➔ CMU.J.Nat.Sci Special Issue on Manufacturing Technology (2011) Vol.

10(1) 39

Coating techniques for biomaterials: A review

Anirut Chaijaruwanich

Department of Industrial Engineering, Chiang Mai University, Chiang Mai

50200, Thailand.
Materials Science Research Center, Faculty of Science, Chiang Mai University,
Chiang Mai 50200, Thailand.
*Corresponding author: E-mail: anirut@eng.cmu.ac.th

ABSTRACT
Biomaterials have been extensively studied for many decades. Surface
modifications play a major role in determining the biological response. The
purpose of this paper is to present an up-to-date progress in the coating
techniques currently applied for biomaterials, including chemical treatment,
anodic oxidation, micro-arc oxidation, sol-gel, plasma spray, electrostatic spray
deposition, electrophoretic deposition and pulsed laser deposition. In the pres-
ent paper, an overview of the basic principles behind the techniques is briefly
given. A large number of research studies have shown a great thrust towards
development of surface modification techniques for biomaterials. Coatings
and films with nanostructures on bio-implants using various techniques have
become a subject of interest.

Keywords: Coating, Biomaterials, Nanostructure, Hydroxyapatite

INTRODUCTION
Biomaterials have been extensively used for many decades. It is well known
that the bulk and surface properties of biomaterials determine their long-term
performance and stability in the biological environment. The bulk properties of a
biomaterial are characterized by its mechanical behaviour and chemical stability
under in vivo condition. On the other hand, the surface properties are evaluated
by surface morphology, surface wettability and surface chemistry (Paital and
Dahotre, 2009).
Metals generally possess superior mechanical properties and find applica-
tions in hip joint prosthesis and dental implants. However, as a result of their
lack of bioactivity, they cannot serve long-term implantations. This limitation
can be overcome by applying bioactive ceramic coating on the metal surface.
Hence, the bioactivity of metallic biomaterials is improved.
Consequently, various surface coating/modification techniques have exten-
sively applied for biomedical applications. Typical techniques include chemical
treatment, anodic oxidation, micro-arc oxidation (MAO), sol-gel, plasma spray-
40 ➔ CMU.J.Nat.Sci Special Issue on Manufacturing Technology (2011) Vol.10(1)

ing, electrostatic spray deposition (ESD), electrophoretic deposition (EPD), and

pulsed-laser deposition (PLD). The basic principle of each technique is first
briefly given and then its applications are reviewed.

CLASSIFICATION OF BIOMATERIALS
Biomaterials can be broadly classified as (i) metals, (ii) ceramics and (iii)
polymers. In this paper, it is mainly focused on the metallic bio-implants as a
substrate and the bioactive ceramics as a coating.

A. Metals
Metallic biomaterials are commonly used for load bearing implants due to
their superior mechanical properties. They include stainless steels (316L), Co-Cr
based alloys and commercially pure titanium and its alloys. However, elements
such as Ni Co and Cr are found to be released from the stainless steel and Co-Cr
alloys due to the corrosion in the body environment (Geetha et al., 2009). Thus,
the surface coatings of these materials have been applied and developed.

B. Ceramics
It is well known that calcium phosphates (CaP) are biocompatible and
bioactive ceramics, which can induce bone regeneration and bone in growth at
tissue-implant interface. Therefore, the CaP can be used in order to increase a
bioactivity of metallic implants without compromising its mechanical behavior.
Hydroxyapatite (HA), for example, has widely been used for coating of metallic
implants.

C. Polymers
Polymers are widely used in surgery, prosthetic systems and controlled drug
delivery. Currently, both synthetic and natural polymers have been extensively
studied as biodegradable polymeric biomaterials.

COATING TECHNIQUES
In this part, the basic principles behind the coating techniques are briefly
described and followed by its current applications for biomaterials. As mention
earlier, only metallic biomaterials as a substrate are considered in the review.

A. Chemical treatment
Chemical treatments involve chemical reactions at the interface between a
substrate and solution using acids, alkalis, and hydrogen peroxide (H2O2). They
have been widely studies for surface modification of biomaterials especially Ti
and its alloys due to their simplicity and flexibility.
Nanostructures such as titania nanorods nanoflowers and nanowires can
be formed by chemically treating using H2O2 at relatively low temperature. Wu
 ➔ CMU.J.Nat.Sci Special Issue on Manufacturing Technology (2011) Vol.10(1) 41

(2004) prepared titania nanorods by oxidizing pure titanium in hydrogen peroxide

solution at 80°C for 3 days and found that the addition of F- and SO42- helped
the formation of pure anatase; while the addition of Cl- favoured rutile structure.
Wu et al., (2005) deposited large-scale titania nanorods on Ti using the previ-
ous method followed by heating in air at 450°C for 1 h. Most of the nanorods
were mixtures of anatase and rutile structures. The post heat treatment kept the
morphology but improved the crystallinity. The same author and co-workers
(Wu et al., 2006) also synthesized titania nanoflowers (Figure 1) by the previous
method, followed by heating at 400°C for 1 h. Varying concentration of nitric
acid resulted in difference in phase composition.
Shi et al. (2009) prepared sandblasted, dual acid-treated (HF/HNO3) and
H2O2/HCl heat-treated Ti-6Al-4V. The authors suggested that the treated Ti alloy
surface had the ability to deposit apatite and enhanced proliferation.

B. Anodic oxidation
Anodic oxidation or electrochemical deposition involves electrode reac-
tions in an electrolyte, resulting in the formation of an oxide film on the anode
surface. Different dilute acids are used as electrolytes in the process. Anodic
oxidation is generally a simple and low-cost technique to produce nanostructures
on the surface of titanium.
Wang et al., (2008) formed a well oriented and uniform TiO2 nanotube
array on the surface of titanium substrate using anodic oxidation. The ano-
dized Ti substrate was electrochemically deposited in an electrolyte containing
calcium and phosphate ions. It was suggested that the surface morphology of
TiO2 nanotube promoted mechanical interlocking between HA and TiO2.

Figure 1. SEM micrographs of titania nanoflowers synthesized by oxidation of

Ti with 30wt% H2O2 solution containing 0.014 M hexamethylene-
tetramine and 0.4 M nitric acid at a temperature of 80°C, followed
by heating at 400°C for 1 h: (a) low (b) high magnifications. (Wu et
al., 2006).
42 ➔ CMU.J.Nat.Sci Special Issue on Manufacturing Technology (2011) Vol.10(1)

Figure 2. SEM top-view images of the first nanotube layer (A), and the second
nanotube layer (inset of A), cross-sectional image for the double nano-
tube layers (B), and cross-sectional images of the interface between
the upper and the lower TiO2 nanotube layers (C) and (D). (Cui et
al., 2009).

Kunz et al., (2008) fabricated the nanotubular layers on titanium by

electrochemical anodization in fluoride-containing electrolytes, followed by HA
coating. It was observed that the nanotube oxide layer enhanced the formation
of a thick apatite layer.
Song et al., (2009) fabricated amphiphilic TiO2 nanotube layers (see
Figure 2) using a double anodization method combined with organic monolayer
grafting. The amphiphilic characteristics with the hydrophobic outside and the
hydrophilic were obtained.
Cui et al., (2009) prepared titanium oxide films using anodic oxidation on
the surface of commercially pure titanium in four different electrolytes: sulphuric
acid, acetic acid, phosphoric acid, and sodium sulphate solutions. Amorphous
titania observed in acetic and phosphoric acids could not induce apatite formation
whereas rutile structure prepared from sulphuric and sodium sulphate solutions
favoured apatite deposition.
Park et al., (2010) formed amorphous titania nanotubes on titanium sur-
face by an anodic oxidation process. The crystallization and corrosion resistance
improved were induced by a post-heat treatment at 500°C for 2 hrs.
Nanotube arrays can also be formed in an F- containing electrolyte by the
competing two electric field-assisted processes (Crawford and Crawla, 2009).
Wang et al., (2009) deposited HA and fluoridated HA (FHA) coatings on titanium
substrates using an electrochemical technique in electrolytes containing Ca(NO3)2,
NH4H2PO4, NaNO3 and H2O2 (NaF added for FHA coating). The FHA coating
showed higher bond strength and lower dissolution rate than HA coating.

C. Micro-arc oxidation
Micro-arc oxidation (MAO) is also known as anodic spark oxidation. In this
process, the component to be coated is connected to a high-voltage power supply
 ➔ CMU.J.Nat.Sci Special Issue on Manufacturing Technology (2011) Vol.10(1) 43

and immersed in an aqueous electrolytic stainless steel vessel, which serves as

the counter-electrode. As an asymmetric alternating voltage is then applied and
exceeds a critical value, micro-plasma discharge occurs on the surface of the
component. The process can be performed at room temperature for components
with complex geometries, therefore it is considered as a simple and economical
coating technique.
Several researchers have studied the possibility Ca-P coatings on metallic
biomaterials using MAO technique (Kim et al., (2007), Sun et al., (2007), Han
et al., (2008)). Nano-crystalline HA films were formed at the surface of Ti by
a single-step MAO using Ca2+ and P5+ ion-containing electrolytes (Kim et al.,
2007). Strong crystallinity dependense on the CaCl2 concentration in the elec-
trolytes was found. The mechanism for HA coating was proposed based on the
formation of amorphous CaTiO3 and its dissolution to TiO(OH)2 by H+ ions.
Sun et al. (2007) proposed a novel method to directly coat HA on
Ti-6Al-4V using MAO in Ca- and P-containing electrolyte. The coatings obtained
were composed of a bi-layer structure of HA/TiO2 (Figure 3). The HA peaks
increased when the applied voltage increased from 430 to 480 V or increased
treated time at 480 V.

Figure 3. SEM micrographs showing the surface morphologies of the MAO

coatings formed at 480 V for (A) 1.5 (B) 3 (C) 10 (D) 20 min. (Sun
et al., 2007).

Han et al., (2008) synthesized HA-based coatings on Ti alloy by MAO in

an electrolyte containing calcium acetate (Ca(CH3COO)2) and β-glycerophosphate
(β-GP) disodium at high applied voltage. It was suggested that hydrolysis of
β-GP and decomposition of (CH3COO)- were promoted by the intense micro-arc
discharge generated at high voltage.
Wei et al., (2009) formed TiO2-based coating on Ti alloy by MAO in
electrolytes containing nano-HA, calcium and phosphate salts. A post-heat treat-
ment resulted in the increase of surface roughness, decreasing in cell adhesion
and proliferation ability.
44 ➔ CMU.J.Nat.Sci Special Issue on Manufacturing Technology (2011) Vol.10(1)

Song et al., (2009) fabricated porous oxide films on pure titanium using
an anodic spark oxidation technique with different electrolytes: H2SO4, H3PO4
and CH3COOH. A TiP2O7 film was mainly observed on the specimens anodized
in the H3PO4 electrolyte whereas TiO2 in the acetic and sulphuric acids.
Micro-arc oxidation has been also applied in other Ti alloys. Chen et al.,
(2009) studied the structure and osteoblast cell compatibility of the TiO2 layer
coated on β-Ti alloy (Ti-13Cr-3Al-1Fe) using MAO in NaH2PO4 solution. Sur-
face morphologies of coating were a function of voltage and treatment time. Tao
et al., (2009) synthesized a porous oxide layer on Ti-24Nb-4Zr-7.9Sn alloy (in
wt%) by MAO treatment using calcium acetate electrolytic solution. A post-heat
treatment at 600°C for 60 min resulted in the oxide films consisting of TiO2,
CaO, Nb2O5 and SnO2 and improved the apatite forming ability.

D. Sol-gel
Sol-gel processing can be described by a serried of steps as followed:
(i) The preparation of a sol formed by mixing of particles in a liquid
vehicle. The hydrolysis and condensation reactions occur when a metal alkoxide is
mixed with water and a mutual solvent in a presence of acid or base catalyst.
(ii) Ageing of the sol is carried out at suitable temperature.
(iii) The aged sol is then subjected to coating, dipping or spraying for
obtaining a gel form through sol-gel transition.
(iv) At the final step the surface modified specimen is subjected to drying,
sometimes followed by sintering.
Nanocrystalline carbonate HA coatings deposited on Ti-6Al-4V by sol-gel
technique using different precursors containing different water/ethanol content were
performed (Hijon et al., 2006). It was revealed that all the sols formed uniform
and homogeneous films, increasing the uniformity in presence of ethanol. Garcia
et al., (2006) developed a double layer coating obtained by sol-gel technique
containing bioactive glass, glass-ceramics or HA particles on Ti-6Al-4V alloy.
Ballarre et al. (2007) investigated an organic-inorganic (hybrid) sol-gel coating
containing glass-ceramic particles in order to improve the bioactivity of AISI
316L stainless steel. HA deposited on the samples after 30 days of immersion
in simulated body fluid (SBF) was detected.
Harle et al., (2006) prepared both pure and composite HA and TiO2 on
commercially pure Ti using sol-gel technique. It was reported that human osteo-
blast cells showed good attachment and proliferation on all coatings. The pure
HA and HA + 10% TiO2 composite coating enhanced proliferation at 4 days.
Ochsenbein et al. (2008) coated pure titanium with different oxides: TiO2, SiO2,
Nb2O5 and SiO2-TiO2 using the sol-gel process. A nanoporous structure in the
TiO2 and Nb2O5 layers was revealed, whereas the SiO2 and SiO2-TiO2 layers
appeared almost smooth.
Arnould et al., (2010) improved the highly purity titanium surface by
forming bilayer coating using both sol-gel and dip-coating techniques. The first
layer was tantalum oxide and the second was formed over the first by three
different organophosphonic acid molecules. The chemical treatment using the
 ➔ CMU.J.Nat.Sci Special Issue on Manufacturing Technology (2011) Vol.10(1) 45

acids led to an increase in the hydrophilic character of the surface. Among the
organic acid used, the ethylene diamine-tetra-methylene phosphonic acid and
amino-tris-methylene phosphonic acid appear to be the best candidates for HA
nucleation.

E. Plasma spraying
In plasma spraying process, materials in the form of powder is injected
into a high-temperature plasma flame, where it is rapidly heated and acceler-
ated at a high velocity towards a substrate. It employs an electric arc to ionize
the gas and creates high-pressure plasma. This technique is currently used in
commercial for HA coating in biomedical application. However, the interface
between the HA and the metal substrate may be defective, as a result of high
degree of porosity and poor bond strength.
Inagaki and Karmeyama (2007) developed highly oriented HA coatings on
titanium using a combination of heat and hydrothermal treatments, following a
radio-frequency thermal plasma spraying method. The orientation degree of the
coating was slightly affected by the post-heat treatment.
Liu et al., (2008) prepared titania nanostructural coatings on titanium
alloy using plasma spraying to investigate the bioactivity of the coating with
UV-irradiation. The ability of apatite formation on the nano- TiO2 surface was
improved with the increase of UV-irradiation time.
Chen et al., (2008) deposited a dense titania coating on stainless steel from
an ethanol-based solution containing titanium isopropoxide using the solution
precursor plasma spray process. A post chemical treatment in 5 M NaOH solu-
tion at 80°C for 2 days was required for apatite formation.
Lu et al., (2008) revealed the surface crystallization of plasma-sprayed
HA coating was revealed during post heat treatment and therefore improved
osteoblastic cell compatibility.

F. Electrostatic spray deposition

Electrostatics spray deposition (ESD), also known as electrospraying, is a
process of liquid atomization by means of electrical forces. In this process, the
liquid flowing out of a capillary nozzle maintained at high potential is forced by
the electric field to be dispersed into fine droplets. These droplets are directed
towards a grounded and heated substrate.
Siebers et al., (2004) noticed that the observed increase in cell proliferation
can be a result of the carbonate apatite formed in the ESD coatings compared
to the apatite in the RF magnetron sputtered coating.
Leeuwenburgh et al., (2005) studied the effect of processing parameters
on the morphology in ESD. From the results, it was pointed that the ESD had
a potential for synthesis of CaP with controlled morphology. The same authors
(2006) further investigated the morphology of CaP coating by in situ measure-
ments of droplet sizes and velocities using Phase Doppler Anemometry (PDA).
It was indicated that the chemical composition of the precursor solutions and
the mixing characteristics of the CaP precursor components strongly influenced
46 ➔ CMU.J.Nat.Sci Special Issue on Manufacturing Technology (2011) Vol.10(1)

the initial droplet sizes, precipitation kinetics of the CaP solute, and subsequent
coating morphologies. Micron-sized surface (Figure 4) features of these mor-
phologies were shown to correspond with the diameters of the droplets.
Kim et al. (2007) developed a well-crystallized HA film on a stainless
steel by the sol-gel assisted electrostatic spray deposition using calcium nitrate
and phosphoric acid as reactants, followed by a post-heat treatment. Crack-free
HA films were obtained at the substrate temperature of 80°C. The amorphous
as-deposited films transformed to HA films at 500°C for 30 min.

G. Electrophoretic deposition
Electrophoretic deposition (EPD) is achieved via two steps: i) motion of
charged particles in suspensions towards the oppositely charged electrode and
ii) deposit formation under the influence of an applied electric field. Generally,
this technique can be applied to any solid that is available as a fine powder
(< 30 µm particle size) or as a colloidal suspension (Corni el al., (2008).

Figure 4. High-magnification SEM micrograph of a reticular CaP coating after

60 minute of at temperature of 350°C. (Leeuwenburgh et al., 2006).

Figure 5. SEM micrograph of the cross-section of a PLD coating, showing a

dense HA film. (Dinda et al., 2009).

Javidi et al., (2008) deposited natural HA on 316L stainless steel using

EPD in a suspension consisting of isopropyl alcohol and polyethylenimine.
 ➔ CMU.J.Nat.Sci Special Issue on Manufacturing Technology (2011) Vol.10(1) 47

The deposited substrates were sintered in a vacuum furnace at 800°C for 1 h.

The coating efficiency and surface roughness increased with increasing applied
voltage and deposition time but the deposition rate decreased.
Kwok et al., (2009) fabricated submicron HA coatings with and with-
out multi-walled carbon nanotube powder on Ti-6Al-4V by EPD, followed by
vacuum sintering at 800°C for 1 h. It was reported that the adhesion strength
of all coatings studied was higher than values commonly reported for plasma
sprayed HA coating.
Sun et al., (2009) developed an electrophoretic deposition method for a
composite HA-chitosan coating on 304 stainless steel. Crack-free composite
coating with needle-shaped crystals in a chitosan matrix was obtained.

H. Pulsed laser deposition

Basically, the pulsed laser deposition (PLD) technique employs laser to
ablate a target material and condense it on the surface of a substrate. The principle
of this technique is a very complex physical phenomenon; readers can refer to
Bao et al., (2005).
Blind et al., (2005) produced HA thin film coating by PLD on Ti and
Ti-6Al-4V substrate. The authors stated that these HA films were adherent to
the substrate and a high degree of crystallinity was obtained.
Yang et al., (2009) deposited HA film on laser gas nitriding (LGN) NiTi
substrate using PLD technique. It was revealed that TiN dendrites provided a
higher number of nucleation sites for HA deposition, thus a lot HA particles
were deposited on LGN NiTi substrates.
Dinda et al., (2009) deposited HA coating on Ti-6Al-4V by PLD. The
as-deposited HA films were amorphous, granular and 2.5 µm in thickness
(Figure 5). It was suggested that post-deposition annealing for 4 hrs at 300°C
had a potential to produce pure, adherent and crystalline HA coatings without
dissolution in a SBF.

CONCLUSION
Various coating techniques have been extensively studied for biomedical
applications. The development of surface modifications of metallic biomaterials
has been received a great deal of attention and a wealth of knowledge has been
accumulated. However, better and simpler techniques need to be developed in
order to achieve optimal and more reliable surface coating characteristics. In
addition, it is essential to evaluate the safety of the functionalized coatings
before clinical uses.

ACKNOWLEDGEMENTS
The author wish to thank the National Research University (NRU) Pro-
ject under Thailand’s Office of the Higher Education Commission for financial
support.
48 ➔ CMU.J.Nat.Sci Special Issue on Manufacturing Technology (2011) Vol.10(1)

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