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A comparative study on corrosion and wear performances of Ti–Nb–(Cu, Co) biomedical shape memory alloys

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Published/Copyright: March 15, 2024
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Corrosion Reviews
From the journal Corrosion Reviews Volume 42 Issue 3

Abstract

The present study presented the systematic investigations on the influence of Co and Cu on the corrosion behaviors and wear resistance of Ti–Nb based shape memory alloys. The results demonstrated that the addition of Co and Cu can effectively enhance the corrosion resistance of Ti–Nb based shape memory alloys. By optimizing the chemical composition, the superior corrosion resistance with (φcorr = –0.95499 V, Jcorr = 357.92 μA cm−2) and (φcorr = –0.96775 V, Jcorr = 467.54 μA cm−2) can be obtained in Ti–Nb–Co1.0 and Ti–Nb–Cu1.5 shape memory alloys, respectively. Similarly, the wear properties of Ti–Nb based shape memory alloys were also dependent on the ternary alloying elements. The friction coefficient of Ti–Nb based shape memory alloy firstly decreased and then increased with the content of ternary alloying element increasing. And then decreased again, as the exceeding ternary alloying element was added. In addition, the wear behaviors of Ti–Nb based shape memory alloys can be attributed to the combination of abrasive wear, adhesive wear, and oxidative wear, irrespective of the types of ternary alloying elements. In contrast, Ti–Nb–Cu5.0 shape memory alloy has the lowest friction coefficient of 0.45, which is smaller than that (0.50) of Ti–Nb–Co5.0 shape memory alloy.

Keywords: Ti–Nb based alloy; biomedical shape memory alloys; microstructure; corrosion behavior; wear performance

1 Introduction

As advanced functional materials, shape memory alloys, of which show the shape memory effect and superelasticity, have been widely applied in various fields, such as aerospace, automotive, and energy exploration industry and so on (Jani et al. 2014; Jiang et al. 2017). In addition to the shape memory effect and superelasticity, shape memory alloys also possess the superior damping properties and good biocompatibility, which promotes to their extensive applications in the biomedical fields including cardiovascular applications, orthopedic repositions, orthodontic application, neurosurgical applications, as well as the surgical instruments application, etc. (Shukla and Garg 2023). Compared with the conventional biomedical devices made from titanium, stainless steel, or cobalt–chromium alloys, shape memory alloy biomedical devices can offer the unique advantage of one-off installation/implantation that can provide real-time adjusted correction/support owing to their functional properties, and this may significantly enhance the healing efficiencies associated with the application of implants and devices in various biomedical fields, including orthodontics, orthopedics, neurology, and cardiology (Petrini and Migliavacca 2011; Tetali et al. 2023; Wang et al. 2021a,b). They not only cannot develop any infections inside the body of the patient but also not infect the bloodstream (Kim et al. 2020). Especially, owing to the significant impact of an aging population overall the world, the shape memory alloys are urgently demanded (Wan-Ting et al. 2021). Among the shape memory alloys, binary Ti–Ni shape memory alloys not only possess the larger recoverable strain but also show the excellent biocompatibility, which are regarded as the most promising materials in biomedical industry (Hao and Zhou 2015). In addition to Ni–Ti shape memory alloys, Fe-based, Mg-based, as well as Cu-based shape memory alloys also have been paid more attention as the biomedical materials due to the degradable and biocompatible performances (Das et al. 2022; Herenda 2023; Liu et al. 2011; Shinato et al. 2022; Yamagishi et al. 2019). For comparison, Ni–Ti shape memory alloys are much more preferable for most applications because of superior biocompatibility, stability, and thermo-mechanical performance (Huang 2002). Nevertheless, the hypersensitivity of Ni in the Ni–Ti alloy still remains as a key concern for the biomedical applications (Farooq et al. 2014). In order to overcome this issue, Ni-free β-type Ti-based shape memory alloys quickly come into the researchers’ sights and have been paid more attentions due to the nontoxicity, the good workability, excellent superelasticity with a relatively large recoverable strain and biocompatibility, etc. (Kim et al. 2006). To date, Ni-free β-type Ti-based shape memory alloys mainly consist of Ti–Mo, Ti–Zr, and Ti–Cr as well as Ti–Nb based shape memory alloys, which can be employed in biomedical applications (Chiu et al. 2021). The perfect combinations of favorable biocompatibility, acceptable recoverable strains, good workability, lower elastic modulus, etc. of Ti–Nb based shape memory alloys have made them a potential candidate for various biomedical applications including orthodontic wires, cardiovascular stents, and orthopedic implants such as bone anchors, stables, spinal vertebra spacers, etc. (Prabu et al. 2020). However, the corrosion properties of Ti–Nb based shape memory alloys are one of the great challenges on the implantation failure, when they are adopted in the biomedical applications. Nevertheless, binary Ti–Nb shape memory alloys own the excellent anticorrosion performances, compared with CP Ti alloys. For instance, Ti–16Nb shape memory alloy has lower corrosion current density (Jcorr = 3.557(±1.281) × 10−3 μA cm−2) and smaller corrosion potential (φcorr = −0.403 ± 0.020 V) in comparison with CP Ti (φcorr = −0.341 ± 0.020 V, Jcorr = 7.616 (±0.145) × 10−2 μA cm−2), the saturated calomel electrode was used as the “reference” electrode in the present literature (Wang and Zheng 2009). When they are subjected to the electrolytes, the stable TiO2 and Nb2O5 oxide film would form on the surface of shape memory alloy, which has an effective barrier effect on the releasing of inner metal ion (Wang and Zheng 2009; Yang et al. 2023). Thus, achieving the superior corrosion properties is mainly related to the formation of stable oxide film. Besides, the corrosion behaviors of shape memory alloys are not only affected by the external conditions (electrolyte condition, exposure time, applied voltage, etc.) but also can be controlled by the changing of chemical composition, microstructural modifications (Qiu et al. 2020). Among, the variation of chemical composition can cause the significant change of corrosion properties (Moraes et al. 2014; Wang et al. 2021a,b; Wu et al. 2022). For instance, the corrosion resistance of the Ti–Nb–Sn shape memory alloys increases monotonously, as Sn content increases from 0 to 6 wt%. While, the corrosion resistance shows a reverse trends, upon the content of Sn exceeds 6 wt%. In the previous work, it has been reported that trace Cu alloying element is essential to the proper functioning of organs and metabolic processes and stimulates the immune system to fight infections and promotes healing in human bodies (Scheiber et al. 2013). Furthermore, the addition of Cu alloying element can improve remarkably the bioactivity, biotribological, antibacterial, and anticorrosion properties of Ti alloys (Ju et al. 2023; Zhao et al. 2016; Zhao et al. 2022). Similarly, Co-based biomedical alloys (CoCrMo alloys) have the various advantages including the good biocompatibility, improved wear, corrosion, and heat resistant, which can be used in total hip and knee replacements and dental devices (Mutlu 2016). This means that the introduction of Co alloying element can contribute to the improvement of biomedical properties in Ti-based shape memory alloys. Furthermore, it has been revealed that the Co or Cu element also belong to β-stabilizing element for Ti-based alloys, similar to Sn element (Li et al. 2017; Song and Ma 2016; Wang and Zhang 2008). In addition, Cu-containing or Co-doping Ti-based shape memory alloys show significantly good bacterial inhibitory properties (Barros and Gomes 2020; Lu et al. 2021; Ng et al. 2011; Zhao et al. 2022).

In our previous studies, it has been revealed that the mechanical properties and functional performances of Ti–Nb shape memory alloy can be optimized by changing Cu or Co content (Yi et al. 2023a,b,c). In addition, the recent studies of biomedical Ti–Nb based shape memory alloys are mainly focused on the improvement of strain recovery characteristics (Sun et al. 2022a; Yi et al. 2023a,b; Yi et al. 2024; Yuan et al. 2016). However, as one of the important biomedical materials, the evaluation of corrosion and wear behavior is very important for biomedical implantation. To our knowledge, the corrosion behavior and wear properties of Ti–Nb–Co (Cu) shape memory alloys are defective. In the present work, β-stabilizing element Co and Cu are added into the Ti–Nb shape memory alloy, respectively. Besides, the microstructure observation of the corrode samples is carried out to clarify the mechanisms of corrosion. Meanwhile, the mechanisms of corrosion for Ti–Nb shape memory alloys with the various Co and Cu contents are analyzed and discussed.

2 Materials and methods

2.1 Materials preparation

Alloy ingots weighing approximately 50 g were prepared via vacuum arc melting of (Ti84–Nb16)100–x–Cox (x = 0, 0.5, 1.0, 1.5, 2.0, 3.0, 5.0, at.%) and (Ti84–Nb16)100–x–Cux (x = 0, 0.5, 1.0, 1.5, 2.0, 3.0, 5.0, at.%) alloys. The raw materials were Ti with a purity of 99.9 %, Nb with a purity of 99.95 %, Co with a purity of 99.99 %, and Cu with a purity of 99.99 %. The raw materials were purchased from Beijing Dream Material Technology Co., Ltd. In order to ensure the homogeneity of the present alloy ingots, they were remelted at least eight times. Besides, the alloy ingots were homogenized at 900 °C for 3 h under vacuum conditions. Subsequently, the alloy ingots were hot-rolled into a sheet with a thickness of 4 mm at a temperature of 900 °C. Finally, the hot-rolled Ti–Nb–Co and Ti–Nb–Cu sheets were subjected with the cold-rolling with a reduction rate of 80 %. During the rolling process, surface oxides and microcracks were removed using the sandpaper grinding and wheel. Finally, the samples were processed for further analyzing through electrical discharge machine. The samples were then sealed in a vacuum quartz tube and solution treated at 900 °C for 3 h, followed by quenching in ice water. After quenching, the samples were initially treated with 400# SiC sandpaper to remove the surface oxide layer. Then, they were successively polished using #800, #1200, #2000, and #3000 SiC sandpapers, respectively. Finally, they were thoroughly polished with the assistant of polishing agent.

2.2 Electrochemical characterization

Electrochemical corrosion behavior was conducted in the 3.5 wt% NaCl solution at room temperature. The electrochemical workstation (Versatat4, Princeton, USA) with a standard three-electrode system was utilized for the electrochemical analysis. The back and sides of samples were sealed with epoxy resin to prevent the contact and reaction with the electrolyte. The sample acted as the working electrode, whereas the saturated calomel electrode (KCl saturated) and the platinum plate with the dimensions of 15 × 15 × 1 mm were adopted as the reference electrode and the counter electrode, respectively. The dimensions of the electrochemical samples were as follows: 10 mm × 10 mm × 1 mm. Prior to performing the electrochemical tests, all samples were sequentially ground with SiC abrasive paper from 400# to 5000#, followed by the polishing treatment. Before conducting the electrochemical impedance spectroscopy (EIS) measurements, all samples were immersed in a 3.5 wt% NaCl solution until the open circuit potential (OCP) reached a steady state. The OCP measurement was carried out for 3600 s to reach a relatively stable condition, which was defined as holding a potential fluctuation of no more than ±5 mV within 600 s. EIS measurements were performed over a frequency range of 0.01–106 Hz. And the potentiodynamic polarization curves were obtained at a scanning rate of 2 mV/s and a scanning range of −1.5 to 1.5 V. Nyquist and Bode plots and curve fitting were analyzed by using ZSimpWin software. The corrosion potential (φcorr) and corrosion current density (Jcorr) were extracted from the Tafel plots of the anodic and cathodic branches. In order to ensure the precision of the experimental data, all electrochemical tests were repeated at least three times.

2.3 Friction and wear test

The wear performances were characterized by adopting reciprocating sliding mode, which conducted on a ball-on disc wear testing machine (HSR-2M, Zhongkekaihua) under a dry condition. The analyzed samples with a dimension of 20 mm × 10 mm × 4 mm were prepared, which were successively polished by using sandpapers of grades 400#, 800#, and 1500#. Moreover, the surface was cleaned by ethanol before performing the wear tests. The friction pairs were Si3N4 ball with a diameter of 6 mm. The stroke length was 10 mm, the frequency was 2 Hz, the normal loading was set as 10 N, and the whole wear tests process lasted 30 min. The width of the scratch was observed and measured by adopting optical microscope (OM) and scanning electron microscope (SEM) equipped by energy dispersive spectrum (EDS). Similarly, all friction tests were repeated at least three times to ensure the reliability of the experimental results.

3 Results and discussion

3.1 Corrosion behavior

The polarization curves of Ti–Nb–Co and Ti–Nb–Cu shape memory alloys with varying Co and Cu contents are shown in Figure 1(a, b) and (c, d), respectively. It can be observed that the polarization curves of Ti–Nb–Co and Ti–Nb–Cu shape memory alloys are almost the similar, regardless of the ternary Co and Cu content. This indicates that the cathodic and anodic reactions occurring on the surfaces are almost equal for the present Ti–Nb based shape memory alloys. Cathodic reactions in Ti–Nb based shape memory alloys can be attributed to the hydrogen evolution reactions (O2 + 2H2O + 4e−→4OH−). For the anodic reaction, it can be classed into three parts including active dissolution zone (II zone), passivation zone (III and IV zones), and pitting corrosion zone (V zone). In the initial stage of II zone (entering the anodic polarization stage), the current density firstly gradually increases with the potential increasing, which can be attributed to the corrosion and oxidation of the alloying elements (Huang 2003). In the following, as the potential continues to increase, the current density of Ti–Nb–Co and Ti–Nb–Cu shape memory alloys gradually decreases or remains unchanged. This is a typical spontaneous passivation behavior, which is largely dependent on the formation of oxide in the materials (Henderson et al. 2021).

Figure 1: Polarization curves of (a) Ti–Nb–Co shape memory alloys, (b) the partial enlarged drawing taken from square zone in (a), (c) Ti–Nb–Cu shape memory alloys, and (d) the partial enlarged drawing taken from square zone in (c).
Figure 1:

Polarization curves of (a) Ti–Nb–Co shape memory alloys, (b) the partial enlarged drawing taken from square zone in (a), (c) Ti–Nb–Cu shape memory alloys, and (d) the partial enlarged drawing taken from square zone in (c).

In the III zone, the polarization curves of both Ti–Nb–Co and Ti–Nb–Cu shape memory alloys could be regarded as the passivation zone. As the potential increases, the current density is unstable, especially for Ti–Nb–Cu shape memory alloys. The variation of current density with the increased potential is dependent on the competition between formation of oxide films and dissolution of oxide films. For Ti–Nb–Co shape memory alloys, the current density with the increased potential almost keeps constant, which indicates that both the formation rate of oxide film and the dissolution rate of oxide film are basically same. However, there exist obvious distinctions between the Ti–Nb–Cu shape memory alloys and Ti–Nb–Co shape memory alloys. For Ti–Nb–Cu shape memory alloys, when transitioning from zone III to zone IV, a trend of first increasing and then decreasing current density with the rise of potential is observed in the Ti–Nb–Cu shape memory alloy. The rate of oxide formation gradually exceeds the rate of oxide film dissolution, resulting in the formation of a relatively stable oxide layer. Compared with zone II, a more stable oxide layer is generated in zone IV, which plays a positive role in improving the corrosion resistance.

The mechanism illustrations of surface electrochemical corrosion in the present Ti–Nb–Co shape memory alloys and Ti–Nb–Cu shape memory alloys are shown in Figure 2, respectively. The standard electrode potential of Ti is the lowest in the present Ti–Nb based shape memory alloys (Zhao et al. 2015). This means that Ti is preferentially subjected to the dissolution reaction in this process, which can be expressed by the following reaction equations:

(1)Ti→Ti3++3e−
(2)Ti+H2O→TiO+2H++2e−
(3)2TiO+H2O→Ti2O3+2H++2e−
(4)Ti2O3+H2O→Ti2O+2H++2e−

When the Ti oxides at surface is dissolved, other alloying elements such as Nb, Co, and Cu are exposed, and forming a series of oxides on the surface of the present Ti–Nb based shape memory alloys. The formation of new oxides has a passivating effect. The formation of Nb oxides can be expressed by the following formula:

(5)Nb+H2O→NbO+2H++2e−
(6)NbO+H2O→NbO2+2H++2e−
(7)NbO2+H2O→Nb2O5+2H++2e−
Figure 2: Electrochemical corrosion mechanism diagrams of (a) Ti–Nb–Co shape memory alloy and (b) Ti–Nb–Cu shape memory alloy.
Figure 2:

Electrochemical corrosion mechanism diagrams of (a) Ti–Nb–Co shape memory alloy and (b) Ti–Nb–Cu shape memory alloy.

Besides, the adding of ternary Cu or Co elements also has a significant impact on the corrosion resistance due to the formation of different types of oxides. The formation of Cu oxides or Co oxides can be expressed by the following equations:

(8)2Cu+H2O→Cu2O+2H++2e−
(9)2Cu+3H2O+Cl−→Cu2(OH)3Cl+3H+
(10)Co+H2O→CoO+2H+2e−
(11)2CoO+H2O→Co2O3+2H+2e−

Comparing the zones III and IV in polarization curves of Ti–Nb–Cu shape memory alloy to the polarization curves of Ti–Nb–Co shape memory alloy, significant fluctuations can be observed in polarization curves of Ti–Nb–Cu shape memory alloy, indicating that the formation rate of passivation layer changes and the proportion of passivation layer changes from Cu2(OH)3Cl to a more stable Cu2O. In contrast, the formation rate of passivation layer for Ti–Nb–Co shape memory alloy remains relatively constant in this zone. Further increasing the potential, the current density sharply increases. This implies that the larger potential causes the breakdown of the passivation film, occurring the pitting corrosion. The breakdown of passivation layer results in a significant decrease in the corrosion resistance properties.

Moreover, in order to obtain the corresponding corrosion properties, the following formula is adopted to fit the data:

(12)J=Jcorr[exp(φ−φcorrβa)−exp(φ−φcorrβc)]

J and φ represent the current density and potential in the polarization curve, respectively. Jcorr is the corrosion current density. φcorr represents the self-corrosion potential, while βa and βc are the anodic and cathodic Tafel slopes, respectively (Shukla and Balasubramaniam 2006). βa and βc can be obtained through the following equation:

(13)1βa=dln|Ja|dφ; 1βc=dln|Jc|dφ

The corrosion parameters of Ti–Nb–Co shape memory alloy and Ti–Nb–Cu shape memory alloy are, respectively, presented in Tables 1 and 2. Herein, the self-corrosion potential reflects the degree of corrosion tendency and the corrosion current density reflects the speed of corrosion (Stern and Wissenberg, 1959). Such data are the most effective parameters for evaluating the quality of corrosion performance. A trend of first increasing and then decreasing of φcorr value with the increase of Co content as well as a variation trend of Jcorr value of first decreasing and then increasing are observed in Ti–Nb–Co shape memory alloys. Ti–Nb–Co1.0 shape memory alloy exhibits significant advantages in terms of corrosion resistance, which may be attributed to the more effective and dense passive film formed in Ti–Nb–Co shape memory alloy. In Ti–Nb–Cu shape memory alloy, φcorr value also shows a trend of first increasing and then decreasing with the increase of Cu content, while Jcorr value exhibits a trend of first increasing, then decreasing, and then increasing again with further increasing Cu content. According to Table 2, Ti–Nb–Cu1.5 shape memory alloy has the best corrosion resistance, and Cu could form a denser oxide layer in Ti–Nb–Cu shape memory alloy. Excessive Cu and Co addition in Ti–Nb shape memory alloys may lead to the formation of loose oxide, which would have a bad effect on the corrosion resistance. By comparing Tables 1 and 2, it can be concluded that Ti–Nb–Co shape memory alloys have the superior corrosion resistance, which may be profited from the physicochemical properties of Co alloying element and the more corrosion-resistant of cobalt oxide film.

Table 1:

Potentiodynamic polarization corrosion parameters of Ti–Nb–Co shape memory alloys.

Co content (at.%) J corr/(μA cm−2) β a/V−1 β c/V−1 φ corr/V
0 153.79 ± 0.02 616.32 ± 0.06 0.12448 ± 0.13 −0.95263 ± 0.08
0.5 663.73 ± 0.08 7219.7 ± 0.08 0.28224 ± 0.04 −0.97212 ± 0.13
1.0 357.92 ± 0.05 24466 ± 0.03 0.25585 ± 0.08 −0.95499 ± 0.10
1.5 538.66 ± 0.08 16701 ± 0.05 0.22062 ± 0.05 −0.97247 ± 0.18
2.0 483.49 ± 0.01 18603 ± 0.05 0.24808 ± 0.07 −0.97855 ± 0.09
3.0 467.3 ± 0.08 8470.9 ± 0.02 0.21717 ± 0.06 −0.9782 ± 0.10
5.0 478.76 ± 0.06 41531 ± 0.08 0.20279 ± 0.06 −0.98316 ± 0.11
Table 2:

Potentiodynamic polarization corrosion parameters of Ti–Nb–Cu shape memory alloys.

Cu content (at.%) J corr/(μA cm−2) β a/V−1 β c/V−1 φ corr/V
0 153.79 ± 0.06 616.32 ± 0.08 0.12448 ± 0.06 −0.95263 ± 0.11
0.5 473.97 ± 0.08 12612 ± 0.10 0.22054 ± 0.08 −0.98615 ± 0.07
1.0 763.44 ± 0.07 24131 ± 0.05 0.23065 ± 0.09 −0.9799 ± 0.05
1.5 467.54 ± 0.10 15459 ± 0.05 0.19258 ± 0.09 −0.96775 ± 0.09
2.0 525.01 ± 0.07 33256 ± 0.07 0.20058 ± 0.03 −0.98547 ± 0.11
3.0 592.83 ± 0.05 19137 ± 0.06 0.19734 ± 0.05 −0.98117 ± 0.08
5.0 586.53 ± 0.02 9818.6 ± 0.03 0.2097 ± 0.02 −0.9882 ± 0.18

To evaluate the corrosion performances of the Ti–Nb based shape memory alloys, the EIS of the Ti–Nb based shape memory alloys was analyzed. Figure 3 displays the Nyquist plots of Ti–Nb–Cox (x = 0, 0.5, 1.0, 1.5, 2.0, 3.0, 5.0) and Ti–Nb–Cux (x = 0, 0.5, 1.0, 1.5, 2.0, 3.0, 5.0) shape memory alloys. It can be clearly seen that the present Ti–Nb based shape memory alloys have only one capacitive loop, regardless of the variation of chemical composition. This implies that there exists a capacitive time constant, which is due to the formation of a protective native oxide film (Mwtikos et al. 2002; Scherer et al. 1999). It has been reported that the capacitive arc radius is closely related to the corrosion resistance of the material (Natarajan et al. 2021). The larger capacitive arc radius is proportional to the superior corrosion resistance (Li et al. 2022; Yi et al. 2015; Zhou et al. 2022). It can be observed from Figure 3(a) and (b) that the capacitance arc radius of Ti–Nb–Co shape memory alloys with 0.5 at.% Co and 5.0 at.% Co is larger, compared with binary Ti–Nb shape memory alloy, indicating the better corrosion resistance. As shown in Figure 3(c) and (d), the capacitance arc radius of Ti–Nb–Cu shape memory alloy exhibits a trend of first increasing and then decreasing, as Cu content increases from 0 to 5.0 at.%. For comparison, Ti–Nb shape memory alloy with 0.5 at.% Cu possesses the largest capacitance arc radius, showing the better corrosion resistance.

Figure 3: The Nyquist plots of (a, b) Ti–Nb–xCo alloys and (c, d) Ti–Nb–xCu alloys.
Figure 3:

The Nyquist plots of (a, b) Ti–Nb–xCo alloys and (c, d) Ti–Nb–xCu alloys.

To further elucidate the effect of Co and Cu addition on the corrosion characteristics of Ti–Nb based shape memory alloys, the circuit in Figure 3 is used to simulate the EIS spectra. Herein, Rs represents the solution resistance and Rf represents the resistance of the dense/porous oxide film. Due to the existence of relaxation times, a constant phase element (CPE) is adopted to improve the fitting quality. The impedance fitting parameters of the equivalent circuit for Ti–Nb–Co and Ti–Nb–Cu shape memory alloys are shown in Tables 3 and 4, respectively. Polarization resistance (Rp) can be employed to evaluate corrosion performance. In the present circuit, the value of Rp is equal to the value of Rf. The results reveal that Ti–Nb–Co0.5, Ti–Nb–Co5.0, and Ti–Nb–Cu1.0 shape memory alloy exhibit higher Rp, implying the superior corrosion resistance.

Table 3:

The impedance fitting parameters for the equivalent circuit of Ti–Nb–Co shape memory alloys.

Co content (at.%) R s/Ω cm2 R f/Ω cm2 CPE/F cm−2
0 1.289 ± 0.11 70014 ± 0.08 0.00014333 ± 0.28
0.5 2.691 ± 0.08 177690 ± 0.06 8.6604E−5 ± 0.18
1.0 1.021 ± 0.03 1103 ± 0.13 0.00047323 ± 0.13
1.5 1.299 ± 0.05 2632 ± 0.12 0.00029384 ± 0.22
2.0 1.154 ± 0.06 1666 ± 0.05 0.00041799 ± 0.11
3.0 1.22 ± 0.06 3068 ± 0.09 0.00027121 ± 0.13
5.0 4.394 ± 0.18 200850 ± 0.07 0.00010647 ± 0.10
Table 4:

The impedance fitting parameters for the equivalent circuit of Ti–Nb–Cu shape memory alloys.

Cu content (at.%) R s/Ω cm2 R f/Ω cm2 CPE/F cm−2
0 1.289 ± 0.08 70014 ± 0.18 0.00014333 ± 0.11
0.5 1.385 ± 0.05 71450 ± 0.08 8.6604E−5 ± 0.18
1.0 1.677 ± 0.06 136660 ± 0.09 0.00047323 ± 0.12
1.5 1.15 ± 0.06 3030 ± 0.09 0.00029384 ± 0.09
2.0 1.975 ± 0.03 7243 ± 0.07 0.00041799 ± 0.08
3.0 1.312 ± 0.05 69762 ± 0.10 0.00027121 ± 0.11
5.0 1.506 ± 0.08 1183 ± 0.05 0.00010647 ± 0.16

Figure 4 displays the Bode plots and phase angle curves of Ti–Nb–Co and Ti–Nb–Cu shape memory alloys with different Co and Cu contents. It can be observed that in the low frequency range (0.01–1 Hz), the absolute impedance of Ti–Nb–Co and Ti–Nb–Cu shape memory alloys decreases with increasing frequency. The absolute impedance at the low frequency range corresponds to the electrolyte penetration process that occurs at the interface between the substrate and the electrolyte (Wang et al. 2011). As the frequency increases, the time required for electrochemical reactions becomes shorter, and the charge cannot be stored and released in time, resulting in a decrease in impedance when the current passes through the interface. In the high-frequency range (1–105 Hz), the absolute impedance of Ti–Nb–Co and Ti–Nb–Cu shape memory alloys with different Co and Cu contents remains almost unchanged, which can be ascribed to the solution resistance (Ruan et al. 2016). Besides, it can be observed that the phase angle of Ti–Nb–Co and Ti–Nb–Cu shape memory alloys remains almost constant in the range of 1–103 Hz, indicating a clear capacitive behavior. The ability of Ti–Nb–Co shape memory alloy to maintain a high phase angle with the increase of Co content showed a trend of first decreasing, then increasing, with Ti–Nb–Co0.5 and Ti–Nb–Co5.0 having phase angle curves that can maintain a phase angle of 70° over a wide range of frequencies. The ability of Ti–Nb–Cu shape memory alloy to maintain a high phase angle with the increase of Co content showed a trend of first decreasing, then increasing, and then decreasing again, with Ti–Nb–Cu0.5, Ti–Nb–Cu1.0, and Ti–Nb–Cu3.0 having phase angle curves that can maintain a phase angle of 90° over a wide range of frequencies. A high and wide phase angle represents that electrochemical corrosion can cause changes in the surface potential of the metal electrode, resulting in a delayed polarization response of the electrode for a certain period of time, which makes the oxide film formed on both shape memory alloys at the above content more stable and thus having better corrosion resistance. In the Bode plot, resistance at high frequencies is related to the charge transfer control process, while resistance at low frequencies should be attributed to the mass diffusion control reaction (Sun et al. 2022a,b). The greater the difference between high-frequency and low-frequency impedance indicates that the present Ti–Nb based shape memory alloys possesses the better the corrosion resistance (Wang et al. 2015). Hence, it can be concluded that the Ti–Nb–Co0.5, Ti–Nb–Co5.0, Ti–Nb–Cu0.5, and Ti–Nb–Cu1.0 shape memory alloys exhibit the largest impedance difference, meaning the better corrosion resistance.

Figure 4: The Bode plots and phase angle curves of (a) Ti–Nb–Cox and (b) Ti–Nb–Cux shape memory alloys.
Figure 4:

The Bode plots and phase angle curves of (a) Ti–Nb–Cox and (b) Ti–Nb–Cux shape memory alloys.

3.2 Friction and wear properties

As the biomedical implant shape memory alloys, the wear performance is a significant factor that should be considered. Figure 5(a, A1 and A2) and (b, B1 and B2) show the variation of the friction coefficient with sliding time for Ti–Nb–Co and Ti–Nb–Cu shape memory alloys. In the initial stage, the friction coefficient of Ti–Nb based shape memory alloys is relatively larger, regardless of the ternary Co or Cu alloying elements. This can be attributed to the embedding of friction pair into the surface during the initial stage and the small contact area between the friction pair and the surface, resulting in the greater pressure on such a small zone (Kong et al. 2022; Thuong et al. 2015). With the prolonging of time, the friction coefficient sharply decreases and then gradually tends to be stable. In contrast, the effect of ternary Co and Cu on the friction coefficient of Ti–Nb based shape memory alloys is distinctive. The overall friction coefficient of Ti–Nb–Co shape memory alloy decreases with the increase of Co content, among which the friction coefficient of Ti–Nb–Co shape memory alloy with 5.0 at.% Co is the smallest, approximate 0.5. However, the friction coefficient of Ti–Nb–Cu shape memory alloys firstly increases and then decreases with the increase of the ternary Cu contents. By optimizing 5.0 at.% Cu, the smallest friction coefficient of Ti–Nb–Cu shape memory alloys can be obtained, which is about 0.45. The friction coefficient of the present Ti–Nb based shape memory alloys shows a slight increase trend in the later stage, which might be related to the rising of temperature at the alloy surface with the prolonging of friction time and the existence of adhesion phenomena (Yildirim et al. 2016).

Figure 5: The friction coefficient curves of (a, A1 and A2) Ti–Nb–Co shape memory alloy and (b, B1 and B2) Ti–Nb–Cu shape memory alloy.
Figure 5:

The friction coefficient curves of (a, A1 and A2) Ti–Nb–Co shape memory alloy and (b, B1 and B2) Ti–Nb–Cu shape memory alloy.

Figures 6 and 7 display the optical electron microscopy images of the scratch morphology of Ti–Nb–Co and Ti–Nb–Cu shape memory alloys, respectively. It is observed that the friction marks of all Ti–Nb based shape memory alloy present obvious plow-shaped grooves and varying degrees of abrasion pits. Figure 8 display the friction-wear width curves of Ti–Nb–Co and Ti–Nb–Cu shape memory alloys with varying Cu or Co contents. Apparently, the wear width of Ti–Nb–Co shape memory alloy is generally reduced as the Co content increases. Similar to Ti–Nb–Co shape memory alloys, the wear width of Ti–Nb–Cu shape memory alloy is also continuously decreased with Cu content increasing. This suggests that the wear resistance of both Ti–Nb–Co and Ti–Nb–Cu shape memory alloys is significantly improved with the addition of the ternary Cu or Co alloying element. Moreover, the scratch width of Ti–Nb–Co5.0 shape memory alloy (1371 μm) is wider than that of Ti–Nb–Cu5.0 shape memory alloy (1209 μm), indicating that Ti–Nb–Cu5.0 exhibits the superior friction and wear performance, which is consistent with the results of the friction coefficient measurement to a certain extent.

Figure 6: Optical images showing the wear scar of (a) Ti–Nb, (b) Ti–Nb–Co0.5, (c) Ti–Nb–Co1.0, (d) Ti–Nb–Co1.5, (e) Ti–Nb–Co2.0, (f) Ti–Nb–Co3.0, and (g) Ti–Nb–Co5.0 shape memory alloys.
Figure 6:

Optical images showing the wear scar of (a) Ti–Nb, (b) Ti–Nb–Co0.5, (c) Ti–Nb–Co1.0, (d) Ti–Nb–Co1.5, (e) Ti–Nb–Co2.0, (f) Ti–Nb–Co3.0, and (g) Ti–Nb–Co5.0 shape memory alloys.

Figure 7: Optical images showing the wear scar of (a) Ti–Nb, (b) Ti–Nb–Cu0.5, (c) Ti–Nb–Cu1.0, (d) Ti–Nb–Cu1.5, (e) Ti–Nb–Cu2.0, (f) Ti–Nb–Cu3.0, and (g) Ti–Nb–Cu5.0 shape memory alloys.
Figure 7:

Optical images showing the wear scar of (a) Ti–Nb, (b) Ti–Nb–Cu0.5, (c) Ti–Nb–Cu1.0, (d) Ti–Nb–Cu1.5, (e) Ti–Nb–Cu2.0, (f) Ti–Nb–Cu3.0, and (g) Ti–Nb–Cu5.0 shape memory alloys.

Figure 8: The scratch width of Ti–Nb–Co shape memory alloys and Ti–Nb–Cu shape memory alloys.
Figure 8:

The scratch width of Ti–Nb–Co shape memory alloys and Ti–Nb–Cu shape memory alloys.

In order to illustrate the reasons for the superior wear performances in Ti–Nb–Co and Ti–Nb–Cu shape memory alloys, the SEM morphologies and the corresponding EDS results of scratching surface for Ti–Nb–Co5.0 and Ti–Nb–Cu5.0 shape memory alloy are displayed in Figure 9. It is clear that both Ti–Nb–Co5.0 and Ti–Nb–Cu5.0 shape memory alloys exhibit the obvious grooves parallel to the sliding direction. Moreover, larger amounts of debris can be found, which can be regarded as the abrasive particles or scratches (Cleary and Sinnott 2021). Besides, adhesion phenomenon is also observed in both Ti–Nb–Co5.0 and Ti–Nb–Cu5.0 shape memory alloy, which is the typical feature of abrasive wear (Sesemann et al. 2013). The peeled abrasive particles produced “cold welding” points at the contact points between the Ti–Nb based shape memory alloy and friction pairs. Under the shear stress, they peel off from the surface again, forming new adhesive points (Attar et al. 2015). In contrast, the size of debris in Ti–Nb–Cu5.0 shape memory alloy is larger than that of Ti–Nb–Co5.0 shape memory alloy. Meanwhile, the differences are that some grooves with the deep depth and pits also can be observed in Ti–Nb–Co5.0 shape memory alloy, compared with the Ti–Nb–Cu5.0 shape memory alloy. The above results also verify that the Ti–Nb–Cu5.0 shape memory alloy show the superior wear performance. From the analysis of EDS results, it can be found that there exist some O elements in Ti–Nb based alloy matrix and abrasive particles. For comparison, the content of O element in abrasive particles is higher than that in Ti–Nb matrix. In addition, the content of Ti element is higher than that of Nb and ternary Cu or Co element in abrasive particles, regardless of the Cu and Co addition. During the wear and friction process, the rapid rising temperature makes the alloying elements to become active and easier to capture oxygen elements, further attributing to the formation of oxides (Attar et al. 2015; Mudali et al. 2016). Combined with the Gibbs free energy of the possible oxidation reactions in the present Ti–Nb based shape memory alloy in Figure 10, it can be guessed that the formed oxide may be TiO2. This indicates that oxidation wear also occurs during the wear experiment. In summary, both Ti–Nb–Co5.0 and Ti–Nb–Cu5.0 shape memory alloys possess the multiple wear mechanisms, including abrasive wear, adhesive wear, and oxidation wear.

Figure 9: SEM images of the scratch morphology and corresponding EDS results of Ti–Nb–Co5.0 shape memory alloy and Ti–Nb–Cu5.0 shape memory alloy.
Figure 9:

SEM images of the scratch morphology and corresponding EDS results of Ti–Nb–Co5.0 shape memory alloy and Ti–Nb–Cu5.0 shape memory alloy.

Figure 10: The calculation results of Gibbs free energy of the possible oxidation reactions.
Figure 10:

The calculation results of Gibbs free energy of the possible oxidation reactions.

4 Conclusions

In the present study, the effect of ternary Co and Cu on the corrosion behaviors and wear performances of biomedical Ti–Nb shape memory alloys was investigated systematically. The main conclusions can be drawn in the following:

  1. The anodic curve part can be divided into three stages in Ti–Nb based shape memory alloys: incomplete passivity induced by the formation of soluble Ti3+ (II), the passive zone (III and IV), and the last over-passive zone (V). The various types of formed oxides (especially cobalt oxides and copper oxides) in Ti–Nb–Cu and Ti–Nb–Co shape memory alloys during electrochemical corrosion process caused the variation of passive zone (III and IV).

  2. By contrast, the superior corrosion performances with (φcorr = −0.95499 V, Jcorr = 357.92 μA cm−2) and (φcorr = −0.96775 V, Jcorr = 467.54 μA cm−2) can be obtained in Ti–Nb based shape memory alloys by adjusting the Cu and Co, which was attributed to the solid solution of Cu or Co into Ti–Nb matrix.

  3. The wear performances of Ti–Nb shape memory alloys can be optimized by controlling the ternary Co and Cu alloying elements. For comparison, 5.0 at.% Cu addition can significantly result in the minimum friction coefficient of 0.45 in Ti–Nb based shape memory alloys. The improvement of wear performances of the present Ti–Nb based shape memory alloy was related to the enhancement of microhardness due to the solution strengthening.

  4. From the microstructural features viewpoint, the wear mechanisms of ternary Ti–Nb–X shape memory alloys were comprehensive effect of adhesive wear, abrasive wear, and oxidation wear.

Corresponding authors: Yuehai Song and Xiaoyang Yi, Department of Nuclear Equipment, College of Nuclear Equipment and Nuclear Engineering, Yantai University, Yantai264005, China, E-mail: (Y.H. Song) and (X. Y. Yi)
Yunfei Wang and Wei Liu contributed equally to the present work.

  1. Research ethics: Not applicable.

  2. Author contributions: Yunfei Wang and Wei Liu: data curation (lead), writing-original draft (lead) and formal analysis (equal). Xinnuo Liu and Haizhen Wang: data curation (equal), investigation (equal) and resources (equal). Bin Sun: formal analysis (equal), methodology (equal) and superivision (equal). Xinjian Cao and Xiao Liu: investigation (equal) and resources (equal). Yuehai Song and Xiaoyang Yi: conceptualization (lead), funding acquisition (lead) and writing-review & editing (lead). Xianglong Meng and Zhiyong Gao: conceptualization (equal) and writing-review & editing (equal).

  3. Competing interests: The authors state no conflict of interest.

  4. Research funding: The authors are grateful for partial financial support from the National Natural Science Foundation of China (nos. 52101231 and 52101232), Development Plan of Shandong Province Young Innovation Team of Higher Education Institutions (2023KJ242) and Shandong Laboratory of Advanced Materials and Green Manufacturing at Yantai (no. AMGM2021F09), the Natural Science Foundation of Shandong Province, China (no. ZR2021QE044) as well as the Gansu Province Science and Technology Foundation for Youths (no. 21JR7RA088).

  5. Data availability: The raw data can be obtained on request from the corresponding author.

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Received: 2023-07-05
Accepted: 2024-01-23
Published Online: 2024-03-15
Published in Print: 2024-06-25

© 2024 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Reviews
  3. Hydrogen in metallic alloys ─ embrittlement and enhanced plasticity: a review
  4. Sacrificial anode materials to protect marine grade steel structures: a review
  5. Original Articles
  6. A new method to estimate the partition of corrosion inhibitors
  7. Corrosion characteristics of in situ hybrid (Al3Ni + Al2O3)/Al composites synthesized by the solid-state combustion
  8. Repassivation characteristics of carbon steel in chloride-free pore solution after thermal cycles of simulated tropical marine environments
  9. A comparative study on corrosion and wear performances of Ti–Nb–(Cu, Co) biomedical shape memory alloys
  10. Distribution of hydrogen atoms at a notch on X52 steel under various loads and displacements studied by scanning Kelvin probe and finite element modeling
https://doi.org/10.1515/corrrev-2023-0063
Keywords for this article
Ti–Nb based alloy; biomedical shape memory alloys; microstructure; corrosion behavior; wear performance

Articles in the same Issue

  1. Frontmatter
  2. Reviews
  3. Hydrogen in metallic alloys ─ embrittlement and enhanced plasticity: a review
  4. Sacrificial anode materials to protect marine grade steel structures: a review
  5. Original Articles
  6. A new method to estimate the partition of corrosion inhibitors
  7. Corrosion characteristics of in situ hybrid (Al3Ni + Al2O3)/Al composites synthesized by the solid-state combustion
  8. Repassivation characteristics of carbon steel in chloride-free pore solution after thermal cycles of simulated tropical marine environments
  9. A comparative study on corrosion and wear performances of Ti–Nb–(Cu, Co) biomedical shape memory alloys
  10. Distribution of hydrogen atoms at a notch on X52 steel under various loads and displacements studied by scanning Kelvin probe and finite element modeling
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