Background
Titanium metal is one of the most widely used biomedical orthopedic materials because of its decent mechanical properties [
1]. However, as an inert material, it cannot induce osteogenesis and has no antibacterial properties [
2]. In order to improve surface bioactivity of titanium substrates, numerous methods have been proposed to cover it with bio-ceramic coatings [
1]. Various clinical studies demonstrated that the hydroxyapatite coating of prosthesis can promote earlier osseous response which could increase the prosthesis fixation and the bonding strength [
3‐
5].
Titanium implants are usually placed in contact with bones and gingival tissues so they are partially exposed to the oral cavity during and after implantation. This increases the hazard of bacterial infection, which is known as peri-implantitis [
6,
7].
For centuries, Zinc (Zn) as one of the essential elements of tissues in the human body has a stimulating role in the metabolism of bones and has been used as bacteriostatic and bactericidal agents [
8,
9]. Zinc can enhance the retention strength and osseointegration of implants [
10,
11], by stimulating alkaline-phosphatase activity and collagen production, thus can increase bone deposition and reduce bone resorption [
12]. Zn deficiency results in skeletal changes, including retardation of skeletal growth [
10] and prolonged bone recovery [
13]. Moreover, Zn species are also known to possess excellent antibacterial qualities. Zinc showed inhibitory effects against several bacteria, including
Streptococcal mutans [
14‐
16].
The metals’ antibacterial activity has been contingent on their contact surface; thus, a greater nanoparticles’ surface area permits larger interfaces and increases their interactions with other particles [
17].
Although HA coatings revealed an enhanced bone attachment and thus better implants integration, long-term coating stability is quite a provoking concern [
18]. Numerous coating techniques like plasma spraying, sol-gel, electrophoretic deposition, electro deposition have been employed to deposit hydroxyapatite on titanium implants. Plasma spraying is the most widely used technique for coating, but it leads to decomposition of HA due to the high temperature used, and it cannot be employed for complex structures. In electrophoretic deposition, high voltage was applied to the metal surface in order to attract the dispersed particles which leads to anodic polarization of metal substrate. This might increase the corrosion risk of metal and suppress the adhesion of HA particles [
19‐
21]. Electro-chemical deposition (ED) is a frequently used approach with increasing popularity, due to variability of coating composition, process simplicity, and its applicability for multidimensional implant surfaces [
22].
The aim of the present work was to develop well-adhered and uniform hydroxyapatite-zinc coatings on titanium metal substrate, through an in vitro electro-chemical deposition method. The coating was characterized for functional chemical group, surface morphology, surface chemical analysis, surface roughness, and coat adhesive bonding by Fourier transform infrared spectrometer (FT-IR), scanning electron microscope (SEM), energy dispersive spectroscope (EDS), profilometer, and tape adhesive test respectively.
Discussion
Metallic orthopedic prosthesis is most commonly used due to its good mechanical properties, but its failure mostly occurs due to the lack of proper bone bonding and/or the occurrence of post-operative infections. Hydroxyapatite is commonly used as a bone filler biomaterial or as a coat for titanium prosthesis due to its decent biocompatibility, osseoconductivity, and bioactivity [
26]. However, as a ceramic material, HA still has lower mechanical properties [
27]. The biological apatite differs from synthetic apatite because the former contains numerous cationic substitutions, such as Zn
2+, Na
+, Mg
2+, and has smaller size than synthetic apatite [
28,
29]. It was proposed that the addition of zinc to hydroxyapatite had led to a reduction in inflammatory reaction and an improvement of bioactivity [
28,
30].
Plasma spraying, sol-gel, and electrophoretic deposition has been all utilized to deposit HA on titanium implants, with some difficulties and worries of suppressing the HA particles’ adhesion, anodic polarization of metal substrate, and increasing metals’ corrosion risk [
19‐
21]. Electrochemical deposition (ED) is the selected approach in this study due to its simplicity, easiness of parameters control, uniform coating thickness produced, and its applicability for multidimensional implant surfaces [
22].
In the current study, an electrochemical deposition was applied to prepare nano-HA-Zn coating on titanium metal aiming to improve bioactivity, osseointegration, and preventing peri-implantitis. At this early point of research, the coatings’ procedure was accustomed to produce a uniform thickness of HA-Zn coating, characterize its chemical structure, observe its surface morphology, and evaluate the surface roughness and coat adhesive properties.
Recycling of natural-derived resources is a challenging task that may have both environmental and economical profits. Cuttlebone fishery is a naturally derived biomaterial that was used as a source of calcium during the electrochemical deposition process in this study. It was confirmed in the IR spectra (Fig.
2) that Ca(NO
3)
2·4H
2O resulted from the reaction of CaCO
3 of cuttlebone and nitric acid [
31]. The selected time for electrochemical deposition of HA-Zn coating was 2 h; as by then, the formation of a white detectable coating had occurred and could be scrapped for IR spectral analysis. After preparation of HA-Zn coating, the analyzed powder appeared to still have the HA characterization. Li et al. prepared Zn-HA coatings through a hydrothermal method and found that the FT-IR spectra of Zn-HA has no significant changes than the as-prepared HA [
32]; this Zn-HA spectrum paralleled with this study.
Yang et al. prepared a Zn-HA coating on Ti plates by an electrochemical process, and the SEM examination showed irregularly shaped rod-like crystals with hexagonal cross-section; this corresponded well with the current study results. They also concluded that a Zn-HA coating improves proliferation and differentiation of osteoblasts and would enhance implant osseointegration [
11].
Ceramic coatings must have good adhesion to the implant to act as a barrier and assure good protection to the substrate. The adhesion test was performed in this study to verify the adequacy of the coating thickness.
An improvement of coating adhesion occurs as their thickness decrease, although very thin coatings may not attain the protection requirements [
33]. Contrariwise, it is recognized that thick ceramic coatings may develop cracks after the deposition procedure [
34]. The adhesive tape test read the highest score (5A); this might be attributed to the fine homogenous, closely packed, coating particles that appear crack free and highly sintered, as proved by the SEM results in Figs.
4,
5, and
6.
Dental implants do exist with various geometries, different lengths and diameters, and features, such as, pits, pores, vents, and slots. Essentially, a highly rough surface produces better initial stability and anchorage. Moreover, a rough surface with a larger surface area facilitates particles exchange between the implant and surrounding tissues. It could be concluded that such coatings with an increased surface area could have better clinical performance [
35]. This developed electro-deposition process, can be applied to deposit a nano-HA-Zr coating to complex implant surfaces and thus increases their surface area, surface roughness, initial stability and clinical performance.
Supplementary, biocompatibility, anti-bacterial activity, and in vivo investigations are required to correlate between the HA-Zn coating properties and their effect on bone formation and osseo-integration.