Authors Accepted Manuscript

A Review of Hydroxyapatite-based Coating

Techniques: Sol-gel and Electrochemical
Depositions on Biocompatible Metals

R.I.M. Asri, W.S.W. Harun, M.A. Hassan, S.A.C.

Ghani, Z. Buyong
www.elsevier.com/locate/jmbbm

PII: S1751-6161(15)00449-X
DOI: http://dx.doi.org/10.1016/j.jmbbm.2015.11.031
Reference: JMBBM1704
To appear in: Journal of the Mechanical Behavior of Biomedical Materials
Received date: 17 September 2015
Revised date: 26 November 2015
Accepted date: 30 November 2015
Cite this article as: R.I.M. Asri, W.S.W. Harun, M.A. Hassan, S.A.C. Ghani and
Z. Buyong, A Review of Hydroxyapatite-based Coating Techniques: Sol-gel and
Electrochemical Depositions on Biocompatible Metals, Journal of the
Mechanical Behavior of Biomedical Materials,
http://dx.doi.org/10.1016/j.jmbbm.2015.11.031
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 A Review of Hydroxyapatite-based Coating Techniques: Sol-gel and Electrochemical

Depositions on Biocompatible Metals

R.I.M. Asri1, W.S.W. Harun2, M.A. Hassan2, S.A.C. Ghani2, Z. Buyong3

1
Institute of Postgraduate Studies, Universiti Malaysia Pahang, Lebuhraya Tun Razak,
26300 Gambang, Kuantan, Pahang, Malaysia
2
Human Engineering Group, Faculty of Mechanical Engineering,
Universiti Malaysia Pahang, 26600 Pekan, Pahang, Malaysia
3
Kuliyyah of Medicine, International Islamic University Malaysia,
25200 Kuantan, Pahang, Malaysia
Corresponding author: sharuzi@ump.edu.my

New promising techniques for depositing biocompatible hydroxyapatite -based coatings

on biocompatible metal substrates for biomedical applications have continuously been

exploited for more than two decades. Currently, various experimental deposition processes

have been employed. In this review, the two most frequently used deposition processes will be

discussed: A sol-gel dip coating and an electrochemical deposition. This study deliberates the

surface morphologies and chemical composition, mechanical performance and biological

responses of sol-gel dip coating as well as the electrochemical deposition for two different

sample conditions, with and without coating. The review shows that sol-gel dip coatings and

electrochemical deposition were able to obtain the uniform and homogeneous coating thickness

and high adherent biocompatible coatings even in complex shapes. It has been accepted that

both coating techniques improve bone strength and initial osseointegration rate. The main

advantages and limitations of those techniques of hydroxyapatite-based coatings are presented.

Furthermore, the most significant challenges and critical issues are also highlighted.
Keywords: Biomaterials; Hydroxyapatite coating; Electrodeposition; Sol-gel Dip Coating.

1.0 Introduction

Metals and their alloys play an important role as biomaterials that can contribute to the

fixation or replacement of load-bearing bones that have been damaged [1-3]. This is due to the

scale that reported around 70-80% of implants are made of biocompatible metals [4, 5]. The

implants are made into various shapes including bone screws, pins, plates and others [6, 7].

There are large demands of the metal implants as the need for malfunction and fracture fixation

of hard tissues increases. Representative applicable implantable metals are restricted to stainless

steel, cobalt chromium molybdenum alloys, titanium (Ti) and its alloys (e.g. Ti6Al4V, Ti6Al7Nb

and shape memory TiNi alloys) [3, 6-8]. They have enjoyed clinical success due to their

immense mechanical features that satisfy the requirement of the human bone [9-11]. The high

mechanical strength and toughness of these biomaterials are the most significant benefits

compared to bioactive ceramics, which are inherently weak and brittle [1, 12, 13]. For example,

the Youngs modulus of an implant should be similar to that of human bone, so as to minimize

the stress shielding effect and to extend the quality of human life [8, 14, 15]. Due to their

physical nature, all the biocompatible metals have a long service life combined with a low elastic

modulus and low plasticity at body temperature. Moreover, they have excellent corrosion

resistance and biocompatibility [16-19].

However, there are some limitations of these metal materials involving the possible

release of harmful metal ions through wear and corrosion processes when they are exposed to

aggressive body environment [20-22]. The release of toxic ions might cause adverse effects to
the surrounding tissues [23-25]. For stainless steel metal, it might expose to a distinct shortage as

it does not form strong chemical bonds with natural bones [26-28]. It is significant in the

enhancement of techniques to improve corrosion resistance and to enhance the bioactivity of

these materials [29-32]. The application of bioactive materials such as hydroxyapatite HAp

(Ca10(PO4)6(OH)2) coatings onto the surface of metallic implant devices have received enormous

considerations [33-36]. This is due to its chemical, crystallographically structural and

mineralogical composition resemblance to human bone and tooth minerals [37-39]. Moreover,

their strong chemical bond creates its metal-implant coating to promote the new bone growth

[40]. Thus, coated alloys with a HAp coating are expected to overcome the weaknesses of

biocompatible metals along with the HAp coating deficiencies such as its brittleness and poor

mechanical properties [41-43]. HAp coating of biomaterials enhanced the corrosion resistance by

forming a barrier against the dissolution of metal ions from the substrate at the same time

promoting its bone bonding ability [44, 45]. Yang et al. [46] reported that HAp coatings can

develop clinical success with a failure rate of less than 2%. It was reported during a mean follow-

up study of 15 years [23, 34, 47-54]. Nevertheless, several attempts have been introduced to

enhance the bonding strength of HAp coating. Introducing a composite coating of HAp with

additional materials such as Ti [55], titania (TiO2) [56, 57], zirconia (ZrO2) [58], poly-(-

caprolactone) [59], calcium silicate (CaSiO3) [60] and others [45, 61-64].

So far, a number of commercial techniques have been developed to create the HAp

coating on metallic implants, such as solgel dip coating [57, 65-73], electrochemical deposition

[56, 74-78], electrophoretic deposition [79-84], plasma spraying process [85-87], sputter coating

[46, 88], hot isostatic pressing [89, 90], pulsed laser deposition [37, 91] and biomimetic

deposition [92]. Amongst the techniques listed, only plasma spraying is commercially approved
by the Food and Drug Administration (FDA), USA for biomedical coatings on implants [93]. It

is due to its excellent coating properties over other coating methods. Minimal requirements for

HAp coatings have been pronounced in the Food and Drug Administration guidelines as well as

in the ISO standards (Table 1) [46]. However, HAp coating by plasma spray technique is limited.

It is due to poor uniformity in coating thickness and its adherence to substrate, phase impurity,

and low crystallinity. Furthermore, the degradation of bending strength and fatigue life is caused

by the dissolution of HAp phase in long-term contact with body fluids [94, 95]. It is also

suffering from poor mechanical properties on tensile strength, wear resistance, hardness,

toughness and fatigue [96, 97]. Moreover, plasma spray deposition is not able to produce a

uniform HAp coating with complex geometry. Other than that, the electrophoretic deposition is

one of the electrodeposition methods and applies a high voltage of 90V to deposit coating [98]. It

is followed by high sintering temperatures to improve the adherence properties. However, the

crystal structures and coating compositions are changed after the deposition. The alternative

coating approaches have been extensively developed and tested to overcome the weaknesses of

plasma spraying and electrophoretic depositions.

Table 1
HAp coating requirements [46]

Comparing to the required sophisticated vacuum systems and apparatus of most methods

excluding plasma spray deposition, solgel dip coating and electrochemical deposition are

widely applied to metal implants. Both of the processes have some similarities and have been

classified to be relatively low-cost and easier methods compared to others. They show promise

due to their relative ease of production, ability to apply a uniform coating over complex

geometric shapes and can be set up easily at room temperature as shown in Table 2. Besides that,
these two methods have the potential to deliver exceptional mechanical properties, corrosion

resistance, and adhesion strength due to their nanocrystalline structure.

Table 2
Different techniques to deposit HAp coatings

This review discusses the effect of HAp-based coatings deposited sol-gel dip coating and

electrochemical deposition techniques. Parameters affecting the high quality for both coating

techniques were examined in detail.

2.0 Deposition methods

2.1 Electrochemical Deposition

Electrochemical methods are widely used for the preparation of thin films and coatings in

biomedical applications [100, 101]. Electrodeposition of ceramic materials can be conducted by

anodic or cathodic techniques. Thus far, anodic deposition has limited utility regarding possible

materials to be deposited on this method and substrates used for deposition. While cathodic

deposition has significant benefits for industrial and medical applications [102]. Two processes

are commonly used to prepare coatings by cathodic electrodeposition: the electrophoretic process

(EPD) based on the use of suspensions of ceramic particles, and the electrolytic process (ELD),

which starts from solutions of metal salts. Electrochemical deposition technique is a well-known

deposition method commonly used in titanium. The calcium and phosphate precursors act as

CaP ratio in distilled water. The resulting filtrate is used as the electrolyte in an electrochemical

cell [103, 104]. This technique is often performed from aqueous solutions similar to those used
in wet-chemical deposition. Most authors use the cathodic deposition since it has been

recommended that high anodic potentials may affect the substrate surface detrimentally [105,

106]. Platinum or graphite is used as the standard anodic material.

HAp coating deposition by the electrochemical method has unique advantages due to its

quick process and capability of forming uniform coating [107]. The process can be operated at

relatively low temperature [108]. One of the significant capabilities provided by fine particle

electrophoresis is the ability to achieve ceramic particle impregnation into a porous substrate and

composite consolidation. It is now well established that the state of agglomeration of ceramic

powders is a major factor in controlling the sintering behaviour. Agglomerate-free structures

made from fine close-packed particles can be densified at lower sintering temperatures [109]. A

significant advantage of electrophoretic processing is that agglomerates can be separated by pre-

sedimentation [110]. Moreover, owing to the insulating properties of the deposit, the electric

field provides a higher deposition rate in defect regions, resulting in better packing and

uniformity of the deposit. In recent years, a significant amount of work has been done on the

electrochemical HAp coating on biocompatible metallic implants. Coating by electrochemical

can produce homogeneous coating and can enhance the adhesion strength between implant and

coating layer. Kuo et al. [111] first reported the deposition of HAp on titanium using an

electrochemical method. The as-deposited coating consisted of dicalcium phosphate dihydrate

(CaHPO4.2H2O, DCPD) and b-tricalcium phosphate (b-TCP, Ca3(PO4)2). This coating was

transformed to HAp by immersing in 0.042 M Ca(NO3)2 and 0.025 M NH4H2PO4 aqueous

solution. Adhesion testing by shear testing showed that the HAp coating has stronger adhesion

strength (106.3 MPa) with the coating thickness (18.6 m). The cross-sectional SEM photograph

of HAp coating deposited at ten mA/cm2 for 30 minutes shown in Fig. 1(a) revealed a dense
underlayer coating. Fig. 1(b) shows the EDS line-scanning diagram of the straight line AB in

Fig. 1(a).

Potentiostatic (constant-potential) and galvanostatic (constant current) are the two

conventional techniques often used to control electrical current [112, 113]. Electrochemical

coating of HAp on metal substrates using conventional methods decreases their degradation;

unfortunately, it does contain defects onto the coating surfaces [113]. During the electrochemical

deposition process, an electric current is passed through the electrodes immersed in an

electrolyte. Initially, the hydroxide (OH-) ions are produced at the substrate (cathode) [114]. This

is due to the electrochemical reaction that is usually the reduction reaction of water, which is

consequential in the formation of a large amount of hydrogen gas [97]. Formation of the

hydrogen gas bubbles might adhere to the substrate as well as avoid nucleation and deposition of

calcium phosphate. Therefore, it might lead to the formation of non-uniform coating [113, 114].

To overcome the imperfections, this means that HAp coating performance should be further

improved and solved by applying higher current density. Several adjustments are suggested to

make the direct current electrochemical deposition method more suitable in the following way.

Fig. 1. (a) Cross-sectional SEM photograph of HAp-coated specimen deposited at 10 mA/cm2

and annealed at 500 oC for 1 h, and (b) EDS line scanning spectrum of line AB in (a) [111]

During the deposition process, H2O2 was added to the electrolyte. H2O2 can substitute for

H2O, which in turn lowers the deposition current and change the mechanism of the whole lot of

electrochemical reaction [115]. The effects of H2 evolution may be removed due to the addition

of peroxide. Consequently, a dense and uniform coating may be formed [108]. Chandrasekar and

Pushpavanam [116] introduced pulse-electrodeposition as a technique to reduce the intensity of

hydrogen evolution reaction during the coating process. The negatively charged layer discharged

during pulse-electrodeposition and the ions are allowed to diffuse toward the substrate. This

would contribute to a more even diffusion of ions. As a result, the hydrogen evolution may not

increase with coating time. Furthermore, Blackwood et al. [115] reported galvanostatic pulse

electrodeposition of HAp on titanium. Periodic pulsed current densities gave a stronger adhesion

of HAp coatings deposited on the substrate surface compared to the continuous current density.

Besides that, the pulsed current is applied for the HAp deposition on 316L stainless steel

substrate [117]. The pulse current holds a relaxation time paralleled with the continuous, direct

current. In the pulsed electrodeposition process, the ions become closer to the cathode adequately

deposited when the current is applied. During the relaxation time, the ions are diffused from the

bulk solution to the surface of the cathode, which is a solution to improve the physical-chemical

properties of coatings [118]. Gopi et al. [119] reported that the coating and cell morphologies

have been profoundly influenced by the increment of pulse off time. Encouragement for the

adhesion and proliferation of cells was obtained at 4 s pulse off time followed by enhancement of

corrosion resistance in simulated body fluid.

Wang And Luo et al. [120] have generated HAp coating on CoCrMo substrates with the

thickness about 200 nm and bonding strength about 17.5 MPa. This is the minimum requirement

for the adhesion strength of CaP coating on metallic biomaterials [121]. Popa et al.[114] have a

similar idea with [120], Ti, and Ti6Al4V alloy proved that HAp coating is more suitable for cell

adherence compared to the uncoated material and brushite coating. This statement is supported

by SEM micrographs in Fig. 2. The morphology of the coatings deposited on the Ti and Ti6Al4V

in Fig. 3 alloy became denser, lower rugosity and less spallation areas after soaking times are

changed for 1 h, 24 h and 48 h. The deposited coating was continuous with isolated remaining
pores of ~1 m after immersion for 48 h, thought to be a favourable structure for cell adhesion

and proliferation. Fig. 4 shows the XRD spectra of electrochemical deposition CoCrMo after

immersion in supersaturated calcification solution (SCS) for 2h, 12 h and 72 h. The addition of

immersion time enhances and improves the morphologies of coating.

Fig. 2. SEM micrographs of primary and final coatings in comparison with uncoated supports of
Ti and Ti6Al4V alloy [114].

Fig. 3. SEM micrographs of hydroxyapatite coating deposited on Ti and Ti6Al4V alloy after 48
h soaking in Ringers solution (pH=7.1) [114].

Fig. 4. XRD spectra of CoCrMo after different immersion terms in Supersaturated Calcification
Solution (SCS) and Octacalcium Phosphate (OCP) standard data, JCPDF 26-1056; HAp
standard data, JCPDF 09-0432; S-substrate [120].

Recently, the pre-treatment of a metal substrate coated by electrochemical deposition has

been introduced [122]. This is called anodization process that is helpful in forming mechanical

interlocks between the metal substrate and the HAp coating [48, 122, 123]. It is demonstrated

that pure and homogeneous HAp coating can be obtained by the anodization and without any

post-treatment. He et al. [124] deposited a thin Al film on Ti substrate and then applied

anodization and hydrothermal treatment, after which the calcium phosphate grew from the holes

of anodized aluminum oxide during the coating process. Yang et al. [125] prepared the bioactive

titanium metal via anodic oxidation treatment. Although the electrochemical HAp coating and

pre-treating routes become more and more important, the investigation on electrochemical

deposited HAp coating on the porous anodized Ti substrate has not been reported to date [104].

Zhao et al. [107] prepared HAp coatings directly on anodized titanium by electro-deposition
method in a modified simulated body fluid (SBF). Fig. 5. shows XRD patterns of pure HAp

coating with Ti substrate after the anodization process.

Fig. 5. XRD patterns of the HAp coating on Ti substrate show homogeneous coating deposition
[107]

Therefore, HAp coatings showed excellent bioactivity and increment of the coatings

thickness after immersion in SBF for four days as indicated in Table 3. SBF that has similarities

to human blood plasma was buffered at pH 7.4 with Tris(hydroxymethyl)aminomethane and

hydrochloric acid (HCl) at 37C.

Table 3
The ratio of n(Ca)/n(P) and thickness of HAp coatings after immersion in SBF [107]

In vivo investigations in rabbits reported that the bonding of a bone with an implant after

such procedure is extensive but not principally high. The cause may be low porosity and

precipitation of apatite-like deposits inside the pores of an oxide layer [126]. After an application

of the electrolyte containing 0.025 M Ca biphosphate, 0.75 M Ca acetate, 0.12 M NaEDTA and

NaOH, the coating with Ca/P = 1.3 is formed, lower than in conventional electrolytes. Such

coating has better mechanical stability and is composed of totally dissolved CaP phase in the

matrix of amorphous and crystalline anatase [127]. The application of micro-arc oxidation results

in an increase in Ti biocompatibility as demonstrated by the increase in the activity of alkaline

phosphatase in osteosarcoma cells and a decrease in proliferation [128]. The in vivo tests show a

threefold increase in bone implant strength.

 In these recent years, many studies have introduced to improve the mechanical property

of HAp by reinforcing materials carbon nanotubes (CNTs), ZrO2, TiO2 [83, 129]. In fact, the

HAp-based coating has been reported the improvement in adhesion strength nearly 70% higher

than pure HAp coating [130]. The incorporation of single-walled nanotubes (SWNT) into HAp

coating leaded to the formation of homogeneous, high crystallinity and crack-free coatings with

bonding strength ranged from 15.3 to 25.7 MPa [130].

Yuan and Golden [131] have used electrodeposition to deposit a double layer of HAp

coating on 316L stainless steel (SS) substrate and sintered in the air (600oC) or vacuum (800oC).

The result showed a more uniform HAp coating with excellent adhesion compared to one layer

coating of HAp. The intermediate layer acts as an oxide layer to keep the oxidative metal ions in

the SS substrate from migrating into coating surface to prevent HAp decomposition [79]. High-

temperature sintering or annealing has been mentioned and exposed to create a denser and

uniform CaP coating post-electrodeposition [62], with greater adhesion properties [103].

Albayrak et al. [132] have applied the same method as [131] by introducing titanium oxide

(TiO2) as a buffer layer for HAp coated on Ti6Al4V substrate. The coated substrates with the

thickness about 30 m were immersed for 1 min with different voltages as 10, 20, and 50 V

showed increasing adhesion strength with decreasing voltage value. Table 4 displays the

comparison of adhesion strength by electrodeposition.

Table 4
Adhesion strength of electrodeposition HAp coatings.

To conclude this part, HAp coatings achieved by electrochemical deposition method has

a uniform structure since they are formed gradually through a nucleation and growth process.
The electrochemical deposition process has a broad range of coating thickness. The process

undergoes at relatively low temperatures which effectively reduces corrosion of the substrate

during coating. Correspondingly, the sintering phase for this technique improves densification

and bonding properties of the coating. However, HAp may decompose during the process. An

interlayer between coating and substrate can be used to overcome the problem of HAp

decomposition. As such, the electrochemical deposition method shows great promise of future

adaptation for metallic substrates.

2.2 Sol-gel Dip Coating

Solgel route combined with the dip-coating technique has been widely investigated to

coat metallic biomaterials for enhancement of adhesion [66, 133]. Calcium and phosphorus are

most commonly used as CaP precursors for the solution (sol) preparation with the addition of

two solvents, often water and ethanol [134-136]. The phosphorus precursor, frequently

phosphorus pentoxide or triethyl phosphite, is dissolved in ethanol [137, 138]. Meanwhile, in

some preparations, a minute amount of water is added to the solution to achieve hydrolysis of the

subsequent sol [139]. The selected calcium precursor, most often calcium nitrate, is also

dissolved in ethanol and then added to the hydrolysed phosphorus sol in a dropwise approach

[140, 141]. The mixed solution is then refluxed at various temperatures and solvents are

evaporated off until a more viscous solution is obtained to achieve a solgel [142, 143].

The chemical activity and the temperature required to form the apatite phase that depends

mostly on the chemical nature of the precursors. The solgel route, as shown in Fig. 6., consists

of producing a homogeneous solution of CaP precursors in an organic solvent that can be mixed
with the reagent used in the next step or water. Secondly, the sol is changed to a gel by

polycondensation. Subsequently, solgel slurry undergoes aging, drying and calcination

processes [144-146]. Solgel preparations are well-known as being cost-effective and simple to

set up, besides having the ability to coat complex shapes, similar to biomimetic coatings. The

major advantage of solgel applications over biomimetic coatings, as tentatively suggested in

prior research, is in the strength of the coatingsubstrate adhesion [147, 148]. Roest et al. [43]

investigated sol-gel derived HAp nanoscale coating to enhance osseointegration and adhesion

strength. It reported the preparation of solgel solutions in a glove box comprising of purified

dry nitrogen by applying previous work [33, 140, 141]. The substrates were coated for 20 s at

2000 rpm with the solution and sintered at 550 C for 2 h. The thickness of the HAp coatings

was about 100 nm after the sintering process and was measured by SEM and ellipsometry. Fig.

7. shows the SEM view of the example of the HAp coating thickness for commercially pure Ti

substrate [149].

Fig. 6. Flow chart of HAp coating preparation by a sol-gel process

Fig. 7. High magnification, SEM image showing the thickness of HAp coating on commercially
pure Ti from a fractured section [149]

Dip coating is a technique that involves three stages: dipping, withdrawing, and drying,

as shown in Fig. 8. The substrate is successively dipped into the solution and withdrawn at a

constant speed, offering a good control of the thickness and producing no waste. Some models

have been proposed to describe the formation of a homogeneous fluid layer by dip coating [150].
HAp can be homogeneously coated onto substrates by this method to obtain coating thickness in

the range 0.05-15mm [95, 151]. However, the coating thickness varies according to the viscosity

of the application approaches used. Even though most researchers have attempted high-purity

HAp nanocoatings, others concentrated their research efforts on improving properties by the

addition of various compounds and chemical modifications [151].

Fig. 8. Fundamental stages of dip coating technique

Sol-gel dip coating technique is able to produce adhesive thin coating layer without

severe cracking by using lower annealing temperature. Severe cracking of the coating layer is

frequently observed due to the rapid temperature fluctuations and solidification of the coating

[152]. Normally extreme temperature for example 6000-10 000oC was used for plasma spray

deposition techniques. Thus, it can easily destabilize the crystal structure of the HAp.

Furthermore, it can decompose into a mixture of HAp, CaO, tricalcium phosphate, tetracalcium

phosphate, and a considerable amount of amorphous phases [153, 154]. D.-M. Liu et al. [155]

have compared the bonding strength of the HAp coatings on the 316L stainless steel substrates at

different annealing temperatures. The interfacial bonding strength performs to be relatively

constant at about 44 5MPa with the uniform coating thickness of about 0.6m as shown in Fig.

9. The adhesion strength between HAp coating and substrate increases with increasing annealing

temperature from 375oC to 450oC, but decreases slightly for 500oC. Even though annealing at

400oC to 500oC proved relatively denser coatings, however, some surface microcracks are visible

for those samples.

Fig. 9. Cross-section view of the coatings annealed at 375 oC shows (a) a uniform thickness of
about 0.6 m and (b) the ability of the solgel method to coat cavities/grooves of different
geometry on the substrates [155]

A. Stoch et al. [156] deposited HAp coating onto commercially pure Ti and Ti-6Al-4V

alloys and then cured it at temperatures 460750oC. Immersion observed the biological activity

of sol-gel HAp coatings in simulated body fluid (SBF) for 19 days, heated at 750oC reported that

the HAp layer can induce the surface in vitro growth of hydroxyapatite deposit. Higher

temperatures are necessary to achieve better crystallization of HAP and higher density of the

layer. Other than that, HAp-coated onto sandblasted and etched acid substrates have been

compared to HAp-coated followed by heat treatment at 550C for 5 min in air undergo dip

coating deposition by Bryington et al. [157]. Both of the coated substrates were implanted for 12

weeks and showed that heat treated surface demonstrated an increase in bone-in-contact (BIC) in

the cortical bone. Also, heated treated substrates have a better bone area within the implant

threads as compared to sandblasted, and acid etched HAp coating as shown in Table 5.

Table 5
Mean bone-to-implant contact (BIC) and bone area (BA) in threads [157]

In recent years, the sol-gel dip coating technique has developed some modifications to

enhance the quality of coating surfaces. Yusoff et al. [158] introduced the effect of poly-(-

caprolactone) (PCL) concentration (0, 10, 30, 50 wt%) on HAp coating properties at a fixed

withdrawal speed of 200 mm/min for 5 dips. The addition of PCL to the HAp caused the

formation of surface level pores, which are considered to promote osseointegration. Ti6Al4V

substrate with 30% PCL/HAp was considered as a good combination since it provided a high

thickness of the coating (184 m); no cracks were observed, and the coating/substrate adhesion
was enhanced. The absence of cracks on the coating is considered essential to protect the

substrate from corrosion and releasing harmful metal ions into body fluid [159]. Several

improvements have been introduced to enhance corrosion resistance and adhesion strength

between bone and implants.

Besides that, the formation of the oxide layer is one of the modern modifications that

have been applied before sol-gel dip coating process. For example, Titania (TiO2) is one of the

oxide layers that is commonly used to improve the bonding between HAp and Ti substrate [160].

Furthermore, the addition of carbon nanotubes (CNTs) to HAp is to enhance the mechanical

performance. Ji et al. [161] reported that HAp-CNT/TiO2 double-layer coatings were

successfully fabricated and had excellent bonding strength, exhibiting values up to 35.2 MPa.

The solgel combined with dip coating technique has been effectively investigated as a

simple and viable coating method for coating biocompatible implants. Also, this method can coat

complex shapes, similar to spontaneous precipitation methods. Further, adhesion and corrosion

resistance of metallic clinical implants and for industrial applications are enhanced by using the

sol-gel dip coating method. This approach shows the potential of using relatively low

temperatures and short incubation times to achieve HAp coatings on metallic substrates. This

would be a beneficial combination of features when considered as a coating application of

metallic biomaterials.

3.0 Conclusion

In conclusion, various promising techniques for coating metallic biomaterials are

continuously being investigated. Overall, those deposition techniques, namely sol-gel dip

coating, and an electrochemical deposition are mostly applied to deposit hydroxyapatite (HAp)-
based coating on metal substrates. Advantages of both techniques were discussed, and a

quantitative comparison was made on both methods of HAp-based coating on metallic

substrates. Based on this review, sol-gel dip coating method can form better coating surface

compared to electrochemical deposition technique. However, pre-treatment such as anodization

has been introduced in an electrochemical deposition to enhance the adhesion strength and

improve corrosion resistance.

Acknowledgement

This facilities and resources for this research are fully supported by Universiti Malaysia Pahang
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Table 1
HAp coating requirements [46]
Property Specification
Thickness Not specific
Crystallinity 62% minimum
Phase purity 95% minimum
Ca/P ratio 1.671.76
Density 2.98 g/cm3
Heavy metals < 50 ppm
Tensile strength >50.8 MPa
Shear strength >22 MPa
Abrasion Not specific
Table 2
Different techniques to deposit HAp coatings

Technique Thickness Advantages Disadvantages References

Sol-gel & dip < 1 m 15 Inexpensive; low Requires high sintering [57, 65-73]
coating mm processing temperatures; thermal
temperatures; relatively expansion mismatch
cheap as coatings are
very thin; high purity;
fairly good adhesion;
can coat complex
substrates; high surface
uniformity
Electrochemical 0.050.5 Low cost, coat complex The bonding strength [58, 76, 77,
deposition mm shapes, rapid, uniform between coating and 99]
coating thickness substrate
is not strong enough

Electrophoretic 0.12.0 Uniform coating Difficult to produce [79-84]

deposition mm thickness; rapid crack-free coatings;
deposition rates; can requires high sintering
coat complex substrates temperatures

Plasma < 20 m Rapid deposition; Poor adhesion; [85-87]

spraying sufficiently low cost; alteration of HAp
less risk of coating structure due to coating
degradation process; non-uniformity
in coating density;
phase transformation
and grain growth of
substance due to high-
temperature procedure

Sputter coating 0.53 m Uniform coating Line of sight technique; [46, 88]
thickness on flat expensive, time-
substrates; dense consuming; produces
coating; high adhesion amorphous coatings

Hot isostatic 0.22.0 Produces dense Cannot coat complex [89, 90]
pressing mm coatings; no substrates; high
dimensional or shape temperature required;
limitation thermal expansion
mismatch; elastic
property differences;
expensive;
removal/interaction of
 encapsulation material

Pulsed laser 0.055 m Coating crystalline and Line of sight technique; [37, 91]
deposition amorphous; coating splashing or particle
dense and porous deposition; needs
surface pre-treatment;
lack of uniformity
Biomimetic < 30 m Low processing Time-consuming; [92]
coating temperatures; can form requires replenishment
bonelike apatite; can and a constant pH
coat complex shapes; simulated body fluid
can incorporate bone
growth stimulating
factors
Table 3
The ratio of n(Ca)/n(P) and thickness of HAp coatings after immersion in SBF [107]
n(Ca)/n(P) Thickness/m
Before soaking 1.6156 16
Day 1 1.6698 16
Day 2 1.6723 19
Day 3 1.6722 32
Day 4 1.6727 76
Table 4
Adhesion strength of electrodeposition HAp coatings.
Composition Thickness Adhesion Reference
(m) Strength (MPa)
CoCrMo + HAp 0.2 17.5 [120]
1. Ti6Al4V + spherical HAp (sHAp) 10 10.7 [83]
2. Ti6Al4V + flake-shaped HAp 10 6.8
(fHAp) 10 8.5
3. Ti6Al4V + needle-shaped HAp 10 10.6
(nHAp)
4. Ti6Al4V + sHAp/ CNT-Ti
1. Ti + HAp 10 15.3 [130]
2. Ti + SWNTs/ HAp 10 25.7
1. Ti + HAp without oxidation 3 5.0 [104]
2. Ti + HAp with oxidation 3 7.3
1. Ti6Al4V + HAp 30 13.8 [132]
2. Ti6Al4V + TiO2 (50 V) + HAp 30 11.9
3. Ti6Al4V + TiO2 (20 V) + HAp 30 13.1
4. Ti6Al4V + TiO2 (10 V) + HAp 30 21.0
 Table 5
Mean bone-to-implant contact (BIC) and bone area (BA) in threads [157]
Implant Micro Macro Total Micro BA% Macro Total
BIC% BIC% BIC% BA% BA%

Heat Treated 62.8 (20.2) 41.5 (25.1) 57.1 (21.0) 77.6 (13.0) 46.1 (27.8) 72.4 (14.0)

(control)

HAp (test) 39.9 (18.9) 27.8 (16.2) 38.7 (17.7) 66.0 (14.2) 31.9 (18.5) 59.7 (12.5)
Fig. 1. (a) Cross-sectional SEM photograph of HAp-coated specimen deposited at 10 mA/cm2
and annealed at 500 oC for 1 h, and (b) EDS line scanning spectrum of line AB in (a) [111]
Fig. 2. SEM micrographs of primary and final coatings in comparison with uncoated supports of
Ti and Ti6Al4V alloy [114].
Fig. 3. SEM micrographs of hydroxyapatite coating deposited on Ti and Ti6Al4V alloy after 48
h soaking in Ringers solution (pH=7.1) [114].
Fig. 4. XRD spectra of CoCrMo after different immersion terms in Supersaturated Calcification
Solution (SCS) and Octacalcium Phosphate (OCP) standard data, JCPDF 26-1056; HAp
standard data, JCPDF 09-0432; S-substrate [120].
 HAp; Ti

Fig. 5. XRD patterns of the HAp coating on Ti substrate show homogeneous coating deposition
[107]
 CaP precursor
(pH~10)

Sol-gel (pH~9)

Aging (ambient
temperature)

Drying

Sintering
Drying

Fig. 6. Flow chart of HAp coating preparation by a sol-gel process

Fig. 7. High magnification, SEM image showing the thickness of HAp coating on commercially
pure Ti from a fractured section [149]
 Wet layer
formation

Solvent
evaporation

Immersion Withdrawal Drying

Fig. 8. Fundamental stages of dip coating technique

Fig. 9. Cross-section view of the coatings annealed at 375 oC shows (a) a uniform thickness of
about 0.6 m and (b) the ability of the solgel method to coat cavities/grooves of different
geometry on the substrates [155]