M. Krzyzanowoski et al. found that conse-
quent layers of bioactive glass induce less cracking tendency [132].
R. Comenana et al. showed that bioactive glass S520 is most
suitable to clad Ti6Al4V by LCT as the bioactive glass S520 showed
less tendency to cracking than 45S5, and have higher bulk strength
(S520 was 355 MPa, while 45S5 was 302 MPa). They found that
higher surface roughness enhances adhesion with bones. Forma-
tion of TiP enhanced the coating adhesion with the substrate [123].
N. Moritz et al. proposed non-uniform bioactive glass multilayer
coating. The coating was droplets of bioactive glass on local points
as shown in Fig. 56, which interface with bones, and sufficiently
adhered to the substrate. This coating technique reduced the
662 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667
Fig. 56. Proposed droplets of Bioglass coating [6].
stresses and resulted in crack-free coating. The laser power was
reduced by 30% in the successive layers [6].
5.4.3. New approaches of cladding bioactive material on metallic
implants
LCT provides in situ fabrication of bioactive coating on metallic
substrate. This approach lead to better controlled composition,
microstructure and enhanced adhesion. D. Wang et al. proposed in
situ prepared CaP coating on pure Ti. The authors investigated the
addition of pure yttria (Y2O3) to improve the mechanical properties,
and sodium silicate (Na2SiO3) as adhesion enhancer. The tensile
strength of the clad coating reached 68 MPa [9]. The same author
proposed in situ prepared HA coating using calcium carbonate
(20 wt %) and calcium hydrogen phosphate (80 wt %) powders. To
improve the bonding between coating and substrate, transitional
layer of 50 wt % Ti with 50 wt % of the above mixture powders was
first layered [131,133].
Dongjiang Wu et al. proposed ultrasonic assisted laser cladding
process of yttria stabilized zirconia to modify the microstructure
and control dilution characteristics. The dilution rate between the
substrate and coating increased (53.09%) when ultrasonic vibration
is applied. While the dilution rate was 37.37% for laser cladding
without ultrasonic applied. The utilization of ultrasonic vibration
increase the clad depth, improve coating microstructure, enhance
linear element transition, and increase the dilution rate that affect
the bonding strength [134].
As a conclusion LCT is promising technique for coating metals
with bioactive materials. LCT provide metallurgical bond, create
full-dense coating, reduced HAZ and is cost-effective process.
However, LCT has many drawbacks and further studies are needed
to overcome them. LCT involves formation of porosity in clad which
reduces the strength of the structure [121]. Also, cracking and
delamination of coating may take place due to thermal expansion
difference between coating and substrate [122]. The process
parameters should be carefully chosen to overcome the decom-
position of bioceramics (as HA) due to high temperature induced,
besides to increase the crystallinity of the developed coating [66].
5.5. Plasma electrolytic oxidation (PEO)
Plasma electrolytic oxidation (PEO) - also known as micro-arc
oxidation - is a relatively convenient technique for producing a
micro-porous, rough and hard coatings on light materials such as
Al, Ti, Zr, Mg, Ta and their alloys [135]. The PEO technique has been
gaining an increasing interest recently as it could provide superior
adhesion between the coatings and the substrate and formation of
high crystalline coatings with porous surface morphologies
[136,137]. Moreover, the PEO process is a low cost, simple to
operate, eco-friendly and versatile [138]. The coatings produced by
this technique can possess a wide thickness range, providing an
effective wear and corrosion protection to the light materials. With
this technique, protective as well as multifunctional coatings can be
produced by adjusting the process parameters. PEO treatments are
usually carried out in apparatus composed of a conventional elec-
trolytic cell and power supply with high voltage output [139].
In a typical PEO process, coatings are deposited onto light ma-
terials from an aqueous electrolyte by applying high voltage/cur-
rent between the anode (light materials) and the cathode (usually
stainless steel of larger area). The electrolyte dissolves in water
dissociates to form anions and cations. Owing to a high electric field
between the electrodes, anions and cations migrate towards the
anode and cathode respectively. At the anode, the oxidation of the
sample begins by forming an insulating layer on the anodic surface,
Fig. 57 shows typical apparatus used for PEO process. With further
increase in the applied voltage, the current is forced to pass through
the coating. Subsequently, the high intense electric field is gener-
ated around the samples, thereby resulting in micro-arc discharges
on the entire surface immersed in the electrolyte solution. The
ensuing micro-arc discharge event produce high temperature,
which assist the oxide layer to be sintered and further incorpora-
tion of elements from the electrolyte solution. The coating is
deposited across the whole surface immersed in the solution
without altering the bulk properties [138].
The PEO process and the final coating characteristics are highly
dependent on several factors, including the electrolyte composi-
tion/concentration, substrate materials, electrical parameters
(voltage and time) and geometry of the electrolytic cell [139]. It
should be borne in mind that these factors are essentially inter-
dependent making the process quite complex.
5.5.1. PEO coatings derived HA coatings
Before 1995, the available reports on the PEO coatings are
majorly concerned with producing highly adherent oxide ceramic
coatings with different chemical compositions on Al and Mg for
anti-corrosion and anti-friction applications [140]. The application
of PEO has been recently expanded into the biomedical area due to
its micro-porous and adherent layer formation on the metallic
substrate. Ishizawa et al. [141,142] were the first research group to
make use of PEO process for the preparation of HA layer on titanium
substrate. But unfortunately they are not successful using only PEO
process. The entrance mechanism of Ca and P ions into oxide film
and preparation of HA via PEO process on the light material sub-
strates have been considered as a difficult and complex. Generally,
PEO process is considered as a multifactor controlled process and
these factors have direct influence on the quality, structure and
composition of PEO coatings [143].
The process where HA is directly produced using PEO technique
without the need of subsequent treatment is called single stage
process. The formation of HA over the oxide layer produced via PEO
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667 663

Fig. 57. Micro-arc oxidation technique setup.

process is possible using long treatment time and voltage. Durdu

et al. demonstrated that by increasing the deposition time, the
coating thickness ranging from 16 to 63 mm and the average pore
sizes of 1e20 mm can be obtained (Fig. 58). The increased in coating
thickness and pore size was attributed to variation in deposition
time [144].
Deposition at high voltage and time improved the surface
roughness, porous structure and HA crystallinity of PEO coating.
However, the incorporation of HA which was accomplished using
high deposition time and voltage has some limitations. When
increasing the amount of HA in the oxide film by increasing either
voltage or time, cracks were generated and failure within the
coating followed (Fig. 58e). Moreover, the obtained HA produced
was often not a single phase but contained by-products such as TiP2
[144], CaTiO3, CaO or Ca3(PO4)2 [145,146].
To increase crystallinity of the films, further treatment using
hydrothermal treatment (HT) or by immersion in simulated body
fluid (SBF) is held. It is a known fact that HA could be grown directly
over the obtained TiO2 layers using PEO process, but the growth
rate is usually very low and the amount of HA is small. Generally,
HA produced by PEO treatment is usually of low crystallinity and
the coated amorphous is not as stable and bioactive as crystalline
HA [147]. Owing to this, further hydrothermal treatment is usually
carried out to transform amorphous calcium phosphate to the
crystalline HA. When HT is applied after PEO treatment, the Ca2þ
and PO34 ions from internal layer of amorphous coating can suc-
cessfully diffuse to the coating surface and dissolve into the solu-
tion during HT and finally precipitate on the outer layer with higher
degree of crystallinity. The hydrothermal treatment is performed
by placing the PEO coated samples in the bottom of autoclave or in
pressure controlled reactors containing neutral or alkaline aqueous
solution and treated hydrothermally within the temperature range
of 100e250
C for 2e24 h at pH 7e11 [148,149]. Fig. 59 reveals the
surface morphologies of the as-prepared TiO2 films after pre-
immersion in 0.1, 1, and 2 M K2HPO4 for 10 min and then soaking
in SBF solutions for 1, 2, 4, and 9 days [150].
The micrographs of the obtained coatings show the existence of
the HA with a thickness layer of about 0.6 mm after immersion in Fig. 58. Surface morphologies of PEO coatings: (a) 1 min, (b) 5 min, (c) 10 min, (d)
SBF. It was shown that simple pre-immersion of oxide layer in 20 min, (e) 40 min, (f) 60 min and (g) 120 min [144].
2 M K2HPO4 solution assisted the growth and nucleation of HA after
soaking in SBF solution for less than 1 day. The content of HA
increased with increasing the soaking time. The growth of HA after oxide film and adsorbent of HPO24 groups on the oxide surface.
pre-immersion in K2HPO4 solutions was attributed to the porous However, the process for obtaining HA over TiO2 is cumbersome
664 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667
Fig. 59. Surface morphologies of the PEO-produced TiO2 films and those after pre-immersing in 0.1, 1, and 2 M K2HPO4 for 10 min and then soaking in SBF solutions for 1, 2, 4, and 9
days at 36:5 ± 0:5
C [150].
and time consuming and moreover, the hydrothermal treatment of
PEO layer reduces the interfacial bonding strength because of
introduction of additional phase [142].
At the current stage of our knowledge, it is difficult to draw a
conclusion on the applicability of PEO to produce hydroxyapatite
coating without introduction of subsequent treatment. Moreover,
PEO technique results in formation of porosities which may lead to
corrosion and delamination of the coating because of the pene-
tration of the body fluids. In addition, this technique is not suitable
to coat bioactive materials on SS or Co-alloy substrate. So, further
treatments are needed to densify the coating which in turn may
lead to cracks. These cracks reduce the lifetime and durability of
implant [151].
6. Conclusion
There is wide variety of metallic biomaterials introduced. Ti, Co
and SS alloys are the most popular alloys used in biomedical im-
plants due to their excellent mechanical behavior. Nickel-free SS
show promising potential in bone-implants with improved me-
chanical and biocompatibility properties.
Recently, the researchers considered the BMG alloys in
biomedical applications because of their superior wear, corrosion
and biocompatibility especially, Fe, Zr and Ti-based BMG. However,
the lack in fatigue properties and limitations to fabricate in large
sizes are the main challenges for application of BMG in bone-
implants.
The metallic alloys failed to show bioactivity properties and to
sustain their mechanical properties in corrosive media, which
result in reduced durability. In addition, the studies reported haz-
ardous ion release from some metallic alloys when implanted in
human body.
In the other side, bioceramics proved superior bioactivity and
biocompatibility properties, as well as corrosion resistance. The
studies reported the excellent osseointegration and osseo-
conduction which promotes the healing of fractured and damaged
bones. The discovery of HA and Bioglass was breakthrough in the
biomedical industry and they are the most common used. However,
the bioceramics exhibited poor mechanical properties and brittle-
ness which limits their application in load bearing implants.
Many techniques have been developed to coat metallic substrate
with bioactive materials to combine the mechanical properties of
metallic alloys and bioactivity of HA and Bioglass, besides pre-
venting further ion release of hazardous elements. The techniques
covered in this review are plasma spraying, sol-gel coating, PVD,
micro-arc oxidation, and laser cladding.
Currently, only plasma sprayed HA coating is approved by FDA
and further researches are needed to improve the properties of
resulted coatings by different techniques which may offer better
adhesion or higher stability for the coating. The research trend is to
present improved performance and durability of biomedical im-
plants as the current technique still lack to meet these objectives.
7. Research gap
Recently, many research works focused on developing materials
for bone-implants with longer life-span (more than 25 years). More
studies and investigations should consider new developed alloys as
Ni-free SS and new Ti-alloys as TiAlNb which offer lower ion release
and less hazardous effect. Also, more studies and investigations are
needed to improve the toxicity and biocompatibility of Co-alloys.
The current implants life is 20e25 years and the objective is to
reach 40 years to minimize the revision surgeries. However, the
coating techniques were presented, are still lack meeting higher
life-span because the lack in improved adhesion strength. The
improvement in adhesion strength will enhance the durability and
will overcome the problems of coating separation and lamination
during implanting process. More studies should focus on depos-
iting Bioglass on metallic substrate using different techniques as
Bioglass exhibited promising potential in biomedical applications.
Also, composite HA/Bioglass coating needs more investigation to
obtain more stable coatings.
A new trend is to develop coatings from BMG on conventional
used metallic bone-implants to enhance the wear and corrosion
resistance. However, BMGs need more investigations to stabilize
their amorphous phase after post processing of the coating.
 M.Z. Ibrahim et al. / Journal of Alloys and Compounds 714 (2017) 636e667
Acknowledgment
The authors would like to acknowledge King Fahd University of
Petroleum and Minerals (Saudi Arabia) and University of Malaya
(Malaysia) for providing the necessary facilities and resources for
this research. This research was funded by Nippon Sheet Glass
Foundation (Japan) and University of Malaya Postgraduate
Research Grant (PPP) Program No. PG057-2016A (Malaysia).
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