Ceramics International 48 (2022) 4377–4400

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

A comprehensive review on biocompatible thin films for

biomedical application
S. Thanka Rajan a, B. Subramanian b, A. Arockiarajan a, c, *
a
Department of Applied Mechanics, Indian Institute of Technology Madras, Chennai, 600 036, India
b
Electroplating and Metal Finishing Division, CSIR-Central Electrochemical Research Institute (CECRI), Karaikudi, 630 003, Tamil Nadu, India
c
Ceramic Technology Group -Center of Excellence in Materials and Manufacturing Futuristic Mobility, Indian Institute of Technology Madras (IIT Madras), Chennai, 600
036, India

A R T I C L E I N F O A B S T R A C T

Keywords: Thin films have emerged as an ideal surface treatment to the permanent implant materials to enhance properties
Thin films such as biodegradation resistance, better mechanical strengths and biocompatibility. A perfect implant ought to
Biocompatibility have the ability of resistance to degradation, stimulate osseointegration, prevent bacterial adhesion, and
Hemocompatibility
decrease prosthetic infection. The clinical success of implants depends on the interaction of cells with material
Corrosion
Mineralization
surfaces, which is an essential factor. Recent development in biomaterials has brought a variety of coatings on
biomaterial to overcome these issues. The coatings impart biocompatibility, better mechanical property, and
bioactivity to the biomaterial. In this review, the recent trends in surface modification by thin films of implants
have been discussed in detail.

1. Introduction 1.1. Requirements of biomedical implants

Biomaterials are materials employed to physically replace missed The biomaterials design depends on the particular function of the
biological parts or hard or soft tissue injured or damaged by some ir­ material. A biomaterial needs to have some crucial features to safely and
rational process. The main objective of biomaterials used for implants is effectively serve for an extended period without any adverse reaction.
to restore the damaged bone’s structural integrity, which in turn de­ The most important requirements for a good biomaterial are good
pends on a complex interplay of device design, materials properties, and biocompatibility, higher resistance to corrosion and wear and better
physiologic requirements [1]. In the coming decades, there is a constant osseointegration [4]. The requirements for a successful bioimplants
expansion and advancement in the study of biomaterials. The essential material is displayed in Fig. 1.
requirement of the biomaterials is their inertness to the body environ­
ment, i.e. the implant should sustain in the harsh corrosive surroundings 1.1.1. Biocompatibility
(pH 7.4 & temperature 37 ◦ C). Another critical factor is that the material The definition of biocompatibility is the material that can execute a
should be biocompatible and not evoke any adverse reaction in the suitable host response in a particular condition. The factor of biocom­
body. Additionally, it should not be carcinogenic and toxic [2]. The patibility is the biomaterial should react with the tissues and not be
biomaterials have the ability to persist in the body environment, devoid ignored by them, and additionally, in some applications, the material
of damaging the ambiences and without getting spoiled in the process. A should degrade in the body [5]. An ideal biomaterial should have the
promising biomaterial must combine better material properties and properties coordinated with damaged tissues and develop strong
biological properties to fit for a specific application. The important bonding with biomaterials and tissues interface [6]. It must not suppress
feature of biomaterials is how it interacts when placed in a human the performance of the action of normal cells and is toxic-free. Addi­
environment [3]. Metals and their alloys, ceramics and polymer are tionally, the material should promote protein adsorption, cell adhesion
reliable materials that are well established and recognized as bio­ and growth in the environment [7]. The biomaterials success depended
materials. The different materials have their unique unrivalled proper­ on the human body’s reaction to the implant, which measures the
ties in their particular arena of application along with drawbacks. biocompatibility of a material.

* Corresponding author. Department of Applied Mechanics, Indian Institute of Technology Madras, Chennai, 600 036, India.
E-mail address: [email protected] (A. Arockiarajan).

https://doi.org/10.1016/j.ceramint.2021.10.243
Received 17 October 2021; Received in revised form 29 October 2021; Accepted 29 October 2021
Available online 2 November 2021
0272-8842/© 2021 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
S. Thanka Rajan et al. Ceramics International 48 (2022) 4377–4400

1.1.2. Corrosion approaches are categorised as improved bone-bonding and accelerated

The material used for implant application must be free of allergenic bone healing [15]. The surface topography of the implants is changed in
and toxic elements and should not be affected by corrosion. So the alloys the enhanced bone-bonding method, which increases the interlocking of
are made of a suitable composition of the alloy, which is immune in body the implant mechanically with the bone. The surface area and surface
fluid. Additionally surface property of the implants are modified, and it energy are increased for the modified surfaces of the material. It im­
makes the biomaterial immune in the body environment, which over­ proves protein absorption, cell proliferation, and cell adhesion and en­
come corrosion and improve biocompatibility [8,9]. hances the implant’s osseointegration with the bone. Inorganic bone
materials are coated onto the implant surface, enhance the bone-forming
1.1.3. Osseointegration cells’ ability and interlocks biochemically the implant with bone [15].
The structural and functional link between the bone and the implant The surface properties of the implant material are changed by several
is osseointegration [10]. It is an exercise of healing bone and formation efficient coatings, which modifies their morphology, structure and
of new bone, which is the essential condition in bioimplants [11]. composition. Various coating techniques are employed for surface
Fibrous tissue formation around the implant makes the implant bonding modification by thin-film coating methods, and they are displayed in
surfaces incapable of the nearby tissues, and head-to-head bone causes Table 1.
micromotion and leads to implant loosening [11,12]. So favourable and This review discusses different surface modifications of biomaterials
suitable surface of the implants is essential to bind well with adjacent by coatings that improve their biocompatibility, corrosion and wear
bone. The surface chemistry and surface topography are the measures resistance and bioactivity by using a number of coatings are discussed.
for better osseointegration [4]. These include transition nitride coatings, thin film metallic glasses
(TFMGs), Diamond like carbon (DLC) and bioceramics. This review fo­
1.2. Need for surface modification cuses on biocompatible coatings and their properties like mechanical
properties, corrosion properties, and biological properties used in
The surface property of the biomaterial, like chemical and physical biomedical applications. This work gives a complete summary of the
properties, control the biological response of the biomedical devices. coating properties, and its outline is displayed in Fig. 3.
Tailoring the surface properties of the biomaterials by modification
delivers a practical approach to enhance tissue–material interfaces and 2. Nitride coatings for biomedical applications
minimises the adverse reactions aggravated [13]. The material’s surface
plays a vital role in the biological response when they are in the body Researchers gain attention to nitride coatings for their favourable
environment. Another more important reason is the bulk properties of properties like excellent resistance to corrosion, hardness, ductility and
the biomaterials are different from the surface property specifically biocompatibility. Transition metals’ binary or ternary nitrides are good
required. For example, bone implants should have better bone form­ in mechanical properties, corrosion resistance, and tribological and
ability to achieve biological integration. For blood-contacting devices biocompatibility properties [16]. The nitrides coatings like TiN, TiAlN,
like heart valves, the crucial one is blood compatibility, and the other ZrN, TaN, NbN, and VN are suitable for the implant as protective coat­
implants need resistance to corrosion and wear, and better biocompat­ ings to upsurge their life expectancy by reducing wear and corrosion
ibility is required. The appropriate surface modification techniques [17].
retain the implants’ excellent bulk properties like modulus and strength
and enhance the necessary surface properties [14]. The various factors 2.1. Mechanical properties
that cause the implant failure and the need for surface modification are
illustrated in Fig. 2. Titanium nitride (TiN) ceramic hard coatings are the most commonly
The response of the biomaterials’ biocompatibility depends on sur­ used for bioimplants application. TiN has superior properties like
face properties. Although remarkable development has been made in greater hardness (2000 kg/mm2), at room temperature, it is chemical
biomedical research, the ideal biomaterial that satisfies all the neces­ stable, has a more significant decomposition temperature (2949 ◦ C), and
sities is not achieved. By modifying the surface of the implant the has good aberration resistance. The most widely used coatings for
composition, structure and morphology can be altered. Two types of different applications are TiN, TiAlN, TiCN CrN, ZrN, CrAlN [18–23]. To

Fig. 1. The requirement of biomaterials for biomedical implants.

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Fig. 2. Need for surface modification and the factors that cause implant failure.

mechanical and tribological properties [25]. The mechanical properties

Table 1
of the different nitride coatings are displayed in Table 2.
Overview of surface modification by thin-film coating methods for implants.
The definition of hardness was the resistance offered by a material to
Surface Thin Film for Modification Purpose exterior mechanical action. For a super hard material, the three condi­
modification
tions should be satisfied, namely: covalent bonding with a higher de­
methods
gree, higher coordination number and bond length to be short [32].
Sol-gel ~10 μm of thin films, such as To enhance biocompatibility,
Generally, the thin films were comprised of minor crystallites, and the
HAp, TiO2 and silica bioactivity or bone
conductivity
density of defects was higher. So the thin films display greater hardness
CVD ~1 μm of TiN, TiC, TiCN, To enhance wear resistance, compared to bulk material [32]. Additionally, for coatings or thin-film
diamond and DLC corrosion resistance and blood decrease in grain size hinders the multiplication of dislocations and
compatibility mobility and the hardness of the materials increases, conferring to the
Thermal spray ~30 to ~200 μm of coatings, To enhance wear resistance,
‘Hall–Pitch’ relationship: H(d) = Ho + Kd− 1/2 [33]. Fig. 4 displays the
of titanium, calcium silicate, corrosion resistance and
HA, TiO2, ZrO2, Al2O3, biological properties hardness as a function of the grain size of a material [33].
PVD ~1 μm of TiN, TiCN,TiC, ZrN To enhance wear resistance, Generally, good mechanical properties of a coating are greater
Thermal diamond and DLC, Thin film corrosion resistance and blood hardness, high toughness, good adhesion to the substrate, low friction,
Evaporation Metallic glass (TFMG) compatibility
and they should be thermally and chemically stable, have load-
Ion plating
Sputtering
supporting capability, etc. Among these, the most important one is the
PLD hardness of the coatings in biomedical and tribological applications.
Nanoindentation is the best method to determine nanohardness and
explore Young’s modulus of the coatings. A Berkovich diamond indenter
increase the hardness and thickness of the film without increasing the tip is forced into the thin film surface to make indentations. The
brittleness and to reduce yield strength, multi-element coatings and indentation was made on the film surface by pressing the tip by
multilayer coatings are used [24]. The appropriate selection of element increasing the load, and the corresponding displacement was recorded
composition, layer materials and coating architecture like morphology, to get a profile with loading and unloading [34]. The load-displacement
thickness and layers plays a significant role in attaining the prime curve is employed to calculate the hardness and elastic modulus.

Fig. 3. The flow chat for enhancing biomaterial by surface modification types and their properties studied.

Table 2
Mechanical properties of the different nitride coatings.
Materials Density g/cm3 Thermal conductivity W/m ◦ C Vickers hardness Elastic modulus GPa Coefficient of Friction Poisson Ratio Reference

TiN 5.40 19.0 18–21 GPa 600 0.65 0.25 [26,27]

TiAlN 4.8 - 2800 kg/mm2 484 0.70 0.19–0.22 [28,29]
TiCN 5.21 29 3000 kg/mm2 300 0.45 - [29,30]
ZrN 7.09 21.9 2500-3100 kg/mm2 510 0.5 0.25 [27,31]

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unloading curve is called ‘pop-out. The ‘pop-out event is due to an

irregular drop in indentation displacement or may be due to phase
transformation in the unloading curve [43]. The ‘pop-in’ events of Fig. 5.
are associated with the plane-slip, and ‘pop-out’ is due to interfacial
delamination between the film and the substrate [38,44].
A Rockwell C indenter scratch tester verified the coating adhesion to
substrates. The critical load Lc1 corresponds to cohesive failure, and it is
defined as the load at which the initial indication of cohesive crack
happens in the scratch track. Lc2 corresponds to adhesive failures at the
load where repetitive spallation failures occur, and at the load Lc3, the
coating is delaminated totally from the film. The failure of the coating at
different stages was evaluated from the parameters like penetration
depth, coefficient of friction (COF) and acoustic emission [45]. Alicja
et al. coated TiN onto SS of three different hardness, and the adhesion of
the coatings was tested by scratch resistance test [46]. The Lc2 spall­
ation failures occurred, and the scratch starts were at the load of 48 N,
36 N and 23 N, respectively. The experiments show the critical load of
adhesion failure for the coatings. The substrate hardness influences the
Fig. 4. Hardness Vs grain size as a function [33]. adhesion of the coating, and an increase in the hardness of the substrate
increases the adhesion [46]. The TiN/Ti coatings on Ar ion irradiated
Babinova et al. evaluated the highest hardness of 30 GPa for the TiN ion-implanted Ti6Al4V was employed for the scratch resistance. They
films, and it’s Young’s modulus was 300 GPa for the TiN films of high showed the highest scratch resistance of 72 N of coatings adhesion
discharge current density and low nitrogen flow rate [35]. The nano­ strength. The nanoindentation studies showed a hardness of 27.06 GPa
indentation parameters of TiN, TiAlN, and TiAlSiN thin films were and Young’s modulus of 365 GPa [47].
analysed by Kong et al. [36]. They found the hardness of three materials The mechanical and tribological characterisation of TiN/a-C: H
are 7.09 (TiN), 15.6 (TiAlN), and 21.7 GPa (TiAlSiN), respectively. The multilayers was studied by Kot et al. TiN/a-C:H multilayers (Fig. 6) of
elastic modulus and plastic deformation energy are measured in the 1:1 ratio exhibited noble adhesion to the substrate which is comparable
order of TiN > TiAlN > TiAlSiN. Anusha et al. coated titanium car­ to the TiN thin film [25]. The scratch resistance was studied for different
bonitride (TiCN) onto stainless steel and evaluated the hardness and nitride coatings, and they showed outstanding adhesion to a substrate
Youngs modulus of the thin films and found to be 21.1 GPa and 303 GPa like TiN [48], TiAlN/TiSiN, TiAlN [49]. Łukasz et al. studied the wear
[37]. Titanium boron nitride (TiBN) thin films were fabricated, and the and degradation of the TiN coated knee replacement in vivo. The knee
nanoindentation was studied by Anusha et al. From the replacements were retrieved from a human after 13–21 months, and a
load-displacement curve (Fig. 5), hardness and elastic modulus of the semi-quantitative scoring system evaluated the damage on the surface,
TiBN was computed as 13 GPa and 242 GPa [38]. SEM, and the adhesion was assessed by indentation. The images show
Fig. 5. presented the indentation curve with the events like ‘pop in’ the (Fig. 7a and b) frosted appearance of the tibial tray of UNI (Fig. 7a)
and ‘pop out’. The thin films were suffering very high stresses and in the unworn areas (white arrow), and the load subjected areas showed
loading yield ‘pop-in’ happenings that are generally considered by a polished, glossy surface with numerous parallel scratches (grey
abrupt excursions in depth which acts as a cause of plastic deformation arrow), corresponding to wear marks which is observable in poly­
or phase transformations [39,40]. The sudden displacement bursts ethylene liner also. The coating worn areas (small patches) are visible on
spontaneously and points out a sharp drop in stress in the pop-in event TKR tibial trays (Fig. 7b). Thus during in vivo use the TiN coated knee
[41]. In indentation at the initial stage of mechanical interaction, the orthopaedic replacements suffer wear and degradation [50].
pop-ins event offers a conversion from reversible elastic deformation to
plastic deformation, which is irreversible [42]. The discontinuity in the 2.2. Corrosion studies of hard coatings

The electrochemical reactions assess the stability in the physiological

conditions and the chemical stability of the nitride coatings. Different
types of electrolyte like simulated body fluid (SBF) [16,48], Tyrode’s
simulated body fluid (TSBF) [51], HCl [52,53], goat blood plasma [54],
artificial saliva [55] was employed for the corrosion studies for different
nitride coatings. TiN, TiAlN and TiON thin films on CP Ti substrates was
developed by Subramanian et al. and studied their corrosion resistance
in the SBF electrolyte solution [16]. TiAlN coatings’ impedance and
polarization measurements (Fig. 8a) exhibited higher corrosion resis­
tance than other coatings [16]. The nitrided Zr layers corrosion and
tribocorrosion properties were analysed by Reger et al. The corrosion
resistance of the nitrided specimens at higher temperature showed
higher corrosion resistance and wore resistance in SBF [73]. Çaha et al.
evaluated the corrosion resistance of TiN in NaCl, and additionally,
tribocorrosion was done using a ball on plate tribometer [52]. TiN
coating (Fig. 8b) of 80 min deposition had greater resistance to corro­
sion, and the tribocorrosion was carried out under OCP (open circuit
potential) and one ball on plate tribometer. When the sliding started, the
TiN samples OCP values are gradually decreased (Fig. 8b). The initial
drop of OCP when the sliding started was due to native damage to the
film. The next drop indicates damage of the coating on the contact re­
Fig. 5. (a) Nanoindentation of TiBN thin films [38]. gion along with the alumina ball, which results in exposure of the

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Fig. 6. Scratch tracks on TiN/a-C:H multilayer (a) 1.5 N, (b) 10 N, (c) 28 N [25].

Fig. 7. Macroscopic images of coating wear in the retrieved UNI tibial tray retrievals displaying (a) frosted unworn areas (white arrow), minor scratches present
(grey arrow) (b) curved patches with coating wear through (arrows) in one of TKR tibial trays; (c) the damage score of the retrieved material [50].

Fig. 8. (a)The potentiodynamic polarization curve in SBF [16]. (b) Representation of OCP COF under sliding of the coatings [52].

substrate(Fig. 8b) [52]. increase in passive current density of the TiN coatings in the potentio­
The titanium nitride coatings are employed for corrosion-resistant dynamic polarization test is due to the oxidation of Ti2N and Ti4N2.33
coatings in implant materials [56]. When the coating thickness in­ phases [60,61]. A similar process was reported by Pohrelyuk et al. [62]
creases, the corrosion resistance is ascribed to the alteration in the phase for the oxidation of the TiN phase, the reaction was given below
stoichiometric that changes the crystalline structure and lattice param­
2TiN + 2yH2 O → 2TiNx Oy + (1 − X)N2 + 4yH + + 4ye− (1)
eters [57]. Additionally, the upsurge in the quantity of Ti2N phase is well
known for its stability and better electrochemical property [58,59]. The

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2.3. Biological properties (Fig. 10a) of BMSCs blue-purple spots, which is a more significant per­
centage of the ALP than control. The calcification by alizarin red
The biomaterials are placed very close and connected to living tissue, staining (Fig. 10b) showed increase in calcium nodules for induction of
and an important issue is that the material implanted should not induce 14 days. ALP activity and calcification validated that the in vitro oste­
any adverse reaction in the human body. Thus the material used as ogenic activity was enhanced by TaN [78].
bioimplants surface should be non-allergic and free of toxic elements. Another essential factor for biocompatibility is the blood compati­
Biological studies like tissue capability inspected the hard coatings’ bility (hemocompatibility) of the implants that act as an interface be­
biocompatibility by cytotoxicity, the blood compatibility by hemo­ tween blood and the material. The important step for thrombus
compatibility and hemolysis, antibacterial activity to assess the bacte­ formation on implants takes place due to the fibrinogen and globulin
ricidal effect in vitro cell line studies and the in vivo animal studies were adhesion. This activates the platelets enzymatically to form clotting of
employed. The titanium nitride was coated onto Ti, and its in vivo blood [51]. The results displayed (Fig. 11) the nitride coatings only less
antibacterial activity was evaluated by Antonio et al. [63]. A detachable adhesion and decreased platelet activation confirms the hemocompat­
TiN-coated and uncoated acrylic device were fixed to the ible nature of the coatings [37,38,51,80–82].
molar-premolar region of the jaws of six volunteers. After 24 h, the SEM The surface properties of the biomaterial are responsible for the
examined the device exhibited a substantial reduction of bacterial enhancement or inhibition of bone formation. The inhibition may
presence on the TiN surfaces. The biocompatibility and cell toxicity of depend on the metal ions released from the implants, and so the surface
the nitride coatings were studied with different types of the cell lines in properties should be optimised to decrease the adverse effects [83,84].
vitro like human bone marrow stem cells (BMSC) [64–66], Saos-2 cells The diffusion of metal ions from the implant material can be reduced by
[67], MG63 osteoblast-like cell [68], L929 mouse fibroblasts [69,70], coating their surface with TiN and thick TiO2, which may be potential in
human fetal osteoblasts [71], murine calvarial osteoblasts and murine vivo applications [85,86]. In vivo biocompatibility studies are carried for
monocytes cells [72,73]. The cytotoxicity studies on different cell lines the TiN coated specimens by implanting them into rabbits [87], rats [88,
showed good viability and proliferation of cells on the nitride coating 89] and dogs [90]. The TiN coated stainless steel was implanted in dog
compared to control. The nitride coatings showed the excellent adhesion
of cells and the original morphology of the living cells with differenti­
ation and metabolic activity of the cells [64–72,74–76].
Fibroblast (HGF) proliferation and inactivation of bacterial biofilm
of TiN and ZrN coatings were compared by Brunello et al. [77]. The IF
staining of vinculin (Fig. 9a&b) signifies the key link between crucial
adhesions. The actin cytoskeleton (Fig. 9c&d) showed the adhesion of
cells onto the surfaces. The ZrN and TiN coatings have effective bacte­
ricidal activity against five bacterial strains [77]. Li et al. demonstrated
the biocompatibility of the TaN (tantalum nitride) by BMSCs [78]. The
images (Fig. 9e&f) display the cell morphology of expanded character­
istic spindle-shaped BMSCs. The TaN coatings deliver exceptional cell
adhesion and spread breed conditions much faster than control [78].
The biological activity of the orthopedic implants depends on the
osteogenesis differentiation of the cells. The ALP activity is a primary
osteoblast indicator, and its activity is related to osteoblastic differen­
tiation [79]. In the later stage of osteogenesis, calcium nodules are Fig. 10. (a) ALP staining of TaN and control at 7 days (b) Alizarin red staining
mineralised from ECM (extracellular matrix). So the calcium deposition of TaN and control at 7 and 14 days [78]. (For interpretation of the references
also reflects as a pointer of osteogenesis, and it is examined by alizarin to colour in this figure legend, the reader is referred to the Web version of
this article.)
red staining [78]. TaN coatings exposed the ALP staining for 7 days

Fig. 9. The HGFs morphology on Ti and coatings displaying (a&b) vinculin staining (upper panels) (c&d) Phalloidin staining display labelling of actin filaments
(lower panels) and blue stained nuclei at 40x magnification [77]. (e&f) Morphology of BMSCs on TaN for (e) 1 h and (f) 2 h [78]. (For interpretation of the references
to colour in this figure legend, the reader is referred to the Web version of this article.)

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Fig. 11. Hemocompatibility SEM micrograph of PRP (plasma rich platelets) [38].

femurs, and the implants did not show any bone opposition for 4 weeks. stability of MGs is the different atomic size of atoms and densely packed.
The bone affinity of the implant is comparable to alumina [90,91]. The atomic size of Zr is 0.155 nm, and Cu is 0.135 nm, which is the
Wistar rats of six-month-old were employed to implant the TiN and motivation for the thermal stability of the Cu–Zr MGs [98]. Chuang et al.
uncoated specimens. The specimens were placed into the femoral fabricated Zr–Ni–Al–Si TFMGs with different nitrogen flow rates [99].
medullary canal of the rat. The samples showed good mineralization and The XRD pattern of ZN-0 and ZN-1 TFMGs are amorphous in nature, and
were labelled with oxytetracycline and confirmed. The implants showed others are crystalline. The corresponding DSC curves of ZN-0 and ZN-1
good alkaline phosphatase activity by observing the bone layer nearby exhibited Tg and Tx because they are glassy and amorphous in nature.
the implants. Improved ALP activity and weaker activity of The other TFMGs did not display Tg and Tx since they are crystalline and
tartrate-resistant acid phosphatase were revealed histochemically [88]. absence of glassy amorphous state [99]. The same response was reported
The implant studies confirm the non-toxic nature and bone formation on by Lee et al. [100] for Ti-based metallic glasses. When the carbon con­
the coatings. centration is increased to the composition, they become crystalline and
forms TiC crystalline phases when the percentage of carbon is 12%
3. Thin film metallic glass (TFMGs) (Fig. 12a) [100]. The crystalline phase formed in the composition
specimens do not show glass transition (Fig. 12b) and they change the
Metallic glasses (MGs) are the amorphous structured material in thermal stability of the specimens [100]. The Ti–Cu–Zr–Ni–Hf–Si
which the molten alloy was rapidly cooled that overcomes the nucle­ TFMGs’ thermal formability was enhanced by the upsurge in bias
ation of crystalline phases to form alloys in glassy nature. The speedily voltage was deduced Kobata et al. [101]. Two different forms of
cooled amorphous frameworks have worthy properties like improved Fe–Cr–Mo–C–B–Y MGs were fabricated as rod and film, and the DSC was
strength, hardness and corrosion resistance properties [92,93]. The carried out. The MG rod showed Tg and Tx, but for TFMG, Tg was found.
vapour metal atoms are condensed to form amorphous layers of solid The amorphous phase in a TFMG was deduced by volume fraction by
thin films called TFMGs. Immiscible super saturated elements can be comparing the ΔH (heat of crystallisation) by the formula given [102].
easily made alloy using vapour to solid condensation [94]. The bio­ ΔHcoating
materials are surface modified with TFMGs provides a humble way to am.% = (2)
ΔHrod
evade the manufacturing hurdles of bulk metallic glass (BMG) with
retaining its ultimate properties. The TFMGs improve the surface
properties like corrosion resistance, glass-forming ability (GFA) and 3.2. Mechanical properties of TFMGs
mechanical properties [95].
The mechanical properties of biomaterials attain exciting impor­
tance owing to their part in orthopeadic applications. The properties
3.1. Thermal property of TFMGs such as hardness and Young’s modulus of the TFMGs are evaluated by a
reliable solo test, namely nanoindentation.
The properties such as glassy nature and thermal stability are eval­ TFMGs mechanical properties are displayed in Table 3. The rapid rise
uated by differential scanning calorimetry (DSC). When a gradual rate of in hardness of Zr TFMGs with the incorporation of nitrogen is due to the
heat is increased to the TFMG, the first stage is the glass transition arrangements of short-range order (SRO) nitrogen atoms. The atoms of
temperature (Tg). The continuous rise in temperature leads to crystal­ nitrogen centred structures displayed a larger elastic modulus due to the
lisation temperature (Tx), later is the melting temperature (Tm) and reach of low configuration potential energy [118]. Similar results of the
liquidous temperature (Tl). The region between Tg and Tx is the super­ increase in nitrogen increase the hardness and modulus were found by
cooled liquid region (SCLR) (ΔTx = Tx− Tg) [96]. Zr based MGs have Chuang et al. for Zr–Ni–Al–Si TFMGs owing to the creation of crystalline
remarkable GFA and large SCLR. Atomic packing density (APD) also ZrN nanograins [99]. Two Ti-based TFMGs systems exhibited Young’s
influence the GFA in which the native atoms’ arrangement is associated modulus of 106.4 GPa and 110 GPa with a hardness of 7 GPa [112,119].
with the structural stability, which is interconnected to Cu–Zr MG Ti-based TFMGs of different boron concentration load-displacement
properties [97]. Another essential criterion for enhanced thermal curves was displayed in Fig. 13, which displayed pop-ins [120]. The

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Fig. 12. XRD pattern and DSC thermogram of the Ti MG [100].

Table 3
Mechanical properties of TFMGs.
Chemical composition(at.%) Elastic Hardness Yield Reference
modulus GPa Strength
Gpa (GPa)

Zr53Cu29Al12Ni6 117 5.5 2.6 [103]

Zr52Cu48 97 5.4 - [104]
Zr86Cu8Ag6 78 4.2 - [104]
Zr73Cu16Ag11 80 4.3 - [104]
Zr47Cu28Ag25 110 5.9 - [104]
Zr46Ti40Ag14 109.15 6.12 - [105]
Zr46Ti43Al11 126.5 5.61 - [105]
Zr60.14Cu22.31Fe4.85Al9.7Ag3 116.1 7.0 - [106]
Zr41.1Ni30.3Al1.3 Si5.2 N17.7 223 14.7 - [99]
Zr48Cu52 123 5.2 - [107]
Zr6Cu7Ni43Al44 159 8.2 - [107]
Zr50Cu50 98 6.2 - [108]
Zr52.2Cu30.4Ni8.6Al8.8 112 4.7 - [109]
Zr32Cu20Al8Ni5N35 190 9.5 - [110]
Zr33.4Cu17.6Al5.4Ni4.1B12.3N26.8 219 15.1 - [110]
Zr48Cu36Ag8A18 112.6 8.92 - [111]
Ti40Cu36Pd14Zr10 106.4 7 - [112]
Ti47Zr41Si12 109 5.2 - [113]
Ti58Zr33Si9 115 5.3 - [113]
Ti66Zr25Si9 116 6.2 - [113]
Fig. 13. Nanoindentation curves of TiCuZrPd:B TFMGs [120].
Ti75Zr19Si6 110 4.8 - [113]
Ti40.8Cu42.3Zr2.5Ni7.3Hf4.7Si1O1 128 6.5 - [114]
Fe37– 33 Zr35 Nb21-26 107–114 8–8.6 - [115]
Zr38– 29 Ti21–17Fe37– 49 102–124 7.3–9.3 - [116]
where, Lc - critical load, dc - track width, E - coatings’ elastic modulus, T-
Fe44Cr15Mo14Co7C10B5Si5 193.4 8.45 - [117] film thickness, W - work of adhesion.
Ti–Cu–Pd–Zr TFMG was employed to identify the work of adhesion
for the Lc3 was found to be 1.4 × 1014 N/m [119]. The sharpness of the
same observation of discrete pop-ins in the load-displacement curves surgical blade was deduced by blade sharpness index (BSI). The formula
with different Fe content of Fe–Zr–Ti TFMGs was studied by Chen et al. used to calculate BSI was [123]:
[116]. The pop-ins are associated with the load drop due to the solitary ∫ δi
shear band formation and rapidly oblige the applied strain. The discrete Fdx
BSI = 0 (4)
displacement in the curves was owing to the formation of shear bands in δi tJIc
the way of nanoindentation [116].
The adhesion of the coatings with the substrates was assessed by Where,
scratch test. The failure of adhesion of the film to the substrates was F- force applied, dx - blade displacement increment, δi - initial
estimated by the critical load (Lc), which is the scratch resistance [111]. indentation depth of blade before fracture substrate, t - substrate
ZrCuAlNi TFMGs adhesion to SS was measured with scratch test and thickness, JIc - fracture resistance.
conveyed that the nucleation, formation and propagation of shear bands Fe based TFMG was coated on SS blade, and the BSI was compared
are accountable for the ploughing and wear deformation behaviour with the uncoated blade. The uncoated SS blade exhibited higher BSI
[121]. The resistance of scratch of ZuCuAgAl and TiCuPdZr TFMGs was (0.31) than the TFMG blade (0.28). This reveals the coated blades
proved by critical loads (Lc), acoustic emission and the penetration improve sharpness, and it is durable even at a cutting length of 50 cm is
depth of the coatings [94,119,122]. due to its superior hardness of 1200 HV [123]. Surgical blades made of
The work of adhesion of the coatings was calculated from the for­ BMG and Zr-based TFMG coated SS displayed lower BSI (0.25 and 0.23)
mula by scratch test [119]: than uncoated SS blades (0.34). Tsai et al. suggested a 26.5%
√̅̅̅̅̅̅̅̅̅̅ enhancement in sharpness of the blades [124]. Additionally, he coated
πd2 2EW
Lc = c (3) Zr based TFMGs on SS blade with different thicknesses and found even
8 t after 20 cm cut, the coated blades were durable, and the BSI was less

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than 0.45. This proposes that the sharpness and durability of the blades content [113]. The resistance to corrosion of the Ti TFMG by the Tafel
are increased by the TFMG coatings [125]. Zr53Cu33Al9Ta5 TFMG was plots and impedance spectroscopy was evaluated by Rajan et al. [112].
coated onto the syringe needles and compared with titanium and tita­ Higher Rct and the nobler potential of TFMG confirmed the corrosion
nium nitride coatings. The TFMG coated needles displayed a reduced resistance nature [112]. When the Ti-based TFMGs was immersed in an
insertion force ~66% and a retraction force of ~72%, with a lower electrolyte, a passive layer was formed, and a stable oxidised layer of
coefficient of friction [126]. TiO2 was formed on the surface is the cause for corrosion resistance. The
The TFMG covered needles’ non-sticky nature was evaluated in vitro Ti TFMG coated specimens have a lower corrosion rate with a passive
using a mouse model similar to human skin. The uncoated needle behaviour than 316L SS [119], Ti and its alloys [6,112]. The amorphous
(Fig. 14A, B) stuck to the tissues clearly, and during retraction, a hump- TFMG display excellent corrosion resistance with the random arrange­
like elevated tissue area was found. No hump was observed during ments of atoms, lack of crystalline defects and vacancy. Fig. 15 exposed
retraction (Fig. 14C, D), evidently clarifying the needles coated with the corrosion resistance of Ti-based TFMG immersed in SBF for 7–21
TFMG are in non-sticky nature. Compared to the uncoated needle, the days with nobler potential than bare specimens [6]. The SBF immersed
needle coated with TFMG showed lower tissue adhesion of 79.6%, specimens form a denser passive film when immersed in SBF for a
which was accredited to the non-stick nature. The grain boundary-free, period, and the passive current density naturally increases [6]. The
smooth surface, and low surface energy may be the reason for the TFMGs amorphous nature and absence of arrangement of ordered atoms im­
anti-adhesion performance [127]. proves the electron activity and reduces the electrons work function, and
the surface was passivated to form stable passive film [140].

3.3. Corrosion studies of TFMGs

3.4. Biological studies of TFMGs
The corrosion studies can evaluate the TFMG coatings stability in
physiological and chemical environments based on the electrochemical Biocompatibility is the primary requirement of the materials used as
reactions. The corrosion property of TFMGs were studied by the in­ implants and hence gets more importance. The bio-implants should not
vestigators in various types of electrolytes like simulated body fluid produce any contrary reaction when interacting with tissues and exist in
(SBF) [6,112,113,119,122,128], Hanks solution [95,113,129,130], the body. The biocompatibility of TFMGs is inspected by cytotoxicity,
phosphate-buffered saline (PBS) [131–133], artificial saliva [106], 5 wt hemocompatibility, bactericidal property and in vivo animal studies. The
% aqueous NaCl solution [116,117,134], artificial sweat solution [135], TFMGs having Ag and Cu in the metallic composition are bactericidal
1 M HCl [102,136], HBSS [132], Ringer’s solution [137,138], 1 mass% and evaluated by gram-positive and negative strains like E.coli and S.
Lactic acid [132]. The positive shift in corrosion potential (Ecorr) and the aureus [104,105,122,141–143]. The Zr–Ag–Al TFMG coated surface
negative shift in current density (Icorr) compared to the uncoated spec­ exhibited the colony reduction bacteria and shrunk or distorted the
imens such as Ti and Ti alloys, SS, recommends the TFMGs are more death of both bacterial cells [142]. The release of Cu or Ag ions that are
degradation resistant and protective in different electrolyte [111,122, feebly bonded or chemical ionization and redox reaction is attributed to
128]. A Zr based TFMG surface forms a passive layer when immersed the antibacterial behaviour of TFMGs [142]. The destruction of E.coli
into an electrolyte, and it is composed of a stable oxide layer of ZrO2 was envisaged by Epi-fluorescent microscopy of Ti-based TFMG. The
[111]. The mechanism of corrosion of the Zr-based TFMG was discussed green-stained E.coli was alive initially later, it turned red after a period
by Chuang et al. [136]. The corroded morphology of the TFMG showed of incubation, endorsing the death of bacteria [119]. The positively
radical wrinkles and circular cracks. The passive film breakdown is the charged metal ions were attracted to the bacterial cell walls, which are
reason for pitting corrosion in the amorphous materials. Additionally, negatively charged by electrostatic attraction force. The cell wall is
radical wrinkles or “river-flow” patterns with cracks and pits are related adhered by the ions and damage the cell membranes, then react with
to the crevice corrosion reactions [136]. The filiform corroded surfaces proteins in the bacteria, leading to death [122,141,143].
are developed with passive layers and covered. The filament propagated The blood compatibility of the material was evaluated by incubating
from corrosion pits randomly [136,139]. the material with blood. Hemocompatibility is also a crucial element for
Ti-based TFMGs with different concentrations of titanium showed an biocompatibility which imitates the status of an interface between blood
improvement in corrosion resistance with the increase of titanium and material. The Zr TFMG and Ti-based TFMG surfaces reveal separate

Fig. 14. Images of injecting the mouse dorsal skin: (A, B) bare needles; (C, D) needle coated by TFMG [127].

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Fig. 15. Corrosion of TFMG (a) AC impedance studies and (b) Tafel plot [6].

RBCs lacking in the agglomeration and no formation of a cluster of RBCs. of the Zr, Ti, Fe, Mg-based TFMGs was confirmed by the increase in cell
The disc structured morphology of biconcave shape retains the shape of viability and proliferation from MTT assay [6,112,120,127–129,137,
the blood cells confirming hemocompatible surfaces [6,128]. The un­ 148,149]. Cell adhesion and proliferation are important features of
coated specimen displayed the aggregated platelets and activated biocompatibility, which can be identified from morphology and the
morphology of 3D fibrin mesh formation. This leads to the agglomera­ number of cells adhering. Two types of TFMGs displayed the MC3T3-E1
tions RBCs and deformation of platelets, and finally, the formation of preosteoblast cells morphology Fig. 17. The viable cells on the surface
thrombus [6,128]. Quartz crystal microbalance (QCM) systems are also indicate that the coloured stretched cytoskeleton and the blue nuclei are
utilized to measure hemocompatibility. Lower absorption of fibrinogen well adhered to and spread on the surfaces. The elongated and
protein and larger albumin absorbed by Zr TFMG coated QCM and spindle-shaped cells show a remarkable growth on the TFMG surfaces
attained fibrinogen/albumin (F/A) ratio was 3.9 and indicated hemo­ when the incubation time increases, indicating the TFMGs are nontoxic
compatibility of the coatings [154]. Ti based TFMG with boron showed in nature [150]. Rajan et al. evaluated the mineralization and differ­
the hemocompatible nature Fig. 16 [120]. The cell morphology of TiB-2 entiation of SaOS-2 cells for Ti-based TFMG. The SaOS-2 cells showed a
was disturbed in morphology may be due to the addition of EDTA, and uniform coverage similar to TCPS control [6]. Rajan et al. studied in vivo
they return to their morphology when there is a change in biological irritation tests of Ti–Nb–Zr–Si TFMG extracts were evaluated on Albino
environment (osmolarity, pH, biochemical and electrical) [120]. rabbits. The test confirmed no formation of erythema and oedema and
The cytotoxicity of TFMG was studied via in vitro cell response and in indicated non-toxicity. The irritation index for erythema and oedema is
vivo animal studies. The nontoxic nature of the TFMGs is evaluated by 0.03 for TFMG and 0 for control for all test animals (rabbits). This is the
MTT assay and cell morphology, adhesion, proliferation and minerali­ indication of non-toxicity [6].
zation. The MTT assay, cytotoxicity and cell morphology of the TFMGS The Zr TFMG coated Ti specimens in vivo bone formation and toxicity
were evaluated by different types of cell lines like mouse fibroblast cells was studied by implanting the specimens into the rat femur for eight
(L929 fibroblast cells) [6,96,106,122], osteoblast SaOS2 cells [6,144], weeks. The new bone formation was found on the TFMG coated pin after
mouse preosteoblast MC3T3-E1 cells [6,105,128,145], MG-63 cells 8 weeks of implantation [128]. The ear vein of rabbits was detained with
[137,146] and NIH3T3 fibroblast cell [129]. MTT assay represents the hypodermic needles coated with Zr–Cu–Al–Ta TFMG for 3 days. After
viable number of cells in any given sample [147]. The non-toxic nature detained the needles, the puncture wounds’ histopathological biopsies

Fig. 16. Hemocompatibility of Ti based TFMG with different boron concentration [120].

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Fig. 17. The MC3T3-E1 cell morphologies a–c) Zr–Ti–Cu–Ag and d–f) Zr–Ti–Co–Ni TFMGs for 3, 4, 6 days [150].

showed (Fig. 18B, C) a pinhole in the epidermis layer prolonging only which is very few for the TFMG coated needle. The statistical results
below to the dermis layer when examined closer to the internal vein estimated the length of venous wall damage was 32.97% ± 9.09 for the
vessel wall exposed endothelial cells of two types. The first one is uncoated needle group and 21.99% ± 7.56 TFMG-coated needle group
recently regenerated endothelial cells with rolling morphology and [127].
quasi-round shape (Fig. 18D); the other one is well-attached and flat
morphology (Fig. 18E). The recently regenerated endothelial cells are 4. Diamond-like carbon coatings in medical applications
due to the vein walls’ inner lining injury by the needles’ rough surface,
Diamond-like carbon (DLC) coated implant materials have gained
extensive interest due to their good tribological and mechanical prop­
erties. The DLC’s arduous nature and low friction with the biocompat­
ibility lead it to be a prominent candidate as coatings on orthopedic
implants [151,152]. DLC has some essential properties like wear and
corrosion resistance and is considered to be chemically inert; these
properties protect implants [153]. Furthermore, DLC can be alloyed
with specific amounts of different elements like Si, Ag, N, F, O, Ti, Co,
Mo and their combinations into the coatings and still, they are amor­
phous in nature [154]. These characters make the DLC coatings noble
aspirants for biocompatible coatings for biomedical devices and tools.

4.1. Mechanical behavior

The wear rate and friction should be low for the materials used for
biomedical applications, and the hardness of the coating should not
produce any excessive wear of the counterface material [155]. Liu et al.
reported when the sliding wear takes place, the external layers of DLC
were transformed to graphite, and the wear and friction rate was
meager. The transformation takes place in two stages: lattice relaxation
in the structure due to hydrogen release and shear deformation forms
graphitic structure from DLC [156]. The essential condition for DLC to
be enabled as a coating for the implant is good adhesion. The adhesion of
the DLC with the metals can be improved by coating a Si interlayer in
between DLC and metal [153,157]. Chromium and tantalum as inter­
mediate layers enhance the adhesion of DLC to the different metals, and
additionally, it can be achieved by modifying the deposition parameters
[153,158].
The adhesion of the coatings with the substrates was evaluated by
scratch test. The primary mechanism of the failure of the coatings was
buckling cracks, clipping spallation and subsequently coating delami­
nation. E. Marin et al. studied the adhesion of the DLC coatings for
different biasing voltages [159]. The scratch test outcome (Fig. 19)
revealed that the adhesion of the coating failed at lower applied loads
Fig. 18. (A) Optical photograph of detain needle; (B,C) histopathological bi­ for the higher bias voltage coatings. The coating without bias voltage
opsies of a puncture wound in-ear vein of rabbit after bare and TFMG-coated stands to a load of about 100 N, and the other specimens with bias
needle was detained for 3 days, respectively (B,C) Zoomed image of the inner voltage coatings, the fracture is due to lack of adherence to the substrate
wall of the vein vessel from (D,E) [127]. and brittleness. The hydrogen presence plays an essential role in

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Fig. 19. The scratch tests for adhesion of the DLC coatings of different biasing voltage [159].

tenacity, which leads to the creation of C–H bonds and structures of is a decrease in hardness and modulus [169]. The hardness and Young’s
hydrocarbon, which release the stress and make the film softer and less modulus decreased in F-DLC due to the formation of C–F and the C–F
brittle [159]. The adhesion of the coatings can be improved by adding an bond being weaker than C– – C [170]. Additionally, Jacobsohn et al.
interlayer, and the other one is doping into the film. The DLC with the suggested that the C–C network is the reason for the hardness of DLC.
content of Zr presented good adhesion compared to the DLC coatings The addition of F interrupts this network, which may be the reason for
with only minor cracks and petty delamination of coating [160]. DLC weaker hardness [171]. The hardness, Youngs modulus and friction
doped with Ti films with interlayers of AlTiN and Ti was prepared by coefficient of different DLC are displayed in Table 4.
Pang et al. [161] and found the adhesion was greater for Ti-DLC with an The tribological properties of the film depend on the type of coating
interlayer of AlTiN; the Lc3 value was about 47.8 N [172]. The critical and contact parameters or working conditions. The coatings coefficient
loads Lc2 for Ti–C: H thin films was from 40 N to 70 N prepared by of friction (CoF) depends on its thermal stability, which depends on the
PEVCD at the laboratory of Vitu et al. [162]. A Ti interlayer was coated structure and coating operating atmosphere [180]. The
on WC–Co substrate, and the adhesion was measured as 39 N by Tsai and hydrogen-containing DLC displayed a very low coefficient of friction of
Chen [163]. Czyzniewski et al. employed RF PACVD to coat Cr-DLC thin 0.05 in dry air, and when the humidity increases, the friction increases
films, and the Lc3 was estimated to be 39 N [164]. Additionally, from 0.15 to 0.3 [181]. Conversely, the carbon amorphous films friction
different researchers studied Cr doped DLC adhesion with different reduces with an increase in moisture [182]. The moist surroundings,
concentrations of Cr as dopant [165–167]. sliding of DLC films induced dangling bonds and passivated by water
In the biomedical application, the hardness and modulus of the molecules. The strength of the bond increases from C–H to C–O bond,
coatings are essential since the contact pressures in hip and joint which results in a more significant interaction between the interfaces of
replacement may cause wear of the material. The hardness and modulus the sliding surfaces and increases in friction [183]. When different
are directly related to the material wear resistance. The coatings hard­ metals are doped in DLC, the mechanical properties are changed like a
ness and modulus are studied by nanoindentation test. The hardness and release in stress, increased adhesion and hardness, and their tribological
elastic modulus of the films increased (Table 4) when the silicon content properties [180]. Kim et al. coated DLC with different Si concentrations,
increased due to the microstructural change [168]. The Si, and their CoF was studied. The Si doping greater than 8% showed lower
nitrogen-doped DLC showed higher hardness due to the formation of CoF. The debris with rich Si and transfer layer directed to the formation
C–Si bonds and C–N bonds, which is weaker and when the nitrogen of low friction film. Si with 17 at % showed the lowest CoF of 0.05, and
percentage increase, the harness decreases due to the poor bond strength when the Si content has increased, the film’s harshness got to reduce,
of N–Si [168,169]. When the fluorine content increases in the DLC, there and the film got destroyed [184].
The wear process of DLC coatings involves mechanisms such as
abrasive wear and polishing wear which is due to carbon diffusion on the
Table 4
Mechanical properties of different DLC thin films.
process of wear. The mechanism of wear of DLC was given in four
different stages (Fig. 20). The first stage was due to applied load; the
Coating Doping Hardness Youngs Friction Reference
harder DLC tries to penetrate the softer counter surface, which results in
element Gpa modulus coefficient
GPa the plastic flow of the material around the coated surface. The second
one is the increase in frictional forces and temperature due to the
DLC - 25.46 184.51 0.17 [168]
Si-DLC Si 26–31 185–209 0.21–0.30 [168]
abrasive wear of coated asperities. The third is the formation of micro-
Si–N- Si, N 26–30 185–212 0.13–0.17 [168] cleavage due to the rise in carbon diffusion, which weakens the
DLC atomic bond strength. The coating surfaces roughness and friction co­
F-DLC F 10–18 90–160 0.04–0.11 [169] efficient is reduced. The fourth stage is the increase in carbon diffusion,
Si-DLC Si 12–18 135–185 - [172]
which weakens the coatings, increases the smoothness, and decreases
N-DLC N 15–65 152–180 0.05–0.27 [173,
174] the friction coefficient. Strengthening of counter surface and smoothness
Cr-DLC Cr 16.6–23.9 166–213 0.05–0.15 [175, of coated surface results in stabilization of friction coefficient [185].
176]
Ag-DLC Ag 13–18.5 ~360 0.05–0.17 [177,
178]
Ti-DLC Ti 9–13 135–156 - [179]

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Fig. 20. Schematic of wear mechanism [185].

Fig. 21. Image of the surfaces after the salt spray test (a) DLC, (b) TiN and (c) uncoated stainless steel [204].

4.2. Corrosion studies b), and the uncoated specimen showed a corroded region close to the
edge (Fig. 21c). The DLC showed more excellent corrosion resistance
Improved protection against corrosion of metals was offered by DLC compared to TiN and uncoated samples. The edges showed corrosion
and DLC doped with different materials [159,186–194]. The addition of due to the plastic deformation when cutting it [204].
Si into DLC films leads to a substantial enhancement of the resistance to The corrosion depends on the film structure and defects in the film,
corrosion of the films by increasing Rct and decreasing Icorr (anodic like the bumps or bubbles and holes. The pin holes reduce the corrosion
current) in polarization, which could be ascribed to the creation of a resistance of the coatings. The pitting corrosion originates from the pore,
coatings which is more denser coating, thus hindering the diffusion of and the substrate is exposed to the solution, and the pit nurtures deeper
water molecules or ions [195–198]. Another critical parameter is the and sideward. They reach the interface, and mechanical support of the
porosity density to assess the protection to corrosion by the DLC films. film is lost; this produces cracks leading to coating failure [197]. After
The nano porosity density increased when the immersion time was the corrosion test, the morphology of the coatings was studied using
raised in the electrolyte [199]. The corrosion resistance of the DLC films SEM (Fig. 22). The coatings with Si-doped DLC and DLC at a bias voltage
was significantly increased by the immersion time in the electrolytic of − 800 V (Fig. 22b&c) showed no indication of penetration of water
solution. The pores were filled, and the film was passivated, and the and ions, and the DLC with lower bias voltage − 400 V (Fig. 22d) showed
electrolyte access to the substrate was prevented [200]. When the the spot and protrusion of the film flaked off due to diffusion of water
thickness of the film was increased, the resistance to corrosion of the and ions. The Si-DLC and DLC at higher biasing voltage are corrosion
DLC increased was reported by Sharma et al. [201]. The influence of resistant without any damage [203]. The surface roughness is also an
adhesion strength on the films corrosion protection was studied by Liu essential parameter for causing craters and surface flaws distributed in
et al. [202]. When the strength of adhesion was higher, the film’s the outer surface of the coating.
corrosion resistance was increased. They decreased the undermining
effect from the corrosive media and enhanced the corrosion resistance.
The DLC and the DLC doped with metals’ corrosion resistance was 4.3. Biocompatibility of the DLC coatings
assessed by electrochemical accelerated corrosion tests in a different
electrolytic solution such as SBF [203], 3.5% NaCl [204], Hanks solution When a material is used as a biomaterial, it should pass through a
[159,205], phosphate buffer saline (PBS) [186] etc. progression of assessments far as its biocompatibility and tissue
The electrochemical corrosion studies assessed the stability of the compatibility (nontoxicity). In vitro cultured cell line studies in
DLC coatings in the physiological conditions and their chemical stabil­ controlled conditions is perhaps the frequently utilized methods. The
ity. Salt spray tests assessed the corrosion resistance of the DLC thin macrophage is an appropriate cell that plays a leading role in inflam­
films in 5 wt% NaCl solution for 100 h. The DLC and TiN coated samples mation and the reaction with foreign bodies, which is an appropriate cell
didn’t present indications of general or localised corrosion (Fig. 21a and for in vitro biocompatibility testing of material. DLC was good in
physiochemical properties [206,207], additionally several in vitro and

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osseointegration was improved when silicon was added to the matrix of

DLC [152,230–232].
It was proved the Si-DLC do not show any cytotoxicity to those cells
endothelial cells. The human endothelial cells attachment and growth
was favoured by increasing the Si concentration [230]. Okpalugo et al.
carried out experiments and confirmed the non-toxicity of the DLC
coatings containing silicon, and it doesn’t disturb the viability of the
bovine retinal pericytes [231]. Nitrogen is one more dopant that en­
hances the DLC thin films biocompatibility. Liao et al. quantified that the
nitrogen-containing DLC coatings enhance biocompatibility and in­
crease mouse fibroblast’s proliferation and attachment [233]. Yang et al.
gained results representing N-doped DLC thin films human microvas­
cular endothelial cells growth by improved MTT activity reproducing
the proper cell metabolism [234]. N-DLC and undoped DLC were
compared by Okpalugo et al. and proved the N-doped DLC had a better
attachment of human microvascular endothelial cells than the other
[232]. Ca containing DLC promotes the proliferation and adhesion of
mouse fibroblasts [235]. Yate et al. fabricated Nb-doped DLC and TiO2
thin films by sputtering and compared their biocompatibility using
preosteoblasts (MC3T3-E1) cell line (Fig. 23). The Nb–C and DLC thin
Fig. 22. Morphology of the coatings after corrosion studies, (a) uncoated films have an improved adhesion of cells of similar size and exhibit
substrate, (b) Si–DLC (− 400 V), (c) DLC (− 800 V), (d) DLC (− 400 V) [203]. obvious rearranged cytoskeleton with distinctive stress fibers inside the
cytoplasm, especially at the border of the cells. The Nb–C films have
in vivo studies confirms the its biocompatibility [186,187,189,192–194, improved alkaline phosphatase (ALP) activity than the other two films
197–199,205,208–211]. The DLC coatings prevent metal ion diffusion [205].
to the body from the implant, and they act as a barrier [212]. This results A key issue for the implant is when the implants are directly in
in the DLC films as a protective coating for the biomaterials, and they are interaction with blood, the ability of the implant surface to prevent
studied in biomedical applications [63,91,152,181,212–215]. The thrombus formation [154]. Krishnan et al. used whole human blood and
body’s reaction and the behaviour of cells with the DLC can be altered by a parallel plate flow chamber and revealed the platelets adherence
embedding different elements into the carbon matrix that are amor­ depend on the shear rate of the exposed material. The platelet adhesion
phous. Concerning the required biological properties, dopants are used was lower on DLC than Ti [236]. Jones et al. evidenced the thrombus
to tailor the parameters of DLC coatings to improve and achieve certain formation, platelet activation and clotting of platelets onto Ti surface,
features [154]. The nontoxic nature of DLC and its biocompatibility was and no such reaction was noticed on the DLC surface. The DLC exposed
confirmed by growing various cell type’s in-vitro onto it and learning the lower platelet coverage compared to titanium, TiN and TiC. DLC dis­
cell’s response. Different types of cell lines like fibroblasts, human played adsorption of albumin and fibrinogen in a higher ratio than Ti,
myeloblastic ML-1, SaOS2, MC3T3-E1 cells, macrophages, embryo kid­ TiN, and TiC coatings and indicated preventing thrombus formation by
ney 293 cells, hBMSCs, etc. and their responses such as cell adhesion, DLC [237,238]. F-DLC showed a higher proportion of albumin to
viability, proliferation, cell morphology, differentiation and cytoskeletal fibrinogen adsorption compared to DLC and polycarbonate films. This
architecture have been examined [88,152,209,216–221]. The viability shows the F-DLC film prevents platelet adhesion, activation, and
of cells was measured by an enzyme named Lactate dehydrogenase thrombus formation was strongly suppressed when the fluorine con­
(LDH), which was released in the death of cells. The cells grow, spread centration was increased [239]. The resistivity, work function, and
on the implant surface and attachment was observed by the glycopro­ surface energy were lowered when Si was added to the DLC matrix and
tein; fibronectin facilitates and encourages the adhesion and spreading improved hemocompatibility. DLC incorporated with Si by PECVD de­
of cells onto biomaterials [213,222]. creases platelet attachment and enhances the attachment of human
The peritoneal macrophages and mouse fibroblast grew on DLC thin microvascular endothelial cells [240,241]. Subramanian et al. evaluated
films without any inflammation, and no toxicological effects were the hemocompatibility of DLC, F-DLC, N-DLC, and Si-DLC coatings. The
observed on the culture cells [223]. The osteoblast cells and fibroblast results suggested the poor initiation of activation of platelets, and the
cells adhere and are well spread on the DLC surface, indicating the doped and undoped surfaces are hemocompatible in nature [209]. The
capability of bone to develop onto a DLC surface implant. CN films also reports demonstrated that DLC would be utilized for hemocompatible
show improved compatibility facilitating cell spreading and attachment gadgets like guidewires, stents, and heart valves.
without inducing changes in cell physiology [224,225]. The biocom­ The interaction of the biomaterial and living cells response directly
patibility of the DLC has positively affected elements such as Ti or Si can be evaluated in vivo. DLC -coated pins were implanted into the fe­
towards osteoblastic cells. The addition of Ti into the matrix of DLC was murs and soft tissue of sheep by Butter and Lettington [242]. The DLC
studied by Shroeder et al. and demonstrated the coatings encourage the coated pins displayed good bonding to the tissues compared to the un­
proliferation of bone marrow cells and simultaneously decrease the coated pins tissue interfaces. DLC-coated pins showed no indication of
osteoclast-like cells’ activity, which is accountable for the resorption of corrosion products or chronic inflammatory reaction [242]. Allen et al.
bone [226]. Francz et al. [227] showed the biocompatibility of Ti- DLC, [243] implanted CoCr cylinders coated with DLC into rats’ intramus­
and Cheng et al. proposed Ti-DLC coatings have excellent biocompati­ cular locations and in sheep’s transcortical sites. After the implantation
bility may be related to the more significant contact area and more of three months, histologic analysis displayed that the DLC coated
negative electrostatic state of the surface, causing to improved adsorp­ specimens were well accepted. The in vivo tests of DLC coated specimens
tion of calcium ions [228]. When the concentration of Ti is 1.1 at.%, the were successful, and biocompatibility initiated the authors a long-term
Ti-DLC showed better biocompatibility by osteoblasts, and Bharathy animal study of a DLC-coated knee arthroplasty [243]. The Bociaga
et al. elucidated that when the concentration of Ti was higher, it may et al. [212] investigated long term and short term in vivo studies on
lead to the titanium ions release and produce a negative impact on WISTAR-herd male rats DLC coated SS316L jewellery. They implanted
growth and proliferation of osteoblasts [229]. Additionally, researchers the DLC coated specimens for 24 h to 26 weeks, and later the animals
suggested the biocompatibility of Si-DLC by cell lines studies and the were euthanized, and the specimen surrounding tissue and spleen were

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Fig. 23. Cells cultured and their morphology on the Nb–C, DLC and TiO2 thin films for 24 h [205].

collected. The evaluation of the tissues and spleen revealed the DLC materials. The bioceramics are bioactive or bioresorbable and non-toxic
coatings are biocompatible and protect metal ion penetrations from the in nature. Bioceramics are key materials for healing bone and unce­
metallic implants in the tissues. No immune reaction was produced by mented implant fixation with the composition and coating method
the tissue and spleen for the coated specimen, while the uncoated caused [244]. Bioceramics can be used as an overlay to enhance the biocom­
a strong response [212]. Mo et al. coted DLC onto PEEK and introduced patibility of metal implants. The bioceramics can act as resorbable lat­
amino groups onto the sample surface, and in vivo bone, formation and tices and offer a temporary framework that is degraded and replaced by
osseointegration were evaluated [221]. The coated and uncoated spec­ the body and rebuilds tissue [244]. The chemical and thermal stability of
imens reconstructed 3D micro-CT images are displayed in Fig. 24. The the bioceramics with good mechanical properties like strength and wear
NH2-DLC coated PEEK displayed a fully covered newly formed bone resistance makes them a worthy aspirant material for medical implants.
layer after 10 weeks of implantation, whereas the uncoated PEEK
showed the discontinuous bone. Thus they confirmed the NH2-DLC
5.1. Mechanical properties of bioceramics in implants
coated PEEK is favourable to the osteogenic performances of hBMSCs
in vitro and can facilitate the peri-implant bone regeneration in vivo
The mechanical properties of the ceramics are brittle in nature, and
[221].
the long span survivability of the implants is crucial. So different bio­
inert ceramics are added to enhance the mechanical properties of the
5. Bioactive ceramics coatings for biomedical applications
ceramic coatings. The coating and processing techniques also improve
bioceramics [245–247]. Stanishevsky et al. fabricated CaTiO3 coatings
The current research has focused on the improvement of the bio­
by sol-gel method, and a TiN interlayer was added, and the effect of
logical properties of implant devices. This led the researcher to make a
adhesion was monitored [248]. The CaTiO3 coatings with TiN interlayer
bioactive interface of bioceramics between the tissue and the metal
improved coating performance in wear resistance, and the adhesive
implant. Bioceramics accomplish a distinctive function as biomedical
strength of the coating was 70 MPa [248]. A. Fomin et al. preheated the
Ti substrate from 400 to 600 ◦ C, and plasma spray coating was done on
the substrate, and the micro-sized layer was formed of nanograins of
20–31 nm. The HAp coatings displayed a high hardness of 0.9–1.2 GPa
and elastic modulus of 7–16 GPa [249]. The mechanical properties were
enhanced for the preheating of substrates, and the adhesion and cohe­
sion were also improved [249,250]. The mechanical properties of
different bioceramics are displayed in Table 5.
The adhesion of the bioceramics to the substrates are investigated by
scratch test. The critical load’s Lc was determined by measuring the

Table 5
The mechanical properties of bioceramics.
Thin film Deposition Hardness Elastic modulus References
process (GPa) (GPa)

HAp Microplasma 1.5–5.0 60–100 [251]

spraying
HAp Microplasma 6.2 ± 1.0 92.3 ± 11.4 [252]
spraying
HAp PLD 2.5–3.0 65–140 [253]
HAp PLD 5–28 – [254]
HAp PLD 2–3 82–92 [255]
HAp Pulsed ion beam 0.92–1.22 47.2–95.2 [256]
HAp RF magnetron 4.5–5.2 100–120 [257]
HAp RF magnetron 7±1 120 ± 9 [258]
Fig. 24. In vivo bone regeneration after implantation for 8 weeks. Left column: HAp Sol-gel 0.25 ± 0.02 28 ± 1.3 [259]
Reconstructed 3D micro-CT images of the bone. Middle column: Sequential Sr Bio Sol-gel 85–92 460-487 Hv [260]
fluorescent labelling of new bone formation. Right column: Histological Glass
observation of the peri-implant tissues stained with methylene blue/acid Mg Bio Sol-gel 90–113 430-450 Hv [260]
Glass
fuchsin [221]. (For interpretation of the references to colour in this figure
Bio Glass Sol-gel - 75 [261]
legend, the reader is referred to the Web version of this article.)

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normal tangential loads with penetration depth and acoustic emission [283–286]. The pure HAp has the ability to reduce the bacteria such as
[262]. The adhesion of HAp coatings to the substrates was measured by porphyromonas gingivalis and Staphylococcus aureus, and the incor­
Barnes et al. and Sopcak et al., and they found the standard strength of poration of fluorine enhances the bactericidal performance. Ag, Zn, Mn,
adhesion [263,264]. The heat treatment achieved a greater crystallinity, and Cu are well-known inorganic antibacterial agents integrated into the
and strong adhesion of coating was also performed by Rocha et al. [265]. CaP phase to attain antibacterial CaP coatings [287]. Copper (Cu) offers
The high temperature encourages chemical bonds formed in a vast required antibacterial activity [288,289] and encourages the associated
atomic zone mixed at the interface of the substrate and the thin film biological events to stimulate osteogenesis, inhibit in-stent restenosis,
[265]. A minor distortion in the interface of the substrate and the thin and cytotoxicity when a required percentage is applied [284]. The
film was observed by Tiwari et al. [266]. The deformation is due to the composition of the bioceramics coating system is essential, which is a
coefficient of thermal expansion mismatch among the substrate and the growth factor of bone and enhances bone osseointegration [290]. The
HAp film, which is an imperfect interface. The adhesion and bonding at composite coating of CaP can be used as a carrier for other biofunctional
the interface can be enhanced by heat treatment [266]. Khlifi et al. agents in addition to the antibacterial molecules or particles [291,292].
compared the HAp coating before and after heat treatment and a scratch Suitable alternate materials for bones are HAp ceramics, which were
track after heat treatment specimen, and the adhesion strength was accepted due to their biological and chemical resemblance to human
increased from 8 to 13 MPa [262]. Azzouz et al. evaluated the adhesion hard tissues [293]. The osseointegration of the titanium implants was
of bioglass coatings with and without thermal treatment and confirmed increased by HAp, which stimulates early osteoblast function [294]. The
the treatment enhances the adhesion of the film to Ti6Al4V substrates biomimetic coatings of CaP on different implant materials in SBF pro­
[267]. Stan et al. fabricated bioglass films, and the bonding strength was mote osseointegration and bone regeneration [295]. HAp coatings with
evaluated by pull-out adherence test, and they obtained an outstanding the addition of Mg and the osseointegration of dental implants were
value of adherence (~73 MPa) [268]. studied by Zhao et al. [296].
The HAp containing MgO and SiO2 are plasma-sprayed onto Ti by Ke
5.2. Corrosion studies of bioceramics et al. The HAp coatings with MgO and SiO2 are implanted into femurs of
rats and found the coatings exhibited increased osteogenesis, osseoin­
The bioactive ceramic thin film-coated surfaces have corrosion tegration and bone mineralization compared with pure HAp. HAp
resistance when compared to the uncoated surface. The corrosion coatings with MgO and SiO2 revealed a higher shear modulus than the
resistance of the bioceramics was endorsed with higher Ecorr lower Icorr uncoated implants in the pushout test. They indicated the better quality
compared to the uncoated specimens. The bioceramics of different of bone-implant interfaces of the coated implants [298]. The in vivo
compositions show resistance to corrosion in different physiological osseointegration and interaction of implants are schematically displayed
solutions [225,269–275,279–285]. Lopes et al. [276] developed an in Fig. 25. When the implant is placed in the body, the local pH is
Mg-Ha composite, and the corrosion resistance was increased when reduced, leading to partial dissolution of the coating surface. The metal
immersed in Hank’s solution. The decrease in the corrosion rate is due to ions of Ca2+ and PO43− are released to the surrounding and interact with
the formation of a passive layer and a shielding layer formed on the tissue and cells and reprecipitate and forms into apatite crystals and
outer surface rich in Ca, P, and O [276]. Mg alloy was coated with HAp form with collagen matrix [297]. The chemical composition, solubility,
and HAp with fatty acid salt by Zhu et al. [277]. The greater corrosion and surface topography play significant roles in the above processes
resistance was HAp, and fatty acid salt surface, which is super­ [287]. Chen et al. fabricated fluoridated hydroxyapatite (FHA) thin film
hydrophobic, and the next is HAp coating. The resistance is due to the
superhydrophobic layer made of a phosphate conversion base and a
fatty acid salt hydrophobic membrane. When the contact angle is too
high, the electrolyte does not adhere to the surface of the coating [277,
278]. Additionally, an air layer forms between the electrolyte and
specimen when the sample is immersed in the electrolyte, and the ion
exchange is prevented with the electrolyte [277]. Thermally sprayed
HAp was coated on stainless steel and post annealed at a different
temperature by Tiwari et al. [266]. The corrosion resistance of the
specimens increased with an increase in temperature and suggested the
protection efficiency was due to annealing. The reduction in porosity
grain size refinement and densification of the film controls the fluid
penetration. Another reason for the enhancement is the improvement in
crystallinity, and the structure provides greater resistance than the
amorphous structure since the atoms are closely packed [266,279–281].
The biostability of the HAp fluorine was added to the HAp matrix (FHA)
by Chen et al. [282]. The increase in fluorine content makes the surface
smoother, and corrosion-resistant and this positive effect were due to the
crystal structure of the FHA. In HAp, the hydrogen atoms are arranged in
atomic interstices neighbouring to the oxygen atoms and are oriented
randomly, which confers a certain disorder to the crystal structure of
HAp. When the F- anions are substituted in the sites of OH- ions, the
hydrogen atoms are bound tightly to F- anions due to the higher
attraction of the fluoride in respect to the oxygen. This forms a
well-organized apatite structure that increases chemical stability [282].

5.3. Biological performances of bioceramics

The flexibility in the crystal structure of HAp can accept both anionic
and cationic substitution. When a selected element is incorporated into
HAp, their biological performances can be favourably tailored Fig. 25. Schematic representation of osteoconduction on HAp [297].

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on Ti screws by PLD, implanted it into the rat femurs, and evaluated in vivo result concerning thrombus formation and blood clot could be
bone formation for 4 and 8 weeks [299]. Fig. 26 displays the recon­ found in the literature to date.
structed 3D μ-tomographs of the rat femur and red implants, yellow In the drug-eluting stents, the adhesion of polymer and the material
cancellous bone, and green cortical bone. Both bones showed the higher is a challenge, and it can be overcome by using the DLC and replacing
trabecular thickness of FHA implants signifying enhanced osteogenesis the polymer. Si-doped DLC coating was employed for drug-eluting
[299]. When FHA has implanted, the coating surface dissolves slowly, stents, and it is advantageous and supports adhesion and surface func­
and the calcium and fluoride are released into their corresponding ionic tionalization by bonding carbon [303]. Si-DLC was coated on a
forms. This accelerates the deposition of calcium salts, and calcium drug-eluting stent with good adhesion onto the metal stent. The amino
nodes are formed, and osteogenesis takes place [300]. The fluoride ions and carboxyl groups are attached to DLC by plasma treatment. The
favour mineralization and crystallisation of CaP during bone formation negatively charged surface of DLC was turned to a positively charged
and prevent caries, and the two ions favour osteogenesis [301]. Thus the surface when amino and carboxyl groups were coated onto the DLC
bone-like apatite coatings can eradicate the interfacial gap between the surface [304].
implant and the new-formed bone through the control of biodegradation The bioceramics coatings should give genuine assistance to ion-
and the good osseointegration abilities (see Fig. 25). doped or composite bioceramics coatings. This is not so effective
because of integration of ions in the HAp lattice is not confirmed. The
6. Challenges and future perspective comparison is between doped and undoped layers coated in the same
parameter and condition is not available because several parameters
The schematic (Fig. 27) displays the different challenges met by thin- play a key part, along with the composition of the coatings. Different
film coated biomaterial and its future research direction. The future compositions of coatings should be compared at the same deposition
direction is to develop coatings with osteoconductive properties and parameter and post coating conditions. Multifunction of the implants are
therapeutic agents. These coatings can offer the skill to stimulate bone provided by composite coatings of multilayer, which is the future trend.
growth, combat infection, and increase implant lifetime. Furthermore, The stress-shielding effect is the most critical issue experienced for
the formation of mesh-like or porous structured coatings enhances the load-bearing implant devices. This issue can be solved by altering the
bone growth at the interface and improvement implant fixation and surface elastic modulus of the orthopaedic implant near bones. The
heals earlier [302]. Apart from the composition, physical and chemical coatings with porosity structures mechanically match the nearby tissues
properties, the micro and nanostructured coatings have been recognized and encourage host bones to grow into them. Thus the porous layers are
as an essential factor affecting cellular responses like cell morphology, fabricated with different coating techniques.
adhesion, and differentiation. The micro and nanostructured coatings Another challenge in the field is biocompatible coatings with anti­
can be created by the plasma spray, sputtering, sol-gel technique etc. bacterial activity and non-toxic nature. The significant elements that
These interdisciplinary technologies will be critical for designing inhibit bacterial colonies and adhesion are silver and copper, which will
biomaterial surfaces and remain an excellent opening for future be suitable substitutions. The concentration of Ag and Cu is also a factor
research. Ag, and that includes toxicity to the human cells and tissues, so their
Many exceptionally encouraging results of in vitro experiments are percentage of concentration used in the coatings should induce bacte­
presented in the literature regarding DLC thin films on stents and heart ricidal effect and at the same time non-toxic to human cells. Addition­
valves focusing on concealment of clots and thrombus formation, typi­ ally, the nanostructures or nanopillars formed on the coatings by ion
cally for a short test span. No clinical follow-up depicting the long-term etching also inhibit bacterial colonies and non-toxic human cells [305].

Fig. 26. Transverse reconstructed microcomputed tomographs of (a,c) Ti and (b,d) FHA-coated implants after (a,b) 4 weeks and (c,d) 8 weeks [299].

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Fig. 27. Demonstration of several challenges met by thin-film coated biomaterial and its future research direction.

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Declaration of competing interest 21870764.2019.1669861.
[16] B. Subramanian, C.V. Muraleedharan, R. Ananthakumar, M. Jayachandran,
The authors declare that they have no known competing financial A comparative study of titanium nitride (TiN), titanium oxy nitride (TiON) and
titanium aluminum nitride (TiAlN), as surface coatings for bio implants, Surf.
interests or personal relationships that could have appeared to influence Coating. Technol. 205 (2011) 5014–5020, https://doi.org/10.1016/j.
the work reported in this paper. surfcoat.2011.05.004.
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