The possibility of the polyurethane layer attachment to the unmodified and diazonium-modified titanium alloy applied as potential biomaterial
Graphical abstract
Introduction
Titanium alloys due to their properties are used in such fields as orthopedics and implantology [1]. One of the most popular alloys in orthopedics as endoprosthesis of bone is Ti6Al4V [2]. Its wide application is associated with great biocompatibility, corrosion resistance and low elastic modulus similar to the human bone [3,4]. Many properties are ideal for materials used for biomedical applications [5]. The main problem during the use of Ti6Al4V is their poor resistance to abrasion, and thus the limitation of their application in elements susceptible to this phenomena [6,7]. Due to the low abrasion resistance of the Ti6Al4V, vanadium and aluminum ions are released from its structure [8]. Both ions are associated with such health problems as Alzheimer's and neuropathy [9]. So far, many different attempts to modify titanium alloys were undertaken. Surface treatment improves the wear resistance, however, it also affects the decline of fatigue strength [10]. Therefore, it is necessary to look for new methods of modification. Reasonable approach is to create thin film of the polymer on the alloy surface, which would increase the abrasion resistance. The problem in this kind of modification is small adhesion between alloys and polymers, therefore the alloy requires pre-modification, which will increase the possibility of formation of a polymer layer.
The prior modification can be conducted using diazonium salts, which were previously used in surface modification of carbon, ceramics, metals and metal oxides [[11], [12], [13], [14], [15], [16], [17]]. These salts were used in the modification of the surfaces in order to create the organic layer which can react with the different monomers to form a polymer layer [18,19]. Titanium surfaces were earlier modified several times. For example Mesnage et al. described in their publication coupling process based on the reduction of nitrobenzenediazonium tetrafluoroborate salt in presence of the vinylic monomer to obtain poly(hydroxyethyl) methacrylate on the surface of titanium oxide [20]. The titanium surface was also modified using diazonium cations with consecutive attachment of poly(methylmethacrylate) [21]. Mechanical tests showed an increase in bond strength between poly(methylmethacrylate) and diazonium modified titanium compared to the unmodified one. The next example of the efficiency of alloy modification and polymer attachment is publication of Pan et al. [22]. The results indicate that the interface bond strength between polyetheretherketone and titanium in the presence of diazonium layer was much higher. The last example is our earlier study, which confirmed the effectiveness of alloy modification using 4-hydroxymethylbenzenediazonium salt and obtaining an evenly distributed aryl layer on the grains of the alloy [23].
Another issue after receiving aryl layer is selection of the polymer. The two main aspects during the selection of the polymer is a high resistance to abrasion and possibility of attachment to the aryl layer. The ideal polymers for this application are polyurethanes. During their crosslinking, hydroxyl groups are involved and thus it is possible to attach polyurethanes to the aryl layer obtained from the 4-hydroxymethylbenzenediazonium salt [24]. Moreover, they are polymers having a high abrasion resistance. The last but not least important feature of polyurethanes is biocompatibility, as evidenced by their wide application as biomaterials [25,26].
In this work, the results regarding the modification of the Ti6Al4V alloy using 4-hydroxymethylbenzenediazonium salt and the possibility of attaching the polyurethane to the modified surface are presented. The research scheme is shown in Fig. 1. The surfaces, both before and after modification, were extensively characterized. During the tests, the effect of acetone on the stability of the obtained layer was also checked.
Section snippets
Materials and methods
Titanium alloy - Ti6Al4V was supplied by Arcam AB, Sweden. 4-aminobenzyl alcohol, hydrochloric acid, sodium nitrite, hexamethylene diisocyanate and 1,3-propanediol were purchased from Sigma-Aldrich.
Results and discussion
The effectiveness of the modification was confirmed by techniques such as FTIR (Fig. 2, Fig. 3, Fig. 4), XPS (Table 1) and Raman spectroscopy (Fig. 5, Fig. 6).
FTIR spectra of Ti6Al4V alloy before and after diazonium modification are shown in Fig. 2. On the modified material surface, there is visible an increase in the number of hydroxyl groups derived from hydroxymethyl groups in the obtained organic layer as evidenced by the bands at 3250 cm−1 and 1160 cm−1 (Fig. 2) [27]. Moreover, there is a
Conclusions
In this work the effective and efficient way to diazonium modification of Ti6Al4V alloy plate and polyurethane attachment is described. The range of research (Raman spectroscopy analysis, Fourier Infrared spectroscopy, X-ray photoelectron spectroscopy and water contact angle) was conducted to demonstrate the formation of the organic and polymer layers on the Ti6Al4V surface. It is proved that attachment of the polymer is possible only when the titanium surface is previously modified using
CRediT authorship contribution statement
Mariusz Sandomierski:Conceptualization, Methodology, Investigation, Visualization, Resources, Writing - original draft, Writing - review & editing.Tomasz Buchwald:Investigation, Visualization, Writing - review & editing.Adam Voelkel:Supervision, Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing financialinterestsor personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgement
This paper was produced with the financial support from the Polish National Science Centre (grant no. UMO-2017/27/N/ST8/00307).
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