Influence of Ag/Ca ratio on the osteoblast growth and antibacterial activity of TiN coatings on Ti-6Al-4V by Ag and Ca ion implantation
Graphical abstract
PIII&D system and the experimental process.
Introduction
Titanium nitride (TiN) is a biocompatible [1], nontoxic, high wear and corrosion resistant [2], high chemically and physically stable [3,4] ceramic coating, which has been demonstrated for use in biomedical applications to enhance hardness and polarization resistance, and reduce wear damage of surgical alloy, orthodontics, orthopedic implants, hip prostheses, and cardiovascular biomaterials [[5], [6], [7]]. Titanium‑aluminum‑vanadium alloy (Ti-6Al-4V) as a widely used dental implant [8,9] as well as hard tissue replacement and fracture fixation device [10] has many good mechanical properties such as the high specific strength, good fatigue strength [11] and corrosion performance. However, the long-term release of toxic metallic ions (Al and V ions) in Ti-6Al-4V may enter the bloodstream, causing inflammation and pain [12,13]. Also, its bio-inert and insufficient osseointegration make the implant passively integrate with the peri-implant bone, which needs a long period for osseointegration [[14], [15], [16], [17]]. It is generally known that a rapid coalescence at the implant-bone interface may not only enhance stabilization of implant, but also shorten the hospitalization [18,19]. More importantly, although full disinfection work and antibiotic drug therapy have been done during and after the surgery, prosthesis implant failures may still occur owing to implant-associated bacterial infections [[20], [21], [22]] because of the poor antibacterial activity of Ti-6Al-4V [23,24]. Therefore, TiN is a good candidate for coating titanium alloy surface to overcome the above problems.
However, the application of the biological and antibacterial abilities of TiN still needs to be improved, because these defects may cause ultimate failure after long-term use. To antibacterial effect, many studies have shown that silver can effectively improve the antibacterial activity of the material [20,25,26]. Silver, as a broad-spectrum antibacterial agent, is able to act on a broad spectrum of bacterial and fungal species, including antibiotic-resistant strains, without local or systemic side effects in many in vivo experiments [27].
Thin film technology is a clean and uniform technology, which can improve the surface properties of samples [3,28,29]. In this work, a plasma immersion ion implantation and deposition (PIII&D) system is used to modify the surface of the sample. This system has four sources, which can deposit a dense coating on the surface of the sample by DC source and implant two kinds of high-speed ions into the sample surface at the same time by pulsed cathodic arc plasma sources. Fig. 1 showed PIII&D system. The advantages of PIII&D include the deposition of the coating with dense and uniform, good surface modification when the implanted ion reaches an appreciate concentration and depths, and the treatment of complex three-dimensional surface [30,31].
In order to improve the antibacterial activity and promote the rapid growth of bone cells, some research groups doped antibacterial silver with other element to promote the growth of bone cells, the purpose was to achieve the synergistic role of the two elements. Zhao et al. proved that co-doping of Mg and Ag exhibited a balance between the antibacterial performance and the osteogenic properties of the titanium [32]. In this work, we chose Ca to replace Mg to combine with antibacterial Ag to achieve synergistic effect of the osteoblast growth and antibacterial performance.
The researches evidenced that the introduction of appropriate amount of Ca, Mg and other elements can promote cell differentiation [18,32,33]. As one of the main components of human bones, calcium is a necessary ion for bone formation, which can regulate mRNA transcription and protein synthesis, and stimulate the growth and osteogenesis of osteoblasts [[34], [35], [36]]. At present, based on our knowledge, there are few reports of combining these advantages for irritating bone cell growth and antibacterial activity. So, in this work, TiN coating was deposited on Ti-6Al-4V firstly, which could not only increase the hardness of Ti-6Al-4V, but also prevent the release of toxic ions. Then silver and calcium ions were implanted into TiN coating via plasma immersion ion implantation and deposition system to form Ag/Ca-TiN, which is expected to enhance both its cell adhesion and its antibacterial ability. In our previous work, it has been proved that TiN coating can improve the mechanical properties of Ti-6Al-4V, and prevent the release of toxic substances such as Al and V in [20,37]. Therefore, in this paper, we focused on the release of the implanted Ag and Ca ions, in vitro osteoblast adhesion and antibacterial activity of Ag/Ca-TiN groups with different Ag/Ca ratios. This is also the difference and innovation in this work compared with our previous work.
Section snippets
Preparation of Ag/Ca-TiN
Silicon wafers (100) and Ti-6Al-4V plates (10 mm in diameter, 3 mm in thickness) were used as substrates in this work. (the samples prepared on silicon wafers and Ti-6Al-4V plates were used for surface characterization and in vitro biological evaluations respectively). The substrates were ultrasonically cleaned in ethanol before plasma immersion ion implantation (PIII & D-700, TONGCHUANG, China) treatment.
First, TiN coatings were deposited on the surfaces of the substrates by sputtering high
Results and discussions
Fig. 2(a–c) shows the SEM images of TiN, Ag/Ca(2.5:1)-TiN and Ag/Ca(2:1)-TiN, respectively. The surface of the TiN film is smooth, homogeneous, crack free and dense, as shown in Fig. 2(a). But after Ag and Ca ions implantation, there are many tiny islands existed in the surfaces of Ag/Ca(2.5:1)-TiN and Ag/Ca(2:1)-TiN, which may be the clusters induced by the implanted Ag and Ca particles. In order to further explore the samples' structure, the phase compositions of TiN and Ag/Ca-TiN are
Conclusion
In this paper, Ag and Ca implanted TiN film is deposited on the Ti-6Al-4V by PIII&D system to improve its osteoblast cell growth and antibacterial activity. The Ag and Ca with different ratios are adjusted by magnetic bias. In vitro corrosion experiment shows that the corrosion resistances of Ag/Ca(2:1)-TiN and Ag/Ca(2.5:1)-TiN are slightly improved after Ca and Ag implanted into TiN. And Ag/Ca(2:1)-TiN shows the best protein adsorption capacity, cell proliferation and adhesion in all the
CRediT authorship contribution statement
Xingming Ji: Almost all experiments, measurements, writing, original draft, editing.
Mengli Zhao: project administration, data analysis, review, revision.
Xiao Han: A part of experiments and measurements.
Dejun Li: Supervision, funding acquisition, conceptualization, review.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
This work was supported by National Natural Science Foundation of China (51772209), Natural Science Foundation of Tianjin (No.18JCQNJC72000), Program for Innovative Research in University of Tianjin (Grant No. TD13-5077), and the Graduate Program of Scientific Research and Innovation of Tianjin (2019YJSS137).
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