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Comparative Investigation on the Adhesion of Hydroxyapatite coating on Ti-6Al-4V Implant: A Review Paper E. Mohseni, E. Zalnezhad, A.R. Bushroa

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S0143-7496(13)00168-1 http://dx.doi.org/10.1016/j.ijadhadh.2013.09.030 JAAD1419

International Journal of Adhesion & Adhesives

Accepted date: 17 July 2013 Cite this article as: E. Mohseni, E. Zalnezhad, A.R. Bushroa, Comparative Investigation on the Adhesion of Hydroxyapatite coating on Ti-6Al-4V Implant: A Review Paper, International Journal of Adhesion & Adhesives, http://dx. doi.org/10.1016/j.ijadhadh.2013.09.030 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Comparative Investigation on the Adhesion of Hydroxyapatite coating on Ti6Al-4V Implant: A Review Paper

E. Mohsenia, E. Zalnezhadb, A. R. Bushroac*

a,b,c

Center of Advanced Manufacturing and Material Processing, Department of Engineering

Design and Manufacture, Faculty of Engineering, University of Malaya, Kuala Lumpur, 50603, Malaysia
a

ehsanmohseni2008@gmail.com e.zalnezhad@gmail.com Corresponding author: cbushroa@um.edu.my

b

Abstract Hydroxyapatite (HA) has been used in clinical bone graft procedures for the past 25 years. Although a biocompatible material, its poor adhesion strength to substrate makes it unsuitable for major load-bearing devices. Investigations on various deposition techniques of HA coating on Ti-6Al-4V implants have been made over the years, in particular to improve its adhesion strength to the metal alloy and its long-term reliability. This review comprehensively analyzes nine techniques mostly used for deposition of HA onto Ti-6Al-4V alloys. The techniques reviewed are Plasma sprayed deposition, Hot Isostatic Pressing, Thermal Spray, Dip coating, Pulsed Laser deposition (PLD), Electrophoretic deposition (EPD), Sol-Gel, Ion Beam Assisted deposition (IBAD), and Sputtering. The advantages and disadvantages of each method over other techniques are discussed. The adhesion strength and the factors affecting the adhesion of HA coating on Ti-6Al-4V implants are also compared. Keywords: Adhesion; Hydroxyapatite; coating; Ti-6Al-4V implant

1. Introduction Biological fixation is defined as the process where prosthetic components become firmly bonded to the host bone by ongrowth or ingrowth without the use of bone cements [1-3]. In the late 1960s, the concept of biological fixation of load-bearing implants using bioactive
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hydroxyapatite (HA) coatings was proposed as an alternative to cemented fixation. Hydroxyapatite (HA: Ca10(PO4)6(OH)2), a pure calcium phosphate phase, is a preferred biomaterial for both dental and orthopedics use due to its favorable osteoconductive and bioactive properties [4, 5]. HA has a similar chemical composition and crystal structure as the apatite in the human skeletal system, and is therefore suitable for bone substitution and reconstruction [6]. Furthermore, HA has shown significant success in implants due to its

favorable in vivo behavior [7, 8] and the presence of HA films prolongs the lifetime of prostheses [9]. However, HA coatings are susceptible to fatigue failure, making it unsuitable for load bearing implants [10, 11]. Nevertheless, there is a large demand for implants with excellent mechanical properties. These implants should possess similar properties to the human bones, such as in the value of its Youngs modulus, which result in less stress shielding effect [12] and extends its service life. The implants can made into different shapes such as plates, rods, screws and pins [13]. Historically, titanium-based alloys are the most common material for this purpose since it is known to be a tolerable metal in the human body [14]. Titanium (Ti) and its alloys are the most commonly used metallic materials for medical implants in orthopedic and dental applications, due to their low density, high strength, nontoxicity and excellent corrosion resistance [15]. However, there have been reports on inflammatory reaction around these implants as a result from the creation of an avascular fibrous tissue that encapsulated the implants [16, 17]. A coating of hydroxyapatite layer can be deposited on the metal alloy to assist the osseointegration of these implants with surrounding tissues [16]. The bond strength between the coating layer and the metal substrate is a very critical factor. Separation of the coating layer from the implant during service in the human body results

in adverse effects on the implants and the surrounding tissue caused by detached particles [18]. The main reason of using HA coating on metallic substrates is to keep the mechanical properties of the metal such a load-bearing ability and, at the same time, to take advantage of the coatings chemical similarity and biocompatibility with the bone [19]. According to Blind et al., the HA coating allows rapid osteointegration as a result of bone tissue bonding properties [20]. The first clinical results from HA coatings on titanium dental implants were promising, showing excellent results, even with poor bone quality. However, after a long period, mechanical failure would occur at the interface of HA and metallic substrate [21]. The HA coating dissolves as a result of poor crystallized structure [22, 23], decrease of adherence with the titanium surface and dramatic late implant failure [23, 24]. Moreover, HA itself has poor mechanical properties, with a bending strength of less than 100 MPa [25]. Thus, it can be concluded that the stability of the HA coating is the most critical factor to ensure the success of this type of implant. Furthermore, the method used to deposit HA powder onto the substrate could influence the coating characteristics such its adhesion strength and reliability. Several techniques have been used to create the HA coating on metallic implants, such as plasma spraying process [26], thermal spraying [27], sputter coating [28], pulsed laser ablation [29], dynamic mixing [30], dip coating [31], solgel [32], electrophoretic deposition [33], biomimetic coating [34], ion-beam-assisted-deposition [35],and hot isostatic pressing [36]. Amongst the techniques listed, plasma spraying is the only process which is approved by the Food and Drug Administration (FDA), USA for biomedical coatings due to its excellent coating properties as compared to other coating processes [37]. However, plasma sprayed hydroxyapatite coatings suffer from poor mechanical properties on tensile strength, wear resistance, hardness,

toughness and fatigue. Improvements in plasma spraying techniques over the years have addressed many of these limitations. However, other coating methods are available which can be used as an alternative to conventional techniques. Limitations such as high porosity, poor uniformity in thickness, phase impurity, limited crystallinity, and poor adhesion are common in HA coating. However, low coating adhesion seems to be the major issue, limiting its extensive use for implants at a commercial scale [38-40]. Hence, improvement of bonding strength between the metallic substrate and ceramic coating is a general requirement regardless of the techniques used. This review focuses on adhesion strengths between HA coating and Ti-6Al-4V substrate, fabricated using various techniques such as plasma sprayed deposition, hot isostatic pressing, thermal spray, dip coating, pulsed laser deposition (PLD), electrophoretic deposition (EPD), solgel, ion beam assisted deposition (IBAD). Parameters affecting the adhesion of coating and other factors influencing the enhancement of bonding strength of coating surface and the substrate are also discussed in detail.

2. Coating techniques 2.1 Plasma sprayed coating technique Plasma spraying process involves melting of ceramics or metal powders using the heat of ionized inert gas (plasma). The molten powders are then sprayed onto the surface to be coated, forming the protective layer which provides a barrier against corrosion, wear or high temperatures. The technique offers advantages such as low cost and rapid deposition rate [41, 42]. In addition, the risk of thermal degradation of the coating and substrate is much less than
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other high-temperature processes since the gas in the plasma flame is chemically inert and the target can be kept relatively cool [43]. However, plasma sprayed coatings suffers from poor adhesion between the coatings and substrates [44], and the process may induce structural changes in the microstructure of the coating material [45, 46]. 2.1.1 Plasma sprayed hydroxyapatite (HA) coatings Plasma spray was the first method used for the production of calcium phosphate coatings, such as HA coating, due to its ease of application [26]. Plasma sprayed hydroxyapatite (HA) coatings are biocompatible and able to bond directly to the bone [38], thus making plasma spraying a favorable choice amongst the many techniques available for coating HA layers onto metallic substrates [47]. Recent studies on plasma sprayed HA coatings (HACs) on titanium have shown encouraging results in orthopedic implant applications. These studies reported that the new bone could appose directly onto the HA coatings and very good adhesion between the HACs and the new bone can be obtained [48-51]. The plasma sprayed HA coatings have also assisted in overall quick bone recovery [52]. Nevertheless, the brittle nature of the HA coating makes it prone to crack and fracture, non-uniformity in density of coating [53], wear of the coated layer, weak mechanical adhesion to the substrate [44, 54], and alteration of structure [55]. Overall, plasma sprayed coating did not show significant improved long-life performance, better mechanical integrity and reliability over uncoated implants [56, 57]. An alternative to plasma spraying is the pulsed laser deposition (PLD) which enables the stoichiometric transfer of sintered HA yields to form a thin and adherent bioactive coating on titanium substrate surface [58]. 2.1.2 Adhesion of plasma-sprayed hydroxyapatite (HA) coatings on Ti-6Al-4V

It is well understood that, the determination of the adhesion between the substrate and coating is one of the main concerns when using plasma spraying techniques [59]. Its quite complicated that how coating adheres to a substrate and by today it is not completely understood. Many theories describe the mechanism of adhesion, although, there is no single clear interpretation for all adhesion behaviors [60]. Many factors seem to affect the adhesion: (1) Van der Waals physical interaction forces mechanical anchorage; (2) mechanical anchorage; (3) metallurgical processes and (4) chemical interaction [59]. Recent reports on alternative orthopedics implant fixation utilizing plasma sprayed HA coatings (HACs) on Ti-6Al-4V have shown that the new bone was able to appose directly onto the HA coatings, which resulted in a very good adhesion between the HACs and the new bone [48-51]. From the viewpoint of materials science, characteristics of HACs are varied with the spraying parameters such as phase composition, the microstructure, OH-ion content, crystallinity, and the ration of calcium to phosphorus for the HACs. Among these parameters, high bonding strength of HACs can be achieved by high spraying power due to a denser microstructure caused by the greatest extent of coating melting. Y.C. Yang, et al. experimented on six plasma sprayed HA on Ti- 6Al- 4V substrates by varying the cooling conditions and the substrate temperatures [61]. The residual stresses and bonding strengths were measured by XRD sin2 technique and a standard adhesion test (ASTM C-633). Results of the bonding strength evaluation shows that the HA coating with the lowest residual stress exhibited a higher bonding strength (9.180.72 MPa). The deposition stress and thermal stress are the two major sources of residual stresses in plasma sprayed coating. Deposition stresses are produced during the cooling of sprayed particles after solidification. Thermal stresses are generated from differential thermal contraction during

the post-fabrication cooling phase after coating [62, 63]. The residual stresses are present near the interface of metal substrate and coating [64-66], due to the difference of thermal expansion coefficients between both materials [62, 63]. These stresses may vary with substrate cooling effects, parameters of spraying [62, 63], and coating thickness [67, 68]. Generally, it is believed that the increased thickness of coating and the temperature of the specimen during plasma spraying are the mains reasons for the rise in the residual stress. In addition, high-powered, dense plasma sprayed HA coatings would have stronger bonding strength than those sprayed using low power. The result is not solely due to the difference in adhesive strength of HA coating. The value for bonding strength reflects the combination of both cohesive (within the coating layers) and adhesive (coating to substrate) strengths of a coating [61]. In a similar study, Tsui, Y. et al. claimed that the cohesive and adhesive integrity of the coatings influence the long term performance of HA coated implants considerably [69]. The adhesive strength is usually evaluated based on surface roughness, coating properties, residual stress, and the mechanical interlocking between the coating and the substrates, whereas the cohesive strength is determined by coating properties, such as microstructure and crystallinity [61]. The bonding strength of HA coatings on metallic substrates can be evaluated using several techniques such as the standard tensile adhesion test [69], interfacial indentation test [58], tensile adhesion strength (TAS) [61], and indentation method [63]. However, there are limitations on these techniques to accurately measure the adhesion strength, such as a probability of penetration of glue into the coating layer , and a dependence of coating failure to the flaw distribution at the edge of specimen [69]. However, Z. Mohammadi et al. have demonstrated that the tensile adhesion strength test measured by the standard adhesion test ISO 13779-4, can be

used in conjunction with the interface indentation test to predict the effects of different parameters on the adhesion properties of the HA coating by plasma spraying [70]. In general, the HA coatings with the densest structure (i.e. lowest porosity, and predominantly amorphous phase) have a higher tensile adhesion strength than those of lower density [61, 71]. The report by Z. Mohammadi et al. [70] also showed that the tensile adhesion strength was in the range of ~25 MPa for HA coated on the Ti-6Al-4V.

2.2 Hot isostatic pressing technique Hot isostatic pressing (HIP) is an enabling technology providing an efficient method for the densification of ceramic powders which allows production of net-shape ceramics with superior and consistent properties [72]. HIP is an alternative method of producing an HA coating on a Ti substrate in which pressurized gas is used to exert the required load at the desired temperature. This requires a gas-tight metal or glass encapsulation around the porous HA coated implant [73]. In the HIP process, pressure and temperature are applied to the workpiece simultaneously [74-77]. In hot isostatic pressing, high-pressure levels can be obtained since there is no dependency on rigid tools with limited strength (such as graphite tools in uniaxial hot pressing) to transmit the pressure to the body. Typical operating pressure ranges are 100-320 MPa (15-50 ksi), with temperatures exceeding above 2000 C conducted in large industrial equipment [72]. The advantages of HIP are better temperature control as compared to uniaxial hot pressing, and a

resultant homogeneous material structure and properties. The reduced sintering temperature enables control or even avoidance of grain growth and undesirable reactions. A very high uniformity of properties as well as freedom from directionality can also, if desired, be obtained [72]. Some researchers have used HIP treatments to densify plasma sprayed coatings, and results have shown that HIP is useful in reducing the porosity and improving the physical and mechanical properties of ceramic coatings [78]. Thus, the most important advantage of the hot isostatic pressing is the ability to control the size and shape of the product to a very high precision without costly diamond machining operations. Under ideal conditions no change of shape (just a change of scale) of the body occurs. It has an inherent ability to produce parts with exceptionally accurate shape, virtually with no dimensional or shape limitation [72]. 2.2.1 Hot isostatic pressing of hydroxyapatite (HA) Coatings Reports shows that, sort of problems such as porosity and crack appearance are conducted with existing dc plasma sprayed Ha coating on Ti-6Al-4V [79]. In medical applications some amount of porosity is needed for bony tissue to grow into the coating for efficient fixation. In addition, the crack propagation needs to be healed for the composite coating to have reasonable mechanical strength during usage. In this sense, HIP introduces its profound advantages by improving the adhesion and physical properties of the plasma sprayed HA coatings as a post- treatment [79]. 2.2.2 Adhesion of hot isostatic pressing of hydroxyapatite (HA) coatings on Ti-6Al-4V K. Khor et al. [79] investigated the effect of post-sprayed HIP on plasma sprayed HA on Ti-6Al-4V. Fig.1 shows the bond strengths of HA coated Ti-6Al-4V for the plasma sprayed samples, and after HIP treatment at different temperatures with respect to the coating thickness.

In general, it was shown that the bonding strength generally improves after HIP. It is also shown that the adhesion strength decreases with increasing coating thickness. The enhancement of the adhesion strength in the 20 wt.% HA coating after HIP is apparent for coating below 160 m. However, the result of adhesion strengths for coatings thicker than 160 m show that HIP may have adverse effects on the coating strengths.

2.3 Thermal spray coating technique Thermal spray technology is a group of coating processes that provide functional surfaces to protect or improve the performance of a substrate or component. Many types and forms of materials can be thermal sprayed to provide protection from corrosion, wear, and heat; to restore and repair components; and for a variety of other applications [80]. Thermal spraying of biomedical coating is a relatively new class of applications for thermal spray coating as compared with other industrial applications, [81]. Thermal spray processes are grouped into three major categories: flame spray, electrical arc spray, and plasma arc spray. These energies sources are used to heat the coating material (in powder, wire, or rod form) to a molten and semi-molten state. The resultant heated particles are accelerated and propelled towards a prepared surface by either process gases or atomization jets. A schematic diagram of thermal spray coating is illustrated in Fig. 2. 2.3.1 Thermal spray deposition of hydroxyapatite (HA) coatings Thermal spraying of HAP on implant devices can be compared with plasma spray coating technique, having the advantage of high deposition rate and low cost [82, 83]. Thermal spray technique has the ability to produce HA layer with thickness from 30 to 200 m depending on

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the coating condition However films deposited by thermal spraying suffers from poor coating substrate adherence and non-uniform crystallinity which reduces the lifetime of implants [84, 85]. In addition, thermal spray requires high sintering temperature which may result in crack propagation on the surface of the coating [86-90].

2.3.2 Adhesion of thermal spray deposition of hydroxyapatite (HA) coatings on Ti-6Al-4V J. Hsiung et al. [91] have evaluated the applications and characterizations of biological coating such as hydroxyapatite on titanium alloy, particularly Ti-6Al-4V, in artificial knee joint by thermal spray coating technology. The process involves melting of HA powder and guiding the molten mass via a jet stream of air to form a coating on the substrate, as shown in Fig. 3. The thermal spray process conditions of the three coating materials are shown in Table 1, highlighting the important parameters affecting the quality of the coating, such as inert gas compositions, currents, voltage levels, powder feeding rates, and spraying distances. The tensile test is commonly used to evaluate the bond strength in accordance to ASTM C633 standard method [92]. A bonding strength of 33.2 Mpa was obtained by J. Hsiung et al. [91] for the HA coating on Ti-6Al-4V by thermal spraying technique. In comparison, this result is not satisfactory when compared to other coatings for the same application such as Al2O3, ZrO2. In addition, results of microstructure analysis shows that the HA coatings suffers from spalling, interface separation and high levels of porosity. Several pre and post-treatments of HA coating were also investigated by J. Hsiung et al. [91]. Treatment conditions include high pressure cleaning, ultrasonic cleaning and cryogenic treatments. [92]. Table 2 shows the result of the bond strength test using ASTM C633 [93],

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indicating the bond strengths of samples cleaned with high pressure air are lower as compared with those ultrasonically cleaned, and the bond strengths with cryogenic treatments are better than those without cryogenic treatments. The result shows that the inclusion of ultrasonic cleaning and cryogenic treatments can effectively improve the coating properties.

2.4 Dip coating technique Dip coating involves the deposition of a wet liquid film by withdrawal of a substrate from a liquid coating medium. The complete process of film formation involves several stages, as shown in Fig 3. The process starts by immersion of the substrate in the solution of the coating material. When the substrate is withdrawn from the coating fluid, a coherent liquid film is entrained on the surface of the substrate. A thin layer of coating is formed upon evaporations of solvents and any accompanying chemical reactions in the liquid film. Normally an additional post-treatment such as curing or sintering is required to obtain the final coating. Dip coating technique is similar to sol-gel coating technique, although the process is significantly faster in which a complete transition can be achieved within a few seconds if volatile solvents are used [94]. Dip coating is fairly popular in the industry and in laboratory applications due to its low cost, simple processing steps and high coating quality. 2.4.1 Dip coating of hydroxyapatite (HA) coatings HA can be homogenously coated onto metal substrates to obtain coating thickness in the range of 0.05 to 0.5 mm. The surface uniformity of HA can be controlled well using this technique, as can be seen in the Fig. 4. In addition, the processing time for dip coating can be very short, even for substrate with complex shapes. The coating layer is deposited on the surface of the substrate without decomposition or reaction with the metal substrate. However, this

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technique requires high sintering post-treatments which may induce crack formations on the surface of the substrate [95].

2.4.2 Adhesion of dip coating of hydroxyapatite (HA) coatings on Ti-6Al-4V B. Mavis et al. [96] had developed several compositions of the liquid coating medium for the dip coating of HA on Ti-6Al-4V substrates, using chemically precipitated hydroxyapatite precursor powders. To evaluate the adhesion strength, two steel cylinders 5 mm in diameter were attached to both sides (coated and uncoated after the coating layer was ground off) of the dipped strips by a thin layer of glue. The adhesive strengths were determined by measuring the tensile stress needed to separate the cylinders from the strips [97]. It is reported that, the HA coatings obtained were highly porous, with bonding strengths of more than 30 MPa.

2.5 Pulsed Laser Deposited Coating Technique Laser processing is a rapid and clean process which can be used for surface modification and controlled micro-structuring of materials. In biomedical applications, laser has been used to modify the surface texture of materials to improve its bio-functionality [98-102]. Pulsed laser deposition (PLD) technique can be used to grow ceramic thin films. By using appropriate laser, thin films such as semiconductor films [103], cuprate superconductor films [103, 104], and ferroelectric films [105] can be deposited onto substrates. PLD process involves using high power laser energy to vaporize the bulk coating material from a target. The vaporized material is ejected from the target and condenses on the substrate. Repeated laser pulses will result in the deposition of the thin film as a coating on the substrate [106].

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The formation of thin film by PLS can be separated into the following three stages [103, 107, 108]: 1- Laser radiation interaction with the target. 2- Dynamic ablation of the materials. 3- Deposition of the ablation materials with the substrate, nucleation and growth of a thin film on the substrate surface. One of the main advantages of PLD technique is the ability to retain the stoichiometry of the target in the deposition films [107]. This is due to the high ablation rate which causes all compounds or elements to evaporate at the same time [106]. Conversely, limitations of PLD include the splashing of the particulates deposition on the film. Some methods have been developed to decrease splashing problem since it is a major issues of the PLD [109]. One method is to apply a mechanical particle filter that includes a velocity selector acting as a high-velocity pass filter to eliminate slow-moving particulate. The second method is using a smooth, highdensity target which can be obtained by polishing the target surface before each coating run. The third method is by applying a lower deposition rate or low energy density. Furthermore, the deposited films have only a small area of structural and thickness uniformity, due to the angular distribution of the ablation plume. Several methods have been proposed to scale up the PLD process for large area thin films, such as laser beam rasterizing across a rotating target. [106]. High quality hydroxyapatite thin films deposited by the PLD was first reported in 1992 [105, 110] and since then the process have been improved significantly to obtained well adhered and highly crystalline HA thin films under certain conditions [29, 111-113]. 2.5.1 Pulsed laser deposited hydroxyapatite (HA) coatings

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Preparing hydroxyapatite thin films by pulsed laser deposition allows accurate control of hydroxyapatite growth parameters at low deposition temperatures and the ability to produce highly crystalline HA coatings[16, 112]. In-vitro evaluations shows that these HA coatings are stable and osteoinductive [114, 115]. Nanostructured hydroxyapatite layer having unique biological properties can be obtained by selection of suitable parameters for the deposition process [16]. 2.5.2 Adhesion of pulsed laser deposited hydroxyapatite (HA) coatings on Ti-6Al-4V Adhesion strength of HA coating on metals depends on the microstructure of the substrate, the surface chemistry and the PLD process parameters such as laser power density and substrate temperature. [58, 116-118]. Various surface modification techniques have been used to improve the metal-ceramic interface such as nitridation, surface oxidation and ion implantation [119-123]. Blind, et al. reported that adhesion of pulsed laser deposited HA films on titanium alloy is due to the existence of an oxide, specifically titanium dioxide, at the interface between the substrate and the coating layer [20]. Another report suggests that there may be some effects of epitaxy between the oxide and coating [124]. Fernandez- Pradas et al. [54] commented whether the presence of a titanium oxide interface would favour adhesion of the HA coating to the Ti6Al-4V substrate is still a cause for debate. Some authors consider that such a layer favours adhesion [125, 126]. Other studies have attributed the weak adhesion in the first calcium phosphate coatings deposited by PLD at high temperatures to the formation of a titanium oxide layer during the process of pressure stabilisation [105]. A study of the adhesion strength in coatings deposited by ion bombardment on passivated and non-passivated substrates, suggest that this oxide layer should be as thin as possible [127].

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C. Koch et al. [16] investigated pulsed laser deposition of hydroxyapatite on Ti-6Al-4V for medical and dental applications. A pull-off testing method was used to determine the coatingto-substrate adhesion strength. Garcia-sanz et al. had also examined hydroxyapatite films prepared using pulsed laser deposition using a pull-off test based upon a modified ASTM C-633 procedure [128]. The measured tensile strength of hydroxyapatite grown at 480 C was 58 MPa and failure was observed at the coatingsubstrate interface. Wang et al. obtained tensile bonding strength values within the range of 30 MPa and 40 MPa for hydroxyapatite coatings grown on Ti-6Al-4V in an argonwater atmosphere at 500600 C [129]. Zeng et al. determined the bond strength values for hydroxyapatite films grown using 3rd harmonic YAG:Nd lasers (=355 nm), and 4th harmonic YAG:Nd lasers (=266 nm) on Ti-6Al-4V substrates in an argonwater atmosphere at 500520 C [116]. Films grown on unpolished titanium substrates had tensile strength values of 30 MPa while films grown on polished titanium possess lower tensile

strength values of 20 MPa. In a study to enhance the bonding strength of HA , Nelea et al. [110] utilized a TiN interfacial layer between the Ti-6Al-4V substrate and HA coating. The study reported that the adhesion was improved due to better bonding of HA to TiN, which is a ceramic, and then to the surface of metallic substrate. Man et al. [40] and Cui et al. [130] described the utilization of a pre-treatment process which included etching and laser surface nitriding on titanium to produce a TiN dendritic scaffold network structure. This coralline-like structure provides additional surface area for interlocking of the coating material. Man et al. [119] reported the influence of pre-treatments on the adhesion of the HA coating to the substrate. Five types of pre-treatments, shown in Fig. 5 were: (i) mirror finished specimen, (ii) 60 grit grinded SiC paper (specimen 2), (iii) 320 grit grinded SiC paper (specimen

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3), (iv) mirror finish with 1-m diamond paste (specimen 1), and (v) 10 s etching with Knoll solution after polishing (specimen 4). The surface roughness of the specimens were determined using a profilometer (Taylor Hobson Surtronic 25) and the adhesion strengths between HA coatings and the substrates were evaluated in accordance to ASTM C-633 [131]. The maximum adhesion strength obtained was ~ 16 MPa for specimen 5 (nitrided+ etching). Figure 5 shows the adhesion strength of deposited HA on different pre-treated specimens and surface roughness. Generally, an increase in surface roughness increases the adhesion strength. Based on these results, it can be concluded that significant enhancement in the adhesion strength of pulsed laser deposited HA on Ti-6Al-4V can be obtained by laser surface nitriding and subsequent etching [119]. A related study has concluded that a controlled surface microstructure can be obtained by using few laser pulses without affecting the bulk mechanical property of titanium substrate [132]. Figure 6 plots the average surface roughness values, measured after laser treatment and after HA coating versus their initial roughness. Figure 7 compares the adhesion strengths of HA coating on substrates treated with 500 18,000 laser pulses with those of untreated, polished titanium. The adhesion of HA to the substrate is examined in accordance to ISO 20502:2005(E) [133] using a micro-scratch tester (micro-combi tester; CSM Instrument Switzerland) equipped with a diamond Rockwell tip of 100 m [132]. It was found that in all cases, the laser treated substrates would have higher bonding strengths, which imply that the surface roughness directly influences the adhesion strength. Varying the laser pulses would affect the surface morphology. Figure 6 shows that the roughness increases with the increase in the number of laser pulses, which starts from ~ 0.4 m at 500 laser pulses/min up to ~ 1 m at 12000 pulses/min. However, there is a significant

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decrease in the roughness value for laser pulses in the range of 12000 to 18000 laser pulses/min. Low rate of laser pulses ( 500, 1,000, and 3,000 pulse/min) would only etch the surface and may not be able to control the surface roughness. The surface roughness is under control only after ~ 3000 pulses/min. A surface with controlled structure/pattern is obtained using 18,000 pulses [132]. The polished surface of specimen does not have much adhesion strength to the coating. However, once the surface is treated with laser, the surface roughness increases which results in increased adhesion (from 0 to 1000 pulses/min) due to the initial material removal from the surface. However, at this stage, certain regions are unaffected by the laser and a control over the adhesion at this stage is not predictable. Once the laser pulses reaches ~3000 pulses/min, the surface attains a certain level of smoothness since the large, number of pulses would completely remove the original top surface to uncover a fresh coating surface. Therefore, the morphology and adhesion can be controlled by the number of laser pulses (3000 to 18000) [132]. Figure 7 shows the trend of adhesion strength versus number of laser pulse, showing that the adhesion strength would gradually increase until 1000 pulse/min, then decreases in between 1000 to 3000 pulse/min, and increases again past 3000 pulse/min. The highest adhesion strength obtained was 10.87 N and 11.21 N at 2,000 and 18,000 laser pulses respectively, while untreated substrate showed a lower adhesion strength value of 4.57 N [132]. HA coatings by PLD exhibit good biocompatible and mechanical properties making it suitable for medical implants. PLD HA coatings, on titanium alloy such as Ti-6Al-4V, resulted in higher adhesion between the coating and substrate and have only minor undesirable phase under optimal conditions [54, 106]. 2.6 Electrophoretic deposition coating technique

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Electrophoretic deposition (EPD) is a process in which particles in a suspension is coated onto an electrode under the effect of an electric field [134]. The colloidal particles suspended in a liquid medium migrate under the influence of an electric field (electrophoresis) and are then deposited onto an electrode. Electrophoretic deposition (EPD) is particularly advantageous for ceramic film and coatings as well as laminar ceramic composites applications [134-137]. Furthermore, the method used low-cost equipment, easy to set-up, and is able to coat complex shapes and patterns. A high degree of control on the coating results can be achieved by regulating the deposition conditions and the ceramic powder size and shape [138]. EPD is a cheaper method than chemical vapor deposition, sol gel deposition, and sputtering for producing films of a wide range of thickness, from less than 1 mm to more than 100 m thick [139]. However, limitations of the technique includes low adhesion strength, and cracking on the coated surface due to post-process shrinkage. EPD has shown its potential use in biomedical applications in recent years [140-142]. The interest in electrophoresis for biomedical applications [143-147] stems from a variety of reasons such as the possibility of stoichiometric deposition, high purity material to a degree not easily achievable by other processing techniques and the possibility of forming coatings and bodies of complex shape [140]. Considering all advantages and disadvantages of this technique, electrophoretic deposition is one of the favorable coating techniques which can be utilized for hydroxyapatite coating.

2.6.1 Electrophoretic deposition hydroxyapatite (HA) coatings

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There is a growing interest in processing of HA powders using EPD technique, owing to its uniformity and good sinterability of the deposits, possibility of impregnation of porous substrates, and composite consolidation [142, 148]. However, reports on the use of EPD for depositing HA on titanium substrate are thus far, relatively limited. Nie et al. [149] and Soares et al. [150] have used EPD to deposit HA on Ti-6Al-4V substrates and have obtained uniform thin coating with good mechanical strength. Stoch et al. [146] have also coated HA on titanium implants with intermediate layer of silica. EPD process of HA is a colloidal process where HA powders are deposited directly from a stable colloid suspension by using a DC electric field [25]. Electrophoretic deposition of HA can be processed at room temperature or lower, which avoids problems related to formation of amorphous phases. The nature of the bond is more metallurgical rather than mechanical, thus HA coatings using EPD are expected to have improved adhesion strength as compared to thermal sprayed techniques. However, a major drawback is the presence of porosities which may later on leads to corrosion and delamination of the titanium caused by penetration of body fluids into the substrate. Post-treatment high temperature sintering can be utilized to minimize the porosity by increasing the coating density. Unfortunately, cracks in the coating can form during high temperature sintering due to the difference in the thermal expansion coefficients and large reduction of the pore volume between the titanium and HA [151]. For nanostructured materials, the mismatch in thermal expansion coefficient is not a significant problem [152]. In nano-ceramics, the thermal expansion coefficient is fairly matched with the metal alloy because the large quantity of atoms located at the grain boundary improves mobility [152-154]. However, the success of electrophoretic deposited HA has been limited to conventional materials in the range of micron-sized grains [134, 140, 154]. Limitations on the

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mechanical properties of the micron size HA are poor fracture toughness, adhesion, and compressive strengths. There is a need for the HA coating and the substrate to have sufficient interfacial bond strength since the coating would endure high interfacial stresses during in vivo service. 2.6.2 Adhesion of electrophoretic deposited hydroxyapatite (HA) coatings on Ti-6Al-4V Zhang, et al. [151] have developed a unique room temperature EPD process to deposit nanostructured HA coating having adhesion strength of 50-60 MPa, which is 2-3 times better than thermal-sprayed HA coating. The interfacial bond strength was measured in accordance to ASTM Standard F 1501-95 using a tensile tester [151]. The corrosion resistance of this nanostructured HA is 50 to 100 times higher than conventional HA coating. Fig. 8 shows the corrosion resistance results for both EPD coatings and thermal sprayed coatings, where the corrosion current of n-HA coating is 50-100 times smaller than the thermal sprayed coating in simulated human body fluid at room temperature.

High quality HA nano-coating can be produced using EPD technique. The adhesion stress obtained was 60 MPa, measured using a direct-pull-tests, which exceeds the 50 MPa requirements of the food and drug administration (FDA) [155]. A 2 months in vitro testing also showed that the bonding strength of the EPD n-HA coating on the titanium alloy was able to be maintained in the range of 50-60 MPa, which is significantly better than plasma sprayed HA coatings [151]. Ma, et al. [139] reported that HA particles were successfully deposited onto a titanium substrate via a single electrophoretic deposition. Good adhesion between the coating and substrate was verified by scanning electron miscopy examination and shear strength tests,

21

following methods outlined by Wei et al. [148] and ASTM standard F1044-87. The shear stress of the HA coating after sintering at 1000 C was 3.34 MPa, indicating a good adhesion of the coating has been obtained. Figures 9 and 10 show SEM micrographs of the cross-section and the surface deposit of the 1000 C sintered HA coating, respectively. It can be seen that a layer of HA coating as thick as 400 m has adhered well into titanium substrate and no delamination or crack was observed at both the interface and the surface. The deposition was found to be uniform with the coating thickness maintained consistently along the surface of the sample. No observable crack, which is one of the common problems of EPD, was detected. It is believed that the good deposition result is due to the stable and dispersed HA suspension used for the deposition [148]. Studies on EPD coating of HA on titanium alloys show that particle size is an important factor for the process as the mobility of the charged particles is proportional to the size of the particles [156]. Ferrari et al. [157] have also reported that the charges, hence the conductivity of the suspension, play an essential role and has an optimum value for the process. Nevertheless, the colloidal stability of the suspension could also be a main factor to obtain good coating uniformity and bonding strength in the EPD process [142]. Like many similar techniques for coatings involving ceramics, EPD coating of HA requires a densification stage involving the sintering of the coated implants. This requirement poses a dilemma, especially since high sintering temperature is sometime necessary. Low sintering temperatures results in weak bond with low-density coatings whereas high sintering temperatures can lead to the degradation of the HA and the metal substrate (oxidation and impaired mechanical properties) as a result of the metal substrate catalyzing decomposition of the HA to anhydrous calcium phosphates [158, 159].

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A high sintering temperature may also lead to phase transformation and grain growth of the metal substrate, causing significant decrease in mechanical properties. It has been demonstrated that the mechanical properties of these titanium alloys degrade significantly when heated above 1050C [138]. Therefore, it is recommended to keep the densification temperatures below 1000C to minimize degradation of the HA and the metal substrate. The sintering phase for EPD implants improves densification and the bonding of the coating. However, HA may decompose in the process [160]. An interlayer can be used in between the HA and the metal substrate to moderate the problem of HA decomposition. Nie et al. deposited a dense layer of titanium dioxide (TiO) as the inner layer between HA top layer and titanium alloy substrate to achieve a very good combination of mechanical integrity, chemical stability and bioactivity [149]. Kumar and Wang [161] investigated the coating of TiO powders on Ti-6Al-4V substrates as the first layer, followed by the HA- TiO composite layers of different weight ratios, coated onto the TiO layer. Wei et al. [138] studied on the adhesion strength of HA coating in which HA powders are used as both inner and outer layer. Hence, no change occurred in the structure of coating layers. Sintering was also applied after the deposition of every single layer. In the HA coating on TiO deposited substrate, the decomposition of HA is decreased; and generally adhesion of coating, which is tested according to ASTM F1044-99, was enhanced with the reduction of voltage value used for TiO coating [160]. Table 3 shows the result of adhesion strengths of HA coated samples with and without TiO2 inner layer deposited using different voltages. 2.7 Sol-Gel derived coating technique

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The Sol-gel method is one of the simplest technique to manufacture thin films which can produce almost any single or multicomponent oxide coating on glass or metals [162, 163]. Solgel derived coating can be used for optical, electronic, magnetic or coating with chemical functions [164]. Sol-gel derived ceramic films are widely used as a protective layer against corrosion and oxidation of stainless steel [165], Ag [166], and Al [167] substrates. The sol-gel process involves the formation of solid materials, mainly inorganic non-metallic materials from solution. This can be a solution of monomeric, oligomeric, polymeric or colloidal precursors [168]. The sol-gel process, shown in Fig. 11 [169], consist of: (i) producing a homogeneous solution of purified precursors in an organic solvent which can be mixed with the reagent used in the next step or water; (ii) shaping the solution to the sol form by using treatment with a suitable reagent, e.g. water for oxide ceramics; (iii) changing the sol to a gel by polycondensation; (iv) converting the gel to the finally preferred shape like thin film, fiber, and (v) finally converting( sintering) the shaped gel to the desired ceramic material at temperatures (~500C) much lower than those required in the conventional procedure of the melting the oxides together [168, 170-172]. Olding et al. [172], reports that sol-gel techniques has considerable advantages such as : 1. Ability to produce thin bond-coating to provide excellent adhesion between the metallic substrate and the top coat. 2. Corrosion resistance performance due to ability to form thick coating. 3. Ability to shape materials even complex geometries in the gel state. 4. Production of high purity samples. 5. Low temperature sintering, usually in the range of 200 to 600 C [173].

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6. A simple, economic and effective method to produce high quality coatings. However, the sol-gel technique has disadvantages such as high permeability, low wearresistance, and difficult porosity control, which has limited its utilization in the industry. For crack-free coating, the maximum thickness of the coating is only 0.5 m [172]. Furthermore, trapped organics during the thermal process would result in coating failure. Recent advancement in high substrate sensitive sol-gel also suffers from thermal expansion mismatch. Nevertheless, there is a wide room for improvement in the technique and further investigation should be done to improve this highly potential method for biomaterial coating.

2.7.1 Sol-Gel derived hydroxyapatite (HA) coatings The sol-gel is a low temperature process, thus does not suffer from the implications of structural instability of hydroxyapatite at elevated temperatures [174-177]. A major processing stage involves solution chemistry, whereby a sol is produced from suitable alkoxides or salts to yield a hydroxyapatite composition upon heating [178]. Gross, et al. [178] described that the production of sol-gel hydroxyapatite coatings on titanium substrates using alkoxide precursors requires more control on firing temperature and the aging time. X-ray diffraction of the coatings heated to various temperatures, as illustrated in Fig. 12, indicated that the titanium substrate would start to oxidize at temperatures starting at 800C. Thus for sol-gel hydroxyapatite coating, it is suggested that the processing temperature should be around 800C to reduce possible phase transformation in the metallic substrate as well as the occurrence of oxidation. [178]. Nanograined hydroxyapatite coating with an average grain size of 50 nm was achieved using this technique. Figure 13 shows a scanning electron micrograph of

25

a coating fired to 800C for 10 min. Densification of the coating can then be obtained with a longer duration of firing at 800C. Fabrication of sol-gel deposited HA on implants HA[173, 179, 180] requires extremely stringent processing parameters, particularly for the thermal processing phase such as the duration and calcining temperature, chemical compositions of the precursor , types of substrate, and number of HA- coated layers. Major issues include the crystalline phases, adhesion strength and biocompatibility of the resulted coatings.

2.7.2 Adhesion of Sol-Gel deposited hydroxyapatite (HA) coatings on Ti-6Al-4V Tests have shown that pure HA suffers relatively high dissolution rate in simulated body fluid that would affects its long-term stability. High dissolution may lead to disintegration of the coatings and hinder the fixation of implant to the host tissue [181, 182]. To address this issue, Zhang, et al. [183] incorporated fluorine ion, which exists in human bone and enamel, into HA crystal structures. Mixing of fluorine into HA, or fluoridation, decreases the solubility of HA while still maintaining its biocompatibility [184]. Zhang, et al. [183] have successfully deposited dense, crack-free fluoridated hydroxyapatite (FHA, Ca10(PO4)6 (OH)2xFx) coatings ( 1.5 m) through solgel dip coating on Ti-6Al-4V substrates. Scratch testing has shown an increase of over 35% in the adhesion strengths of the coating to Ti-alloy. The increase in adhesion is more prominent for high annealing temperatures. This increase is most likely due to the formation of chemical bonding at the interface and the incorporation of fluorine in HA which provided relief of thermal mismatch. Figure 14 illustrates the coefficient of friction in terms of relative voltage as a function of normal load while scratching (a) pure HA coating; (b) fluoridate HA (FHA6) coating on Ti-6Al-

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4V. At the beginning of the scratch and because of the soft nature of the coating, coefficient of friction increases as load increases. The fluctuation in the diagram, before point 1, is caused by the surface roughness. After point 1, the indenter would start to advance into the coating, resulting in a sharp increase in friction coefficient. The indenter would completely peel off the coating and scratches the substrate as the load increases to point 2, or 370 mN for pure HA (shown in curve a), which results in a sudden increase in friction at about 470 mN for FHA6. Comparison of curves (a) and (b) in Fig. 14 shows that curve b appears to have less fluctuation before the indenter completely digs in and the adhesion of coating and substrate is better since there is a slower gradient rise after the indenter digs in. A sharp increase of friction would indicate a brittle peeling-off of the coating from the substrate surface. Since curve b lacks the sharp change in friction, it is thus a more ductile interface and subsequently have better coating-substrate bonding than those of curve a (pure HA) [185]. Figure 15 shows the upper critical load,Lc, of all FHA coatings as a function of firing temperature and fluorine. Both firing temperatures and fluorine content seems to have a significant effect on the adhesion strength of the coating. Increasing firing temperature or fluorine concentration results in a dramatic raise of the critical load. For coatings with the same amount of fluorine content, higher adhesion is due to higher annealing temperatures. Similarly, at the same firing temperature, adhesion strength increases with fluorine content. Zhang, et al. [186], in similar studies [183], reported that FHA is a potential

replacement for pure HA coating on metallic implants due to FHAs significant biocompatibility and resistance to biodegradation [184, 187]. Ding, et al. [188] identified two critical aspects as the main contributors for long-term stability of the ceramic-coated implants: high adhesion strength of substrate to coating and low solubility of the coating. Incorporation of fluoride ions

27

into HA lattice structure results in reduction of HA solubility. However, reports on adhesion improvements, especially on adhesion studies after in vitro dissolution test have yet to be studied extensively. In vitro dissolution tests can be used to investigate the influence of dissolution behavior on the adhesion. Zhang, et al. [186], evaluated the adhesion of FHA coated on Ti-6Al4V using sol-gel technique before and after dissolution tests. The dissolution tests were conducted by soaking FHA coatings in a Tris-buffered physiological saline solution (TPS) (0.9%NaCl, pH7.4) at a fixed temperature of 37 C for a duration of 3 weeks (Fig. 16). It worth to mention that the P value in the Fig. 16 is one-way ANOVA test was conducted to assess the statistical significance of the adhesion and toughness results. Figure 16 shows the nominal adhesion strength between the coating and the Ti-6Al-4V substrate. Adhesion failure and cohesion failure cannot be recognized by nominal. Without fluoridation (sample F0), the adhesion strength is about 19 MPa. Fluoridated samples (F1 and F2) show significant increase in adhesion strength to about 2627 MPa. Zhang, et al. [186] concluded that, the strength range starts from about 19 MPa for pure hydroxyapatite (x=0) up to about 26 MPa for x=1. However, after 21 days of soaking the coating in Tris-buffered physiological saline solution, the adhesion strength increases to about 30 MPa for pure HA and to over 40 MPa for FHA. Comparing the solgel and thermal spraying methods for the same FHA coatings on Ti6Al-4V, Gu, et al. [189] described that after soaking, the adhesion strengths of thermal sprayed specimens tends to decline, with reductions up to 75%. For example the adhesion strength had decreased from 27 MPa before soaking down to 19 MPa after soaking in synthetic body fluid (SBF) for 2 weeks. The reduction in adhesion strength of thermal spray deposited HA coatings is probably due to the presence of cracks in the coating [83].

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Cheng, et al. [190] used a pull-out method and scanning scratch technique to evaluate the bonding strength of FHA coatings on Ti-6Al-4V. Figure 17 shows the result of measurements by pull-out strength, showing the strength is about 11 MPa for pure HA coating (FHA0), with considering of F content, the strength intensifies up to about 22 MPa, and then decreases to around 1718 MPa. Coating peeling-off value is about 390mN for pure HA. In contrast, the coating peeling- off increases with increasing F content, 447 mN for FHA1, 450 mN for FHA2, 449 mN for FHA3 and 478mN for FHA4. The result of the study confirms that the presence of F in FHA coatings has improved the adhesion strength [190]. 2.8 Ion beam assisted deposition technique Surface modification techniques based on the bombardment method have been used since the mid-1970s, and many have been developed and are now widely used for surface engineering of materials such as ceramics, bioceramics, and metals. Examples of such methods are ion beam deposition, ion beam mixing and ion beam assisted deposition (IBAD) [191-195]. IBAD is a vacuum deposition process based on the combination of ion beam bombardment and physical vapor deposition. The major characteristic of IBAD is the bombardment with a specific energy ion beam during coating deposition. Many parameters can affect the composition, mechanical properties, chemical properties, and structural properties of the deposited coating in the IBAD process. The most important processing parameters in IBAD are evaporation rate or sputtering rate, coating materials, ion species, ion beam current density and ion energy [196]. IBAD has the ability to prepare bio-coatings with considerably higher adhesive strength as compared to traditional coating methods. The high adhesive strength is the result of interaction between the substrate and coating atoms, assisted by ion bombardment. This results
29

in an atomic intermixed zone in the substrate-coating interface [196]. IBAD process is highly reliable, reproducible and is conducted at low substrate temperature, without unfavorably affecting the bulk substrate characteristics. Furthermore, the process has superior control over coating microstructure and chemical composition [197].

2.8.1 Ion beam assisted deposition of hydroxyapatite (HA) coatings As it mentioned earlier, there are several methods to make HA coating on Ti-6Al-4V, among which plasma spraying is the most frequently used [198, 199]. However, long-term clinical follow-up has demonstrated that there are significant deficiencies in the plasma-sprayed HA coatings. The limited cohesive strength of the coatings and the limited strength of the coating-metal substrate interface are the main problem with plasma-sprayed coting technique. Moreover, heat treatments in plasma-sprayed HA coatings results in cracks in the coating layer because of thermal expansion mismatch between the metal substrate and coated layer. This leads to a severe decreasing in bond strength [200-203]. In order to produce more permanent bonebonding calcium phosphate coatings, ion beam assisted deposition (IBAD) is introduced as an alternative technique for plasma spraying technique. Previous studies shows that implants coated with HA by the IBAD method demonstrate a very good adhesion to the substrate [204]. 2.8.2 Adhesion of ion beam assisted deposition of hydroxyapatite (HA) coatings on Ti-6Al-4V In the IBAD process, a wide atomic intermixed zone between the coatinsg material and the substrate can be created, assisted by the bombardment with energetic ions during deposition. This creates a strong adhesion of the coating to the substrate [205, 206]. Ohtsuka et al. first used 50 keV Ca+ implantation into Ti, followed by Ca+ IBAD to deposit HA coating on Ti substrate and has obtained higher adhesive strength than conventional methods [204]. It has been demonstrated that Ca+ implantation alone into Ti was unable to provide the bioactive surface.
30

Cui, et al. [207] proposed using Ar+ IBAD to form highly adhesive hydroxyapatite coatings on titanium alloy. The coatings prepare by IBAD was compared to those formed by ion beam sputtering deposition (IBSD) of calcium phosphate coatings. Scratch test is used to investigate the adhesive strength of the IBSD and IBAD coatings on the substrates. Figure 18 shows the typical Fz- Fy curves of scratch test results for the specimens prepared by IBSD and IBAD. Markers A and B indicate the points of the first occurrence of coating detachment from the substrate. Fz and Fy , as the normal and tangential forces respectively, are affecting the diamond indenter during the test. A load speed of 2000 gf /min was chosen for the tests. The results have shown that the critical loads were 660 gf for IBSD and 1050 gf for IBAD samples. Generally, it was seen that the adhesive strength of the coatings prepared by IBAD technique is almost twice that of the IBSD coatings. It has been shown that the adhesion strengths of coatings prepared by IBSD and plasma sprayed technique are generally similar [127]. Thus, it can be deduced from the comparative results between IBSD and IBAD that the adhesive strength of IBAD coatings would be reasonably higher than that of plasma sprayed depositions. The main benefit of IBAD is the improved adhesion strength due to the wide atomic intermixed zone at the interface of the coating and substrate [204, 206]. Thus, the issue of low adhesion strength, which exists in plasma sprayed coatings can be significantly eliminated by using the IBAD technique [207]. Choi, et al. [35] have used an Ar ion beam in the coating of HA on Ti-6Al-4V deposited by IBAD technique. Figure 19 illustrates the bonding strength as a function of the ion beam current, before and after the heat treatment. Increasing the current would increase the ion bombardment and broadens the atomic intermixed zone during the deposition. This results in the increase of adhesion strength between the substrate and coating layer [207].

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Several studies have shown that heat treatments would decrease the bond strength [200203]. Figure 20 shows the SEM micrographs of the coating layer before and after heat treatments. The morphologies were found to be relatively similar regardless of the current level. Before heat treatment, the layer was rather featureless, as shown in Fig. 20 (A). The lines at the interface are Wallner lines frequently observed when hard coating layers are detached from a metal substrate [208]. However, after heat treatment, the layer became severely cracked, as shown in Fig. 20 (B). This is probably due to the thermal expansion mismatch between the coating and the substrate [209]. These cracks are the main reason for the reduction in bond strengths. The micrograph also reveals that the metal surface was slightly oxidized, presumably by OH in the coating layer [209]. Overall significant improvement in the bond strength is resulted by Choi, et al. [35] using an Ar ion beam while deposition. Hamdi and Ide-Ektessabi [197] have proposed the deposition of hydroxyapatite layer using a combination of technique of IBAD and simultaneous vapor deposition (SVD), namely ion-beam-assisted simultaneous vapor deposition (IBASVD). Figure 21 illustrates the result of coating detachments for two sets of IBASVD samples as function of different annealing temperatures. Both types of samples resulted in similar curve patterns with the minimum detachment forces recorded at 700 C annealing temperature and the maximum adhesion strength at 1200 C. In all cases the adhesion strength for the 260 A/cm2 sample was higher than the 180 A/cm2 sample. In general, the recorded data for both samples are extremely higher than the maximum adhesion strength obtainable by the SVD samples, which was less than 100 mN [210]. It is suggested that the increase in adhesion strength was the result of the formation of a mixed layer between the substrate and the HA film , consisting of a gradient fill of Ca, P and the element of the substrate [207, 211]. Hamdi and Ide-Ektessabi [197] described that the energetic

32

ions assisted the reactions between the migrated atoms and the substrate atoms to generate an intermixed layer, which have specific properties different from the deposited films and the substrate. It was also understood that high current density of ion beam resulted in a wider atomic intermixed zone, which consequently improved the overall adhesion strength. 2.9 Sputter coating technique Sputter deposition is a physical vapor deposition (PVD) method of depositing thin films by sputtering. This involves ejecting material from a source, known as a "target", onto a "substrate" such as a silicon wafer. It was reported that initial sputtering using multi-component ceramic targets such as superconducting oxides, HA and other CaP materials would produce coatings whose chemistries were different upon deposition than the bulk target [212, 213]. Sputtering utilizes a gas plasma (argon, neon, krypton or xenon) to remove material from a negatively charged target which is then deposited as a thin film coating onto the substrate. Studies have shown successful deposition of thin HA layers on titanium substrates using RF magnetron sputtering [214]. 2.9.1 Sputter coating of hydroxyapatite (HA) coatings Sputtering techniques have been used to deposit homogeneous thin films coatings of high adhesion strength with thicknesses ranging from 0.5 to 3 m. However, sputter coated HA films on metals were found to be of low crystallinity [214-216]. The low crystallinity increases the rate of dissolution of the coating in the living body. Post-treatment thermal process can be used to crystallize the film, hence reducing the possibility of dissolution. However, conventional thermal treatment in the electric furnace increases the likely formation of cracks and may degrade the HA films. 2.9.2 Adhesion of sputter coating of hydroxyapatite (HA) coatings on Ti-6Al-4V

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K. Ozeki et al. [217] compared the thermal treatments of the HA coated on titanium alloy substrate prepared by sputter coating with those prepared by plasma spraying technique. The substrates were sandblasted using Al2O3 (125-180 m) abrasive before coating. The specimens were post-treated with a hydrothermal process for 24 hours. The film thickness obtained for sputter coating was 1.2 m while the thickness for plasma spraying was 60-100 m. Figure 22 shows the shear strength results of the sputter coating, the plasma sprayed coatings and the non-coated columns over a period of time. The sputter coating showed the highest bonding strength overall with recorded strengths of 3.3 0.2, 5.7 0.5, and 8.6 1.6 MPa after two, four, and 12 weeks, respectively. The plasma sprayed coatings resulted in strength values of 1.9 0.25, 4.0 0.3, and 6.6 0.7 MPa, respectively, for the same period of time. The strength values of the non-coated columns were 0.4 0.3 and 1.1 0.3 MPa after four and 12 weeks, respectively. The strength of the sputter coating exceeded that of the plasma sprayed coating by more than 70, 40, and 30% after a period of two, four and twelve weeks, respectively. K. De Groot et al. reported that coating thicknesses above 100 m were associated with fatigue failure under tensile loading [218]. According to S. Hasegawa et al., thin plasma sprayed coatings are bound more strongly than thick coatings [219]. S.J. Ding et al. [220] investigated on a series of thin (<10 m), single layered HA/Ti coatings deposited on Ti-6Al-4V substrate using an RF magnetron-assisted sputtering system. For the experiments, six HA/Ti targets with different compositions (95HA/5Ti, 90HA/10Ti, 85HA/15Ti, 75HA/25Ti, 50HA/50Ti, and 25HA/75Ti) were prepared. Generally it was found that the coating with higher Ti contents resulted higher adhesion strengths. The highest adhesion strength (of the 25HA/ 75Ti coating), evaluated using a Sebastian adhesion test system (Sebastian Five, Quad Group, Spokane, WA) [127] was even higher than 80 MPa, which

34

exceeded the maximum value achievable using the bonding resin in the pull-out test. Table 4, reports the adhesion strength and their corresponding failure point for different compositions and Fig 23 shows the adhesion strength for each composition. The high adhesion strength of sputtered monolithic HA coating is higher than most plasma sprayed HA coatings [221, 222], and is believed to be attributed to the sputter cleaning and ion bombarding processes. The sputter cleaning process would remove contaminants and adsorbed gas molecules from the surface of the substrate to produce a clean, highly active surface [223]. The ion bombarding process during sputtering would enhance atomic diffusion and mixing near the interface region [207, 224]. Mechanical interlocking effect may have contributed to the higher average adhesion strength of coating sputtered on the rougher surface (Ra = 0.7 mm) as compared to the lower value obtained for the smoother surface (Ra = 0.06 mm). However this effect was not as significant for sputtering with Ti-containing targets. Results from S.J. Ding et al. [220] have shown that all coatings had adhesion strengths between 60 and 80 MPa. Furthermore if the sputtering uses a target comprising of more than 15 vol % Ti, the resulting coating adhesion strength and hardness were significantly higher than those of monolithic HA coating. 3. Discussion There have been numerous studies on coatings of hydroxyapatite (HA) onto Ti-6Al-4V because of its significant utilization in orthopedic prostheses and implants. Table 5 summarizes the previous discussion on the various techniques for coating of HA on Ti-6Al-4V, with comparison on their advantages and disadvantages. Plasma spraying is the most frequently investigated method to coat HA onto Ti-6Al-4V specimen, [198, 199]. Plasma spray is the first method used for HA coating, owing to its ease of
35

application [26]. Moreover, the determination of the adhesion between the coating and the substrate has been always a main concern when using plasma spraying technique [59]. High spraying power results in high adhesion strength of HACs due to significant melting of the coating material which forms dense microstructure. However, the high-temperature process can lead to phase transformation and grain growth of the metal substrate which may cause significant decrease in the mechanical properties of the metal. Results of the study [61] has established the relationship between residual stress and bonding strength especially for plasma sprayed hydroxyapatite coatings. This stress in the coating is influenced by the spraying parameter, coating thickness [67, 68], and substrate cooling effect (i.e. temperature of substrate) [62, 63]. Generally, the residual stresses increase with the increase in the thickness of coating and the temperature of the specimen during plasma spraying. Moreover, high-power sprayed HA coatings generally possess higher adhesion strength than those sprayed with lower power. In some cases, the adhesion of the plasma sprayed HA can be significantly improved by a subsequent hot isostatic pressing operation. The adhesion strength is a reflection of the combination of cohesive (within the coating layers themselves) and adhesive (coating to substrate) strengths of a coating [61]. The cohesive strength is obtained by coating properties, such as the microstructure and crystallinity, but the adhesive strength is mostly influenced by coating properties, such as surface roughness, residual stress, and the mechanical interlocking between substrate and HACs [61]. Overall, it was found that plasma sprayed coating has not improved the service-life performance of uncoated implants. In addition, there are issues with poor reliability and mechanical integrity [56, 57]. The pulsed laser deposition (PLD) is a better alternative than the plasma spray technique because the PLD transfers sintered HA stoichiometrically to deposit a

36

thin adherent coating onto titanium substrate surface [58]. The substrate temperature is lower in PLD as compared to plasma spray and different calcium phosphate compositions can be deposited by changing the parameters of deposition [112, 114, 225]. In addition, undesirable phases of HA coatings by PLD are reduced under optimal conditions and generally have better coating to substrate adhesion [54, 106]. TiO2 and TiN layers can be used as an interfacial layer between coating and the metal substrate as reported in studies related to the adhesion of crystalline PLD HA thin films on Ti6Al-4V substrates [20]. Some authors consider that this interfacial layer favours adhesion due to better bonding of HA to TiN which is then,directly bonded to the substrate [125, 126]. These layers can be created using pre-treatment processes, such as laser surface nitriding and etching on titanium, which have been reported to improve the bonding strength of the coating. Thus, laser surface nitriding and subsequent etching of the substrate is an effective pre-treatment method for improving the adhesion strength of HA coated onto Ti-6Al-4V by PLD [119]. EPD is a technique which is gaining attention due to its ability to economically produce films of a wide range of thicknesses as compared to conventional methods such as thermal spraying, sol gel deposition, and sputtering [139]. Moreover, EPD of HA has ability to be processed at room temperature, reducing the possibility of formation of the amorphous phase in HA. The good uniformity and bonding strength results is mostly due to the colloidal stability of the suspension [142]. The EPD technique can also produce nanostructured HA coating having bond strength 2-3 times better than thermal sprayed HA coating. Similar to PLD, studies have shown that an intermediate layer, such as silica or TiO2, improves the adhesion strength of coating fabricated using EPD [146]. Dense titanium dioxide (TiO2) films possess a very good combination of bioactivity, chemical stability and mechanical

37

integrity [149]. A TiO2 inner layer would also reduce the decomposition of HA and increases the and overall adhesion strength of coating [160]. The sol-gel technique is a simple technique which can create single or multicomponent oxide coating on glass or metals [162, 163]. However, there is a coating thickness limit of 0.5 m [172]. Fluoridation of HA can enhance the coatings resistance to biodegradation while still maintaining good biocompatibility [184, 187]. An increase in fluoridation ratio would increase the adhesion strength by about 40%. The strength range for FHA is about 26 MPa which is higher than the value of the bonding strength of 19 MPa for pure hydroxyapatite. The fracture toughness increases about 200 to 300% and the scratch test results in adhesion improvement of 35 % for fluoridated HA coatings as compared to pure hydroxyapatite coating [183, 186, 190]. The enhancement in adhesion strength is believed to be caused by the formation chemical bonding at the interface and the relief of thermal mismatch resulting from the incorporation of fluorine (F) into the HA structure. Dip coating can be generally compared with sol-gel coating technique. The technique is simple, economical and is able to generate high coating quality. Dip coating process is rapid, where the complete transition can be completed within a few seconds or less if volatile solvents are used. IBAD technique can deposit highly adhesive HA coating on Ti-6Al-4V due to atomic interactions between the substrate and coating materials, assisted by ion bombardment [196]. The main advantage of IBAD compare to other methods, such as IBSD or plasma spraying, is that there is a wide atomic intermixed zone at the coating-substrate interface which significantly improves the adhesive strength of the coating. Heat treatment of IBAD coated samples reduces

38

the adhesion strength, due formation of cracks in the layer and the thermal expansion mismatch between the coated layer and the metal substrate [200-203]. Figure 24 shows adhesion strength values of HA coatings on Ti-6Al-4V coated using various techniques. The sputtering technique has the highest adhesion of coating to the substrate compares to other methods which can be attributed to the sputter cleaning and ion bombardment processes.

4. Conclusion Adhesion strength of HA on Ti-6Al-4V substrate has been reviewed in detail. Nine common techniques of deposition such as plasma sprayed deposition, hot isostatic pressing, thermal spray, dip coating, pulsed laser deposition (PLD), electrophoretic deposition (EPD), solgel, ion beam assisted deposition (IBAD), and sputtering were evaluated and discussion were made on the coating parameters affecting the adhesion strength of the coating. Advantages and disadvantages of each method were discussed and a quantitative comparison was made on the different techniques of HA coating on Ti-6Al-4V substrate. Based on this review, the best adhesion of HA coating to substrate is obtained by sputtering deposition technique while the worse bonding strength was obtained by PLD at 1000 laser pulses. Using an interfacial layer (such as TiO2 or TiN) as the initial coating layer on the substrate followed by HA coating layer can enhance the bonding strength. Pretreatments such as nitriding, followed by etching, can enhance the adhesion strength in PLD. Moreover, post-treatments also have similar effects on other techniques such as IBAD and thermal spray.

Acknowledgement

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The authors would like to acknowledge the University of Malaya for providing the necessary facilities and resources for this research. This research was fully founded by the Ministry of Higher Education, Malaysia with the high impact research grant number of um.c/625/1/HIR/MOHE/ENG/27.

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Table 1 Thermal spray condition of HA powders [92].

Parameters Argon (l/min) Helium (l/min) Current Voltage Powder Rate (g/min) Setting 41 60 700 52 30 Spray Distance (mm) 115 Surface Speed (m/min) 75 Travers Speed (mm) 8 yes Cooling

Table 2 Bond strength test results with different pretreatment and cryogenic treatment [92]. Coating Bonding Strength ( MPa) Without Cryogenic Treatment Ultrasonic High Pressure Air HA 26.56 18.91 36.65 Ultrasonic High Pressure Air 29.30 With Cryogenic Treatment

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Table 3 Adhesion strengths of HA coated samples with and without TiO2 inner layer deposited using different voltages [160]. Samples (substrate + inner layer + Ha) Ti-6Al-4V + ----- + HA Ti-6Al-4V + TiO2 (50 V)+ HA Ti-6Al-4V + TiO2 (20 V)+ HA Ti-6Al-4V + TiO2 (10 V)+ HA Note. S: standard deviation. Shear Strength (MPa) 13.8 ( s=1.8) 11.9 ( s=1.8) 13.1 ( s=1.8) 21.0 ( s=1.8)

Table 4 Adhesion Strength and Failure Mode of Coatings [220]. Adhesion Strength (MPa) Coating Code HA 95HA/5Ti 90HA/10Ti 85HA/15Ti 75HA/25Ti 50HA/50Ti (Ra= 0.06 m) 59.9 12.4 (41) 59.5 6.5 (20) 58.4 6.2 (18) 64.8 6.2 (17) 64.0 6.9 (32) 75.1 5.5 (22) (Ra= 0.7 m) 71.814.7 (25) 60.75.8 (23) 54.56.1 (12) 69.5 10.3 (19) 65.3 6.5 (50) 72.9 5.4 (28) Failure Mode (Ra= 0.06 m) R/C, C/S R/C, C/S R/C, C/S R/C, C/S R/C, C/S R/C

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25HA/75Ti Ti

81.9 5.2 (19) 79.5 9.1 (15)

79.8 6.3 (17) 85.1 5.1 (34)

R/C R/C

Table 5: Different techniques to deposit HA coating.

Technique Plasma Spraying Thickness < 20 m Advantages rapid deposition ; sufficiently low cost; fast bone healing, less risk for coating degradation Disadvantages Poor adhesion, alternation of HA structure due to coating process; non- uniformity in coating density; extreme high temperature up to 1200 c, phase transformation and grain grow of substance due to high temperature procedure; increase in residual stress; unable to produce complete crystalline HA coating Line of sight technique; high temperatures induce decomposition; rapid cooling produces amorphous coatings; lack of uniformity; crack appearance; low porosity; coating spalling and interface separation between the coating and the substrate Line of sight technique; expensive time consuming; produces amorphous coatings; low crystallite which accelerates the dissolution of the film in the body Line of sight technique; splashing or particle deposition; need surface pretreatment; lack of uniformity

Thermal Spraying

30- 200 m

High deposition rates; low cost;

Sputter Coating

0.5- 3 m

Pulsed Laser Deposition

0.05- 5 mm

Dip Coating

< 1 m

Uniform coating thickness on flat substrates; dense coating; homogenous coating; high adhesion Coating with crystalline and amorphous; coating with dense and porous; ability to produce wide range of multilayer coating from different materials; ability to produce high crystalline HA coating; ability to restore complex stoichiometry; high degree of control on deposition parameters Inexpensive; coatings applied quickly; can coat complex substrates; high surface uniformity; good speed of coating; Can coat complex shapes; Low processing temperatures; relatively cheap as coatings are very thin; simple deposition method; high purity; high corrosion resistant; fairly good adhesion

Requires high sintering temperatures; thermal mismatch; crack appearance

expansion

Sol-gel

0.1- 2.0 m

Some processes require controlled atmosphere processing; expensive raw materials; not suitable for industrial scale; high permeability; low wear resistance; hard to control the porosity;

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Electrophoretic Deposition

0.1- 2.0 mm

Hot Isostatic Pressing

0.2- 2.0 mm

Ion Beam Assisted Deposition

<0.03 m

Uniform coating thickness; rapid deposition rates; can coat complex substrates; simple setup, low cost, high degree of control on coating morphology and thickness, good mechanical strength; high adhesion for n-HA Produces dense coatings; produce net-shape ceramics; good temperature control; homogeneous structure; high uniformity; high precision; no dimensional or shape limitation Low temperature process; high reproducibility and reliability; high adhesion; wide atomic intermix zone are coating-tosubstrate interface

Difficult to produce crack-free coatings; requires high sintering temperatures; HA decomposition during sintering stage

Cannot coat complex substrates; high temperature required; thermal expansion mismatch; elastic property differences; expensive; removal/interaction of encapsulation material Crack appearance on the coated surface

Figure 1 Tensile bond strength result of plasma sprayed Ti-6Al-4V/ 20 wt.% hydroxyapatite coating (as sprayed and HIPed) [79].

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Figure 2 A schematic diagram of thermal spray coating [82].

Figure 3 Fundamental stages of dip coating (the finer arrows indicate the flow of air) [94].

56

Figure 4 SEM micrographs from cross-sectional view of HA coatings (via SOL 2) on Ti6Al-4Vsubstrates after heating at 840C [96].

57

Figure 5 Comparison of adhesion strength for HA on substrates with different pre-treatments [119].

Figure 6 Average surface roughness of titanium substrates treated with different laser pulses and HA coating compared with control sample [132].
58

Figure 7 Failure values obtained by scratch test (Lc1, Lc2 and Lc3) for the HA coatings on different irradiated and non-irradiated titanium substrate [132].

Figure 8 Electro-polarization corrosion curves for both EPD n-HA coating and HA thermal sprayed coating [151].
59

100m

Figure 9 Cross section SEM micrograph of the EPD deposited under the identified optimum suspension condition [140].

Figure 10 SEM micrograph of the uncrack deposit surface [140].

60

Figure 11 Steps in the sol-gel process for ceramic materials [169].

Figure 12 X-ray diffraction of sol-gel coatings preferred to 500C on titanium substrates and then fired at various temperatures [179].
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Figure 13 A scanning electron micrograph of a coating fired to 800C for 10 min, the field of view is 250 nm by 250 nm [179].

Figure 14 Coefficient of friction in terms of relative voltage as a function of normal load while scratching (a) pure HA coating; (b) fluoridate HA (FHA6) coating on Ti-6Al-4V [174].
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Figure 15 Adhesion strength of pure HA and fluoridated HA coatings on Ti-6Al-4V substrates as indicated by upper critical load in scratch test. Firing temperatures are indicated [174].

Figure 16 Pull-out adhesion strength of FHA coating before and after soaking in TPS solutions. * indicates a significant increase of adhesion strength with respect to F0 (as prepared coatings);
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** indicate a significant increase of adhesion strength with respect to F0 (after soaking in TPS for 21 days) [186].

Figure 17 Pull-out strength of coatings with different F content [190].

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Figure 18 Fz-Fy curve of scratch test from specimen prepared by (a) IBSD and (b) IBAD [207].

Figure 19 Layer-metal substrate bond strengths, before and after heat treatment, as a function of ion beam current [207].
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Figure 20 SEM micrographs of the coating layer (A) before and (B) after the heat treatment [208].

66

Figure 21 Adhesion strength of the IBASVD samples at different elevated temperatures [197].

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Figure 22 Bone bonding strengths of sputtered films [217].

68

Figure 14 Adhesion strength of coatings [220].

69


Plasma Spray PLD (1000 Pulsed Laser) PLD (Nitrided/ Etching) Pretreatment EPD (n-HA) EPD (Without TiO2 Interfacial Layer) EPD (TiO2 Interfacial Layer) Sol-Gel Sol-Gel (FHA) IBAD IBAD (Heat Treatment) Thermal Spray Thermal Spray (with treatment) Dip Coating Sputtering Hot Isostatic Pressing (after Plasma Spray)

Figure 24 Quantative comparison of different coating techniques.

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