Materials Technology

Advanced Performance Materials

ISSN: 1066-7857 (Print) 1753-5557 (Online) Journal homepage: http://www.tandfonline.com/loi/ymte20

Surface modification of metallic biomaterials for

enhanced functionality: a review

A. Mahajan & S. S. Sidhu

To cite this article: A. Mahajan & S. S. Sidhu (2017): Surface modification of metallic biomaterials
for enhanced functionality: a review, Materials Technology, DOI: 10.1080/10667857.2017.1377971

To link to this article: http://dx.doi.org/10.1080/10667857.2017.1377971

Published online: 21 Sep 2017.

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 Materials Technology, 2017
https://doi.org/10.1080/10667857.2017.1377971

Surface modification of metallic biomaterials for enhanced functionality: a

review
A. Mahajana,b and S. S. Sidhuc
a
Department of Mechanical Engineering, IKGPTU, Kapurthala, India; bDepartment of Mechanical Engineering, Khalsa College of Engineering
& Technology, Amritsar, India; cDepartment of Mechanical Engineering, Beant College of Engineering & Technology, Gurdaspur, India

ABSTRACT ARTICLE HISTORY

Surface modifications of biomaterials play a vital role in matching the complexities of the Received 4 April 2017
biological system and improving the performance of bioimplants. Suitably customised surface Accepted 6 September 2017
modifications can substantially enhance the relation of material towards biocompatibility, KEYWORDS
bondability and host cells associations. In addition, materials surface engineering accelerates Biomaterials; surface
the progression and configuration of next-generation biomaterials and restorative gadgets.
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modification; electrical
This review article dedicates to the surface modification techniques of several essential metallic discharge machining
biomaterials, viz. stainless steel, magnesium, titanium and chromium–cobalt. It presents the
unique novel futuristic method of surface modification via electrical discharge machining (EDM)
process which still awaits to prove its potential in the biomedical domain. Previously established
research work on this nonconventional machining process elucidates that an adequate surface
integrity can be achieved by control of crucial EDM process parameters such as pulse on, pulse
off, current, polarity, dielectric medium and tool electrodes. Therefore, there is ample scope for
the EDM process in examining the issues related to the synthesis and precise shaping of the
bioimplants.

Introduction The twenty first-century science observed research

Biomedical is an area in which biomaterial applications
hold extreme significance in clinical medicine, ortho-
paedic surgeries and material science [1]. Biomaterials
are an artificial content that is implanted into living
organisms to substitute body organs for fulfilling typical
functionalities of the whole body for an extended span
of time or even for the entire life [2]. As such, these must
be nontoxic, non-cancerous, synthetically dormant, sta-
ble, and mechanically sufficiently solid to withstand the
rehashed strengths for the lifetime [3]. It is rare to find
the material that satisfies all the requirements suitable for
human body environment. Hence, researchers attempt
to combine the properties of various materials to cope
with these challenges. Often, surface engineering offers
the key phenomenon that renders a most important
alternative to deal with these surface-related problems
such as wear, toxicity and corrosions.
Based on the structural, chemical and biological
characteristics, biomaterials can be broadly classified
into various types such as ceramics, glasses, metallic,
polymeric and composite systems each with a varied
degree of bioactivity. Some typical implant biomaterials
are pictured in Figure 1.
on biomaterials drastically incriminating the collabo-
ration between therapeutic science, materials science,
biochemistry, biomedical engineering and clinical sci-
ence. The restoration of long bones and tissues pro-
motes the growth of metallic implants in living beings.
In the 1860s, the endeavours of implanting metallic
products like iron, gold or silver spinal wires and bone
pins were rejected by the body and cause severe infec-
tion after implantation. During that time, the Scottish
surgeon, Lister, anticipated and initiated the aseptic
surgical strategy in which carbolic acid was utilised
as an antiseptic to get rid of infections [4]. Later on,
metallic materials continued to prevail in orthopaedic
surgery, temporary devices (bone plates, hooks, and
screws), long lasting implants (e.g. total combined
replacements), dental and orthopaedic practice [5,6].
Recently, Melbourne-based medical device company
CSIRO successfully implanted 3D printed titanium
sternum and rib cage in the cancer patient suffering
from chest wall sarcoma (Figure 1(d)) [7].
It is evident that the metallic implants are directly
associated with the human body performance (i.e.
mechanical properties) and biological reactions (i.e.
biocompatibility) in the host. Thus, for overall health, it
is extremely important to maintain the balance between

CONTACT  S. S. Sidhu  sarabjeetsidhu@yahoo.com  Department of Mechanical Engineering, Beant College of Engineering &
Technology, Gurdaspur 143521, India.
© 2017 Informa UK Limited, trading as Taylor & Francis Group
 2   A. MAHAJAN AND S. SINGH SIDHU
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Figure 1. Some applications of biomaterial in different biological systems (a) Artificial Knee joint comprises metallic (Ti or Co–Cr
alloys) and UHMW polymer component (b) Hip joint comprises metallic, polymers and high wear resistant ceramic component (c)
Mesh type stent for coronary artery and (d) 3D printed sternum and rib cage of titanium alloy[5,7].

Table 1. Parameters considered for selection of biomaterials.

Properties Explanation
Biocompatibility • It is the capability of biomaterial that comes in contact with organs, tissues without creating any unwanted degree of
damage to the body [93].
• Biomaterial should have excellent biocompatibility (non toxic).

Corrosion resistance • Corrosive body fluid in a human body causes corrosion to metallic implants [94].
• Corrosion resistance should be high.

Mechanical properties • A mechanical property such as Young’s modulus; ultimate tensile strength and toughness should be properly examined for
selection of biomaterial.
• Some important mechanical properties of metallic materials implants are illustrated in Table-2.

Wear resistance • It is erosion of material from the surface due to interaction between surfaces.
• Wear resistance and coefficient of friction of the implant should be high [95,96].

Osseo-integration • Development of integration between an implant and bone without intercede the delicate tissue [97].
• For great Osseo-integration, the aspects such as surface science, surface unpleasantness and surface geography are the
significant factor [69,98,99].

the bulk and the surface properties of the biomaterials. Metallic biomaterials and surface engineering
Significant parameters that need to be considered for
Till date, researchers in the area of metallic and non-me-
selection of biomaterials are listed in Table 1.
tallic biomaterials have done a lot of work. This article
Some important mechanical properties of metallic
highlights the surface treatments of routinely applied
bioimplant materials and natural bone are shown in
metallic biomaterials such as stainless steel, magnesium,
Table 2.
titanium, and chromium–cobalt. Surface biocompati-
This article reviews surface modification techniques
bility can be achieved by either changing the surface
employed on some of the most dominating implanting
chemical composition or enhancing physical properties
materials such as stainless, magnesium, titanium and
or coating the parental materials with different materials.
cobalt–chromium. The advantage of electrical discharge
Figure 2 shows some of the important factors that are
machining (EDM) process on surface modifications
needed to reconcile for the biological and mechanical
also highlighted the futuristic aspects in the biological
challenges in tissue engineering. In this section, various
domain.
 MATERIALS TECHNOLOGY   3

Table 2. Mechanical properties of metallic implant materials and natural bone [100].
Mechanical properties Stainless steel Ti alloy Mg alloy Co–Cr Natural bone
Modulus elasticity (GPa) 190 110 44 210 3–20
Yield strength (MPa) 331 485 162 448–648 77–114
Tensile strength (MPa) √ 586 760 250 951–1220 42–109
Fracture toughness (MPa m ) ̴100 ̴80 15–40 ̴100 2–12
Density (g/cm3) 7·9 4·5 1·84 9·2 1·8–2·1
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Figure 2. Some of the important characteristics contributing the outcome of a bioimplants.

Table 3. Classifications of stainless steels and typical medical applications [5].

Material type Application grade Examples
Martensitic Dental and surgical instruments Bone curettes, chisels and gouges, dental burs, dental chisels, cu-
rettes, explorers, root elevators and scalers, forceps, haemostats,
retractors, orthodontic pliers, and scalpels
Ferritic Very limited surgical instruments Solid handles for instruments, guide pins, and fasteners
Austenitic Large number of non-implantable medical devices. Many short- Canulae, dental impression trays, guide pins, hollowware, hypo-
term implants Total hip replacements dermic needles, steam sterilisers, storage cabinets and work
surfaces, and thoracic retractors
Duplex Not yet applied in the biomedical field

modification techniques on the surface of these bioma-
terials are delineated in the following sections.
Stainless steel
In 1920s, 316L stainless steel became a candidate implant
material that has good mechanical properties and
numerous applications such as healthcare products. Now
the studies have revealed that 70% of Orthinox stainless
steel is utilised for hip substitutions in U.S. [8]. It is an
iron-based alloy containing 11–30% wt of chromium
and undefined amount of nickel [9].
Stainless-steel metals are mainly classified into four
main categories: Martensitic (BCT-hardest crystal struc-
ture), ferrite (BCC crystal structure), austenite (FCC
crystal structure) and duplex (austenitic (FCC) plus-
ferrite (BCC) phase), which are represented in Table 3.
Except for duplex, the other three categories of stain-
less steel confirm importance in medical equipment
and are commonly utilised for implantation applica-
tions. The utility of stainless steel is attributing to (a) its
availability (b) low cost, (c) excellent manufacturing (d)
good biocompatibility (e) toughness and (f) excellent
corrosion resistance [9]. However, the main limitation
of stainless steel is associated with fissure and fretting
corrosion due to the damage of the defensive chromium
oxide surface film [10]. It is observed that often stain-
less steel causes undesirable biological reactions in the
human body when appropriate surface treatment is not
actuated [11,12]. As opposed to the surface treatment
 4   A. MAHAJAN AND S. SINGH SIDHU
of metals like titanium, aluminium, gold, silicon-based
materials and polymers, the investigation related to the
surface modification of stainless steel is fewer [13]. As
such, it is essential to analyze the surface moderation of
stainless steel to acquire improved surface engineering
via chemical balance, mechanical properties, corrosion
resistance, blood interface and longevity [14,15]. Liu
et al. [16] exploited the water-based sol–gel technique
for the deposition of thin hydroxyapatite film on rough
316L stainless-steel specimen. It was witnessed that the
presence of microcracks reduces the interfacial bonding
strength of the film but still the adhesion of this coat-
ing was observed 40% more prominent than the plas-
ma-sprayed coatings.
Shih et al. [17] investigated the corrosion behav-
iour on the surface of 316L stainless steel wire used for
biomedical applications. They reported that the stain-
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less steel wire coated with an amorphous oxide layer
enhances the corrosion resistance as compared to the
electropolish-treated surface. To overcome this draw-
back of the electropolished process, Fattah et al. [18]
employed electrochemical pretreatment [ECPT] tech-
nique on 316L stainless steel in a non acid ionic liquid,
which improved the surface roughness of specimen.
Ionic liquid comprised ethylene glycol (EG) and vita-
min-B4 in the ratio 2:1. The researchers claimed that
the ECPT method at the current density of 0·14 A/cm2
and the voltage of 1·5 V reduced the roughness of 316L
SS specimen by 85%. Further, Latifi et al. [19] utilised
the electropolishing method combined with acid dip-
ping method for surface modification of 316L stainless
steel. This hybrid method (i.e. electropolishing method
coupled with acid dip treatment) provides homogenous,
super clean, very sleek, excellent quality and good cor-
rosion-resistant surface. The surface roughness of the
hybrid specimens was reduced by more than fifty-fold
as compared to the utilisation of stand-alone electrop-
olished surface.
Habibzadeh et al. [20] scrutinised the effect of elec-
trolytic composition (i.e. 60% (v:v) phosphoric acid (85
wt-%), 20% (v:v) sulphuric acid (95–97 wt-%), 10%
(v:v) glycerol (99·5 wt-%) and 10% (v:v) DI water) and
potential voltage (2·5, 4, and 10 V) on the electrochem-
ical polishing of 316L stainless steel specimen. Their
investigation revealed that a thick passive oxide film
enriched with Cr was formed by the new electrolyte
solution when processed at 10 V and results in excellent
corrosion resistance; outstanding biocompatibility and
hemocompatibility surface.
The main constituent of natural bones is calcium
phosphate that is closely matched with the structure
of synthetic hydroxyapatite (HAp, (Ca10(PO4)6(OH)2).
In this way, HAp has selected as bioactive material for
coating and employed in several biomedical applica-
tions. However, due to the presence of microcrack in
sol–gel HAp coatings the surface adhesion strength
to the substrate is poor [16]. Hence, the coatings of
hydroxyapatite(HAp) mixed strong adhere properties
materials composite have been explored by the research-
ers such as Karamian et al. [21] scrutinised HAP/zircon
composite coating on 316L stainless steel, Ramires et al.
[22] analysed the coatings of HAp/TiO2 on the titanium
substrate. The biomedical properties viz. biodegradation,
osseointegration and bioactivity of the specimen were
enhanced due to the inclusion of zircon/TiO2 in HAp.
Zhang et al. [23] studied the MC3T3–E1 cell adhe-
sion characteristics of the 316L stainless steel specimen
possessing polished, aluminium oxide-blasted and
hydroxyapatite (HAp) coated surface. Their research
work originated that the rougher surface with HAp coat-
ing confirms improved cell binding and cell morphology
in comparison with the polished surface.
Zhong et al. [24] employed the atomic layer depo-
sition (ALD) technology for deposition of a microfilm
(10  nm) of Al2O3 on the 316L stainless steel surface.
The modified surface was observed more hydrophilic
and cell layer imitated as compared to the unmodified
stainless steel surface. The Al2O3 coating on drug-elut-
ing stents (DES) sufficiently enhanced the quality and
adhesion of polymer coating. Chang et al. [25] exam-
ined the coating of CuAlO2 layers on 316L stainless
steel specimen, using a radio frequency (RF) magnetron
sputter apparatus. Their experiment results highlighted
that the CuAlO2 film increases the surface hardness and
corrosion resistance of 316L stainless steel. Similarly,
Kheirkhah et al. [26] exploited the nanostructured for-
sterite (Mg2SiO4) coating for the surface modification
of 316L stainless steel substrate. It was observed that the
corrosion resistance and the in vitro bioactivity of fors-
terite coating specimens were improved in comparison
with uncoated specimens. Surface modification of 316L
austenitic stainless steel by coating with zirconium car-
bonitride was presented by Wang et al. [27]. They found
that the corrosion resistance of the AISI 316L stainless
steel substrate increases by zirconium carbonitride coat-
ing, and the preparation of ZrCxN1−x coating at higher
temperature decreases the surface roughness and surface
energy which leads to enhanced blood capability.
Balla et al. [28] considered the laser engineered net
shaping (LENS™) method to modify the surfaces of 316L
stainless steel with bioactive hydroxyapatite (HAp). They
established that the thickness of the modified surface
increases by increasing the laser energy input but at
the same time the surface hardness of the specimen
diminishes.
Bagherifard et al. [29] deployed severe shot peening
surface modification method on AISI 316L stainless
steel. The results demonstrated that shot peening mod-
ification technique could improve the grain refinement
and mechanical properties such as surface roughness,
surface topography, surface wettability, and residual
stresses. This method also enhanced the biocompatibil-
ity of the material and reduced the chance of loosening
and migration of the device.

Magnesium
In 1808, Sir Humphry Davy discovered the element
magnesium, and thereafter research on the biodegrad-
able magnesium implant for the biomedical purpose
was initiated. Towards late nineteenth-century, mag-
nesium wires and implants began to utilise in clini-
cal applications like cardiovascular, draining vessels,
musculoskeletal and general surgery [30]. The density
and elastic modulus of magnesium implants and nat-
ural bones are nearly equivalent as compared to other
commonly used implants of stainless steel, cobalt-based
alloys, and titanium alloy. Thus, it significantly reduces
the stress shielding impact of bone restoration [31,32].
The requirement of secondary surgery for removing
the magnesium implant is evitable because magnesium
degrades in vivo and it is extracted from urine [33].
It has also been recognised that Mg2+ contaminants
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help in the growth of new navicular bone tissues and
abbreviate crack-retrieving time [34]. A related study
has shown that human body consumes 250–500 mg of
magnesium particles per day by physiological functions.
The presence of Mg in an average 70 kg human body is
about 20 g; the harmful amount is still unidentified [35].
The utility of magnesium is attributed to inherent use-
ful properties such as (a) its higher strength-to-weight
ratio, (b) good thermal electric conductivity (c) excellent
vibration and cushioning, (d) higher damping capacity
and (e) electromagnetic shield efficiency [36–38].
The main restriction in use of magnesium com-
ponents as an implant is the presence of unprotected
Figure 3.  SEM of the calcium phosphate coated AZ91
magnesium alloy using different coating methods: ((a), (b))
randomly dispersed coating via constant-potential and ((c), (d))
Compact coating via pulse-potential method [46].
MATERIALS TECHNOLOGY   5
or imperfect oxide film on the specimen surface that
results in increasing the corrosion of the component
[39]. Another problem is the growth of uncontrollable
hydrogen bubbles during corrosion; if the formation of
hydrogen gas is very quick, an inflatable impact of blood
circulation blockage may occur [35]. There are two pos-
sible approaches to enhance the corrosion resistance of
Mg and Mg amalgams: (i) modify the composition and
microstructure, accommodating grain sizing [40,41],
and (ii) surface treatment or structure coatings [42].
In order to improve the corrosion resistance and
the invitro bioactivity of magnesium alloys, Razavi et
al. [43,44] utilised the micro-arc oxidation method in
combination with electrophoretic deposition process
for developing the nanostructure akermanite and diop-
side (CaMgSi2O6) coating on biodegradable magnesium
alloy. To protect magnesium from initial degradation,
Chen et al. [45] proposed the strontium phosphate (SrP)
conversion coatings process. It is reported that the coat-
ing solution containing 0·1 M Sr and 0·06 M PO34 pro-
−
duces strontium apatite (SrAP) surface coating at 80°C
in minimum essential medium (MEM) that increases
the corrosion resistance of magnesium specimen.
Consequently, it retarded the toxic impact of hydrogen
gas formations from magnesium implants affecting the
surrounding cells and tissues.
The performance of calcium phosphate film on mag-
nesium alloy by electrochemical method was analysed
[46]. The pulse and constant-potential techniques were
employed for the coating of magnesium specimen, and
their results revealed that the pulse-potential coated
alloy had better corrosion resistance and three times
higher polarisation resistance than constant-- poten-
tial coated alloy. SEM micrographs of coated alloy by
pulse-potential and constant-potential methods are
shown in Figure 3.
The team of Lu [47] also utilised β-tricalcium phos-
phate (Ca–P) coating via chemical reaction of Mg in
a simulated Hank’s solution. It was found that Ca–P
coating ameliorated the bioactivity, degradation rate and
the corrosion resistance of the specimen. In the follow-
ing research work, they modified the Ca–P coating by
including strontium (Ca–Sr–P) and deposited on the
pure magnesium specimen in the electrolyte solution
[48]. The (Ca–Sr–P) mixture delivered very smooth,
fine and improved microstructure layer on the surface.
Along with that, it also helped to protect the magnesium
substrate from degradation. Nanostructured self-assem-
bled monolayers (SAMs), for surface modification of Mg
and its alloys, were overviewed by Mahapatro et al. [49].
They concluded that SAMs are a promising technique
for altering the surface of biodegradable Mg substrates
and enhancing their biological interfacial performances
and responses.
White et al. [50] utilised the plasma electrolytic oxida-
tion (PEO) coating technique for enhancing mechanical
properties ofAZ31 magnesium alloy. They compared the
 6   A. MAHAJAN AND S. SINGH SIDHU
performance of three different electrolytes containing
varying concentration of chemicals such as NaOH,
Na2SiO3, KF and NaH2PO4. The outcomes validated
that the PEO-coated alloy with fluoride (KF) has better
corrosion resistance, wear resistance, surface hardness
and elastic modulus in contrast to the uncoated AZ31
magnesium alloy substrate.
Titanium
In late 1940s, the professional growth of titanium began,
and its evaluation soon trailed it as a surgical implant
material with remarkable tissue similarity [51,52].
Earlier, titanium devices were employed as an implant
only in countries like England and the United States.
Later, because of its exceptional properties such as
lower elastic modulus, excellent biocompatibility and
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outstanding corrosion resistance, it came to be widely
utilised all over the world for biomedical applications
such as dental, orthopaedic implants and implantable
electronic devices [53,54]. Due to superior specific
strength (strength/density), titanium joints such as hip,
knee, shoulder, spine and wrist make a good physical
association with the host bones and have admirable
stability as compared to stainless steel and cobalt alloys
[55].
In case of load-bearing applications, titanium and its
alloys are not normally preferred due to inferior tribo-
logical properties such as poor fatigue and unfavour-
able wear resistance. Subsequently, efforts were made
to enhance the properties of titanium and its alloy in
a controlled atmosphere. Amongst all methodologies,
surface modification of titanium and its alloy proved to
be a standout technique in which the surface proper-
ties could be precisely adjusted while retaining the mass
characteristics of the materials. The surface treatment of
implant can be executed by different strategies such as
grit blasting, chemical etching, titanium plasma spray,
laser treatment, electrochemical therapy, or a combina-
tion of these techniques [54].
The evidence of allergic reactions of Ti–6Al–4 V in
the human body will be overcome by the introduction of
the second generation β-alloy stabilising elements, such
as Nb, Ta, and Zr. in the titanium implants. Kuroda et
al. [56] considered the d-electron alloy design method
for the fabrication of new β-type titanium alloy for
implant materials consisting of nontoxic elements like
Nb, Ta, Zr, Mo or Sn. Their experiment work illustrated
that the tensile strength and elongation of conventional
titanium alloy were less or equivalent to designed
Ti–29Nb–13Ta–4·6Zr alloy, whereas the Young’s mod-
ulus of designed alloy was certainly close to the natural
bone tissues which stimulates new growth and stability
to the implants. Taddei et al. [57] adopted powder met-
allurgy technique to blend Nb, Ta, Zr and Ti powders for
generating Ti–35Nb–7Zr–5Ta alloy for porous ortho-
paedic implants. The outcome verified that the newly
designed alloy would be used as an effective biomaterial
due to its outstanding mechanical properties, controlled
porous structure and bonding strength. The mechanical
properties of the titanium alloys for medical and dental
fields implant materials revealed that the crack propa-
gation rate, Vickers hardness and fracture toughness of
biomedical titanium alloys remained unchanged in the
simulated body environment [52]. In order to enhance
the mechanical, chemical and biological properties of
implants, Liu et al. [58] suggested the plasma surface
modification techniques namely plasma spraying and
plasma immersion ion implantation deposition (PIII-D)
to introduce biocompatible minerals into the Titanium
metal. The results demonstrated that as compared to
plasma spraying method, the PIII-D produced a strong
bond between the surface modified layer and the tita-
nium substrate. By including the elements like calcium,
phosphorus and sodium in titanium, the bioactivity, and
biocompatibility of specimen can be improved by PIII-D
technique.
The laser beam energy processing technique had a
broad range of application in engineering and medical
operations and reputed as a precise and rapid method.
The work published by Trtica et al. [59] revealed the
perspective of surface modification via Nd–YAG laser
technique for the preferred surface characteristics of the
titanium implant. They observed that the laser irradiation
technique could modify the morphology, surface rough-
ness and the bio-integration of the titanium implant. In
another similar technique, Braga et al. [60] employed an
effectual Nd–YVO4laser for surface modification of Ti
dental implants. The laser beam can precisely control the
passivation membrane of titanium oxide on the surface,
as a consequence, the good osseointegration and clinical
stability. Mendes et al. [61] considered the powder met-
allurgy method for introducing the low Young’s modulus
Ti–27Nb–13Zr alloy. The alloy was immersed in artifi-
cially prepared supersaturated calcium and phosphate
solution known as simulated body fluid for exhibiting
that biomimetic coating on the alloy. The formation of
surface acts as apatite inducer and enhanced mechanical
properties such as microhardness and elasticity modulus
confirmed that Ti–27Nb–13Zr alloy could be used in
orthopaedic and dental applications.
Cobalt–chromium
Initially, in 1930s, cobalt chromium alloy was extensively
used in dental implant and then in 1940s it adapted for
artificial hip and knee replacement. The significant con-
stituents are cobalt, chromium and molybdenum [62].
Chromium and cobalt both lead to resist corrosion
by producing an oxide layer on the material surface.
However, the addition of molybdenum decreases the
grain size and thus delivers stability, mechanical strength
and bulk resistance from corrosion [62,63].The circulat-
ing physiological levels of Co and Cr in the human body
 MATERIALS TECHNOLOGY   7

are usually < 0·25 μg/l. The elevated level of Co and Cr
ions leads to toxicity in both the hip synovial fluid and
peripheral blood [64]. The bio-corrosion of these alloys
is one of the worrying issues to be managed, as there is
a massive emission of metal ions during utilised as an
orthopaedic implant that causes unfavorable impacts
[65]. This complication can convalesce through surface
engineering of chromium–cobalt specimen.
Hukovic et al. [66] developed an incredibly intended
passive oxide layer on Co–Cr–Mo alloy in Hank’s solu-
tion. The corrosion resistance and compatibility of the
Co–Cr–Mo alloy were observed to have escalated by
the use of Hank’s solution. Liu et al. aimed to improve
the surface properties of medical grade Co-Cr mate-
rial by using plasma surface alloying for the diffusion
of nitrogen and carbon molecules [67]. The metallur-
gical, mechanical, corrosion and wear properties can
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biomedical applications. Further, Bhure et al. charac-
terised phosphonic SAMs in their research [70]. They
utilised the deposition technique for development and
depiction of the octadecylphosphonic acid (ODPA)
SAMs on the oxide surface of cobalt chromium (Co–Cr)
alloy. They claimed that the self-assembled mono lay-
ered Co–Cr alloys are the essential candidates for poten-
tial use in biomedical implant services. Further, Zhou
and his co-workers introduced Co-based bulk metallic
glasses (BMG) as one of the notable biomaterials that
significantly reduce the undesired fouling of implants
[71]. They reported that the corrosion resistance and
biocompatibility of these materials were found excellent
as compared to 316L stainless steel, and it was verified
that the Cr10Mo10 was the best Co-based BMG for the
biometric applications.
Table 4 summarises the literature reports of surface

efficiently be improved while treating the surface with
plasma nitriding and plasma carbonitriding processes.
Furthermore, Diaz et al. [68] made the similar observa-
tions for plasma surface modification. They conducted
an experiment with plasma immersion ion implantation
for lowering the emission of ions from Co–Cr alloy. A
thick layer of chromium oxide was produced on the
surface of Co–Cr alloy that enhanced the corrosion
resistance and successfully reduced the wear rate and
emission of ions from the substrate.
Mani et al. [69] suggested the coating of self-assem-
bled monolayers (SAMs) of octadecyl trichloro silane
(OTS) on Co–Cr alloys. The results demonstrated
that SAM layers provide better stability to alloys for
modification methods on the metallic biomaterials.
Surface modification by EDM
Various nonconventional methods of surface alteration
are available, viz. electron beam, laser machining or
electric discharge machining (EDM), which produces
complicated shapes with high accuracy as compared to
standard conventional methods [72–74]. Amongst the
non-conventional methods, EDM is an efficient tech-
nique that can be utilised for machining any complex
material and for producing messy geometrical shape
[75]. Figure 4 represents the basic components of EDM
setup and the morphology of machined surface. In

Table 4. Literature summary of surface modification of different materials by various effectual techniques.
Material Coating Method References
Stainless steel Hydroxyapatite Water based sol gel [16]
Non acid Ionic liquid Electrochemical pretreatment [18]
Electrochemical polishing Chemical surface treatment [19]
Electrochemically Polishing Chemical surface treatment [20]
Hydroxyapatite/zircon nano-biocomposite Plasma spray method [21]
Hydroxyapatite, Aluminum Oxide Blasting, polishing Plasma spraying [23]
AL2O3 Atomic Layer Deposition [24]
CuAlO2 Radiofrequency magnetron sputtering method [25]
Mg2SiO4 Sol-gel dip [26]
Zirconium Carbonitride Radiofrequency magnetron sputtering method [27]
Hydroxyapatite LENS [28]
Uncoated Severe shot peening [29]
Magnesium Nanostructured diopside, nanostructured akermanite Micro arc oxidation with electrophoretic deposition [43,44]
Strontium Phosphate Minimum essential medium [45]
Calcium Phosphate Pulse potential method [46]
Calcium phosphate and calcium phosphate with Strontium Hank’s solution [47,48]
NaOH, Na2SiO3,KF and NaH2PO4 Plasma electrolytic oxidation [49]
Titanium Nb, Ta, Zr, Mo, Sn powders D-electron alloy design method [56]
Nb, Ta, Zr, Ti powders Blended Element Method [57]
  (a) Hydroxyapatite Plasma Spraying and Plasma Immersion Ion (PIII-D) [58]
  (b) Calcium Silicate
  (c)  Phosphorous powders
  (d) Sodium powders
Uncoated ND:YAG Laser [59]
Uncoated ND: YVO4 Laser [58]
Biomimetic Powder Metallurgy [60]
Chromium-cobalt Passive oxide film Hank’s Solution [66]
Nitrogen and carbon powder Plasma surface alloying method [67]
Chromium Oxide PIII [68]
Self assembled mono layers Octadecyltrichlorosilane(OTS) [69]
Self assembled mono layers Octadecylphosphonic(ODPA) [70]
Uncoated Co-based BMGs [71]
 8   A. MAHAJAN AND S. SINGH SIDHU
this operation, the application of potential difference
between the electrodes resulted in the formation of short
electrical plasma in the dielectric medium. The plasma
consisting of spark channel is highly conductive and
capable of sustaining large current (104A) and gener-
ating temperature of around 0·7 eV (8100 K) [76]. Due
to high temperature the small part of material melted/
vaporised and removed, creating craters as well as re-so-
lidified layers on the surface. The volume removed by
the single spark is small in the range of 10−6 to10−4 mm3
however, this process was repeated typically 10,000 times
per second.
This thermal material erosion principal of EDM pro-
cess leads to surface metallurgical changes in the form of
grain structure, chemical composition and recast layer
deposition. In this section, the surface modification of
different materials by EDM process is elucidated. The
Downloaded by [Australian Catholic University] at 02:45 22 September 2017
EDM plasma is composed of species coming from the
breakdown of dielectric medium and the erosion of
electrodes. Thus, the selection of dielectric medium, the
electrode material and process parameters shows a sig-
nificant impact on the surface modification of the work-
piece. Guu et al. [77] investigated the surface of AISI D2
tool steel by EDM and found that the thickness and sur-
face hardness of recast layer were improved by increas-
ing spark plasma energy within the electrodes. The
impact of process parameters on material erosion rate,
Figure 4. (a) Schematic diagram of EDM setup (b) propagation of positive streamer and spark formation in dielectric medium (c)
pictorial view of spark formation between tool and workpiece and (d) SEM of porousED machined surface (as marked).
electrode wear and surface hardness of AISI H13 tool
steel was also elaborated by the researchers [78]. They
conducted an experiment with partially sintered WC/
Co tool electrode and reported that modified layer had
fewer micro-cracks, and surface hardness significantly
increased from 640 to1319 HK. Chen et al. [79] pursued
a study of the surface modification of Al–Zn–Mg alloy
by the hybrid machining (i.e. EDM coupled with ultra-
sonic vibrations). They observed that as compared to
conventional EDM, combined process induced solid film
deposition with lower surface roughness. Sidhu et al.
[80] demonstrated another variation of powder- mixed
EDM for surface modification of three essential metal
matrix composites viz. 65 vol.-% SiC/A356.2, 10 vol.-%
SiC-5 vol.-% quartz/Al, and 30 vol.-% SiC/A359. They
concluded that by increasing the reinforced particles
density in the matrix phase, the decomposition of rein-
forcement at high operation temperature coupled with
materials transfer resulted in the enhanced surface integ-
rity of the machined surface. The surface customised by
copper electrode proved to be superior as compared to
graphite electrode because of a significant amount of
metal transfer from the copper electrode. Another study
by Marashi et al. [81] reported that the superior surface
integrity of AISI D2 steel was obtained due to the inclu-
sion of Ti-nano particles transported from the Ti-mixed
dielectric medium. Kumar et al. [82] considered the
 MATERIALS TECHNOLOGY   9

powder mixed dielectric method in which tungsten
powder was mixed in a dielectric medium for surface
modification of three selected die steel materials. By
modifying the surface, the micro-hardness for all the
three die steels was improved by more than hundred per-
cent. The beneficial conditions obtained from the study
for material transfer by EDM were as follows: low dis-
charge current (under 5 A), shorter pulse on-time (less
than ten μs), longer pulse off-time (more than 50  μs)
and negative polarity of the tool electrode. Khan et al.
[83] contemplated TiC powder mixed dielectric for the
machining of mild steel specimen with Cu–W as a tool
electrode. They observed that the layer produced by TiC
powder was thin and hard as compared toAl2O3 powder.
The layer thickness and the splits on the surface were
increased by the escalation of the input current.
These breakthrough capabilities of EDM process
Downloaded by [Australian Catholic University] at 02:45 22 September 2017
[88] claimed that the EDM treated surface reduced the
corrosion resistant ability.
The porous structured implants may be the appropri-
ate approach for efficient interfacial bond between the
implants and the host cells. In this context, numerous
attempts were made to underline the effect of porous
implants in vascularisation and bone growth. Shin et
al. [89] studied the cellular performance on the porous
surface ranging from ~2 to 5 μm, using MC3T3–E1 oste-
oblast bone cell. They concluded that the surface with
~2 μm pores significantly enhances the bioactive prop-
erties. In another study, the team of Li [90] implanted
the porous specimen Ti6Al4 V scaffolds of pores size
ranging from 300 to 400  μm in the living animal. In
this experiment, they reported that the porous surface
showed better morphological fixation and favourable
bone ingrowths (as shown in Figure 5).

attract the researchers to explore the suitability of EDM The characteristics of EDM process suggest the
in the biomedical field. Harcuba et al. [84] conducted the researchers to obtain the porous surface with synchro-
study to examine the various surface treatments impact nised adjustment of process parameters. Peng et al. [91]
on Ti–6Al–4 V alloy for orthopaedic applications. Their performed EDM on F67 Grade IV Ti sheet using cop-
work illustrated that the samples that were customised per electrode in the distilled water dielectric medium.
by EDM had excellent biocompatibility with bones, cells They concluded that short duration electric discharge
and other organs of the human body as compared to and evolution of hydrogen yield nanoporous bioactive
TiO2coated sample. This coating can also efficiently sus- titanium surface. Recently, Ekmekci and Ekmekci [92]
tain the joints loads and contributed to enhancing the studied the deposition of HAp layer on the surface of Ti
reliability. The maximum range of joints force applied
at hip and knee joints during various activities is listed
in Table 5.
One recent study reports that the powder mixed
EDM treated β-phase Ti alloy exhibited a potential
improvement in its fatigue endurance and surface fin-
ish [85].Further, Mahmud et al. [86] utilised the advan-
tages of pulse power generator in EDM process for the
high-quality surface finish of micro-pits for the lubri-
cation purpose on the hip implants. The uncontrolled
biodegradability of magnesium in the human body leads
to toxicity and early structural in stability. Klocke and
his team [87] suggested the combination of EDM with
Plasma Electrolytic Conversion process for the surface
modification of implants; by this process, they demon-
strated the improvement in the magnesium degrada-
tion kinematic and tissue response. The introduction
of EDM in dentistry demonstrated the clinical success
in the passive fitting of implants. However, Ntasi et al.

Table 5. Average maximum force values at hip and knee joints

during various activities [101].
Maximum joint force (Multiples of body weight)
Activity Hip Knee
Level walking
Slow 4·9 2·7
Normal 4·9 2·8
Fast 7·6 4·3
Up stairs 7·2 4·4
Down stairs 7·1 4·9 Figure 5. Presentation of Vivo experiment (a) porous implant of
Up ramp 5·9 3·7 Ti alloy (b) Specimen at 3 months (c) at 6 months (d) 12 months
Down ramp 5·1 4·4 of implantation.
 10   A. MAHAJAN AND S. SINGH SIDHU

Figure 6. Structural section investigation of Ti6Al4V machined surface using + polarity (a) General view (b) grain structure and(c)
EDS peaks [92].

Table 6. Literature summary of surface modification of different materials by EDM process.

Method for surface mod- Electrode; Dielectric
ification with EDM medium Work piece Discharge current (A) Pulse-on duration (μs) References
Downloaded by [Australian Catholic University] at 02:45 22 September 2017

Eroding tool electrode Cu; Hydrocarbon oil AISI D2 1–10 20–180 [77]
PM electrodes and PMEDM WC–Co; Hydrocarbon oil AISI H13 1–3 20–40 [78]
PMEDM Cu; TiC additive Hydro- Al–Zn–Mg 3–15 50–500 [79]
carbon oil
Eroding tool electrode Gr; hydrocarbon oil Ti–6Al–4V 21–79 5–20 [84]
PMEDM Cu; Tungsten with Hydro- Die steel 2–6 5–20 [86]
carbon oil
PMEDM Cu; kerosene mixed TiC Mild steel 2·5–6·5 10 [82]
and Al2 O3
PMEDM Cu, Gr, Cu–Gr; EDM oil Metal Matrix Composites 4–12 10–50 [80]
mixed Cu, Gr powder
PMEDM Cu; Ti with Hydrocarbon Die Steel 6–20 120–340 [81]
Oil
PMEDM Ti; HAp mixed deionized Ti6Al4V 7–72 3–100 [92]
water

Notes: PM: Powder Metallurgy; PMEDM: Powder Mixed EDM; Gr: Graphite.

alloy resulted from EDMin the presence of HAp – mixed
in deionised water as a dielectric medium (Figure 6).
Consequently, it is evident that the process combina-
tion of various ED machining parameters opens the new
pathway to accelerate the invention of next-generation
bioimplants suitable for the biological systems.
The dominating surface modification techniques used
in EDM, powder-mixed dielectric and powder metal-
lurgy electrodes are discussed briefly and summarised
in Table 6.
Conclusions and future scope
nonconventional machining process is the modernist
method for the synthesis of biomaterials. Surface mod-
ification route via EDM process enables the depositions
of minerals, open porous structure and metallic residues
compatible to the human body environment through
the intelligent selection of tool electrodes composition
and machining parameters. The combined selection
of EDM process parameters ameliorates the essential
component properties. Moreover, the method is also
capable of developing the replacement bone near to the
architecture of natural bone in all scales and performs a
significant role in the biological systems.

Surface modification of biomaterials is an extensive sub-

ject with a broad range of contemplation for improving
the implant performance and its service life in a human
body. Stainless steel, titanium, magnesium and the
chromium-cobalt are the leading implant materials in
orthopaedic applications. In-depth sophisticated anal-
ysis of the published work on surface modification of
biomaterials highlights that the surface alteration pro-
cess enhanced biocompatibility, chemical slothfulness,
lubricity, sterility, asepsis, thrombogenicity, and hydro-
philicity of biomaterial. Besides that, it also improves
the outstanding mechanical properties viz. corrosion
resistance, surface hardness, Young’s modulus and wear
resistance. The surface engineering of biomaterials by
Disclosure statement
No potential conflict of interest was reported by the authors.
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