In vitro corrosion behavior of TiN layer produced on orthopedic nickel-titanium shape memory alloy by nitrogen plasma immersion ion implantation using different frequencies

In the present work, the NiTi surface was modified by nitrogen plasma immersion ion implantation (PIII) in an effort to improve the corrosion resistance and mitigate nickel release from the materials. The implanted nitrogen depths and thicknesses of the surface TiN barrier layers were varied by changing the pulsing frequencies during PIII. In order to determine the optimal parameters including the pulsing frequencies, electrochemical tests including open circuit potential (OCP) measurements and potentiodynamic polarization tests were conducted on the untreated and N-implanted NiTi in simulated body fluids (SBF). Our results reveal that the nitride layer produced using a frequency of 50 Hz has the best stability under the OCP conditions and the TiN layer produced using 200 Hz has the highest potentiodynamic stability after immersion in SBF for a long time. The observation can be correlated to the temperature during PIII and the thickness of TiN layer. The TiN layer on the NiTi surface favors deposition of Ca-P composites thereby compensating for the instability of the TiN layer produced at a higher frequency.     

镍钛形状记忆合金在热压缩变形下的动态回复和动态再结晶

通过获得镍钛形状记忆合金在应变速率(0.001～1 s-1)和变形温度(600～1000℃)下的压缩真实应力—应变曲线,研究镍钛形状记忆合金在热变形下的力学行为.通过显微组织演变研究镍钛形状记忆合金的动态回复和动态再结晶,获得应变速率、变形温度和变形程度对镍钛形状记忆合金的动态回复和动态再结晶的影响规律.镍钛形状记忆合金在600℃和700℃下,动态回复和动态再结晶共存,但在其他温度下表现出完全动态再结晶.增加变形温度或降低应变速率,导致较大的等轴晶粒.变形程度对镍钛形状记忆合金的动态再结晶具有重要的影响.在镍钛形状记忆合金的动态再结晶中存在临界变形程度,当大于临界变形程度时,较大的变形程度有助于获得细小的等轴再结晶晶粒.     

Rapid Obtaining of Nano-Hydroxyapatite Bioactive Films on NiTi Shape Memory Alloy by Electrodeposition Process

Nano-hydroxyapatite (n-HA) crystalline films have been developed in this study by electrodeposition method on NiTi shape memory alloy (SMA). The electrodeposition of the n-HA films was carried out using 0.042 mol/L Ca(NO₃)₂ · 4H₂O + 0.025 mol/L (NH₄) · 2HPO₄ electrolytes by applying a constant potential of ?2.0 V for 120 min and keeping the solution temperature at 70 °C. The characterization of n-HA films is of special importance since bioactive properties related to n-HA have been directly identified with its specific composition and crystalline structure. AFM, XRD, EDX, FEG-SEM and Raman spectroscopy shows a homogeneous film, with high crystallinity, special composition, and bioactivity properties (Ca/P = 1.93) of n-HA on NiTi SMA surfaces. The n-HA coating with special structure would benefit the use of NiTi alloy in orthopedic applications.     

In situ synthesis of nanostructured titania film on NiTi shape memory alloy by Fenton＇s oxidation method

Fenton＇s oxidation method was successfully used to synthesize an ideal titania film in situ on NiTi shape memory alloy（SMA） for medical applications. Characterized with scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffractometry, inductively coupled plasma mass spectrometry and electrochemical tests, it is found that the titania film produced by Fenton＇s oxidation method on NiTi SMA is nanostructured and has a Ni-free zone near its top surface, which results in a notable improvement in corrosion resistance and a remarkable decrease in leaching of harmful Ni ions from NiTi SMA in simulated body fluids. The improvement of effectiveness to corrosion resistance and the reduction in Ni release of NiTi SMA by Fenton＇s oxidation method are comparable to those by oxygen plasma immersion ion implantation reported earlier.     

Effect of Aging Treatment on the Compressibility and Recovery of NiTi Shape Memory Alloys as Static Seals

The improvement of the compressibility and recovery of the gaskets can decrease the leakage occurrence in bolted flange connections. In this study, the effect of aging treatment on the compressibility and recovery of NiTi shape memory alloys is investigated as static seals together with thermal analysis. The experimental results indicate that different phase transformations of NiTi alloys are exhibited in the DSC curves during aging treatment. The recovery coefficient of NiTi alloys aged at 500 °C for 2 h is quite low accompanied with a large residual strain. With increasing aging time at the aging temperature of 400 °C, the residual strain and area of hysteresis loop of NiTi alloys are both increased, whereas the recovery coefficient is decreased. Since the deformation associates the phase transformation behavior, aging treatment could improve the compressibility and recovery of NiTi alloys as static seals.     

Multiple plastic deformation mechanisms of NiTi shape memory alloy based on local canning compression at various temperatures

A Ni-rich NiTi shape memory alloy (SMA), which was in its austenitic state at ambient temperature, was subjected to plastic deformation by means of local canning compression at various temperatures ranging from room temperature to 800 °C. Depending on temperatures, NiTi SMA exhibited multiple plastic deformation mechanisms, such as dislocation slip, deformation twinning, grain boundary slide, grain rotation, dislocation climb and grain boundary migration. Amorphization, dynamic recovery and dynamic recrystallization of NiTi SMA were also observed at various temperatures. Mechanism of localized amorphization, in particular, was investigated based on dislocation slip and deformation twinning. Statistically stored dislocation (SSD) and geometrically necessary dislocation (GND) were found to play an important role in the amorphization of the current NiTi SMA. There appeared a critical dislocation density below which NiTi SMA was unable to amorphize. Accordingly, at a fixed deformation strain, there should be a critical temperature above which amorphous phase would not occur in the NiTi SMA matrix. Furthermore, when NiTi SMA experienced plastic deformation at the critical temperature, amorphization and crystallization would occur simultaneously and compete with each other.     

Effect of Surface Alloying by Silicon on the Corrosion Resistance and Biocompatibility of the Binary NiTi

This paper presents the study on changes in element and phase compositions in the near-surface layer and on surface topography of the NiTi specimens after the silicon ion-beam treatment. The effect of these parameters of the near-surface layer on corrosion properties in biochemical solutions and biocompatibility with mesenchymal stem cells of rat marrow is studied. Ion-beam surface modification of the specimens was performed by a DIANA-3 implanter (Tomsk, Russia), using single-ion-beam pulses under oil-free pumping and high vacuum (10^?4 Pa) conditions in a high-dose ion implantation regime. The fluence made 2 × 10¹⁷ cm^?2, at an average accelerating voltage of 60 kV, and pulse repetition frequency of 50 Hz. The silicon ion-beam treatment of specimen surfaces is shown to bring about a nearly twofold improvement in the corrosion resistance of the material to attack by aqueous solutions of NaCl (artificial body fluid) and human plasma and a drastic decrease in the nickel concentration after immersion of the specimens into the solutions for ~3400 and ~6000 h, respectively (for the artificial plasma solution, a nearly 20-fold decrease in the Ni concentration is observed). It is shown that improvement of NiTi corrosion resistance after treatment by Si ions occurs mainly due to the formation of two-layer composite coating based on Ti oxides (outer layer) on the NiTi surface and adjacent inner layer of oxides, carbides, and silicides of the NiTi alloy components. Inner layer with high silicon concentration serves as a barrier layer preventing nickel penetration into biomedium. This, in our opinion, is the main reason why the NiTi alloy exhibits no cytotoxic properties after ion modification of its surface and leads to the biocompatibility improvement at the cellular level, respectively.     

A facile and cost-effective practical approach to develop clinical applications of NiTi: Fenton oxidation process

ABSTRACT

To date, numerous attempts have been made to modify the surface condition of NiTi shape memory alloy to fully benefit from its desirable characteristics, and develop its potential clinical applications. In this survey, the Fenton oxidation process as a newly presented technique for surface modification of NiTi, was employed to address two major priorities in biomedical applications of NiTi, i.e. corrosion improvement and suppression of Ni ion release. To meet these priorities, two important variables involved in the Fenton oxidation process, namely immersion time and electrolyte temperature, were controlled. Results suggested that the application of such an oxidation process may considerably improve the corrosion behaviour of NiTi. The Fenton oxidation process carried out at 65°C for 24?h yields the lowest corrosion current density, 74% lower than bare NiTi. Additionally, Ni ion releases from the surface of NiTi after Fenton's oxidation decreases by ～97%.     

Investigation of the Self-Healing Behavior of Sn-Bi Metal Matrix Composite Reinforced with NiTi Shape Memory Alloy Strips Under Flexural Loading

Utilizing intelligent materials such as shape memory alloys as reinforcement in metal matrix composites is a novel method to mimic self-healing behavior. In this study, the bending behavior of a self-healing metal matrix composite made from Sn-13 wt.% Bi alloy as matrix and NiTi shape memory alloy (SMA) strips as reinforcement is investigated. Specimens were fabricated in different reinforcement vol.% (0.78, 1.55, 2.33) and in various pre-strains (0, 2, 6%) and were healed at three healing temperatures (170°C, 180°C, 190°C). Results showed that shape recovery was accomplished in all the specimens, but not all of them were able to withstand second loading after healing. Only specimens with 2.33 vol.% of SMA strips, 1.55 vol.% of SMA, and 6% pre-strain could endure bending force after healing, and they gained 35.31–51.83% of bending force self-healing efficiency.     

基于变温度场的镍钛形状记忆合金管滚珠旋压有限元模拟(英文)

作为一种新的尝试,在高温下应用滚珠旋压制造镍钛形状记忆合金管。将名义成分为Ni50.9Ti49.1(摩尔分数)的镍钛形状记忆合金棒料进行固溶处理,制成用于滚珠旋压的镍钛形状记忆合金管坯。以变温度场和本构方程为基础,用刚粘塑性有限元法来模拟镍钛形状记忆合金管的滚珠旋压,获得了温度场、应力场和应变场,并进行了旋压载荷预测。有限元模拟结果表明,在旋压件的主变形区有大约160℃的温升。从应力场和应变场可以看出,镍钛形状记忆合金管的外壁比内壁更容易满足塑性屈服准则,塑性变形区处于三向压应力状态。径向应变和切向应变为压缩应变,轴向应变为伸长应变。旋压载荷伴随滚珠旋压行程的变化对于预测旋压件的稳定流动具有重要的意义。     

Comparison of Optical and SEM-BEI Inclusion Analyses of VIM-VAR Nickel-Titanium Alloy

The ASTM Standard for NiTi alloys does not specify the method to be used for the analysis of inclusions. Quantitative analysis is generally done by optical metallography with a computer program to measure size and area fraction. This study gives a comparison of quantitative analyses of inclusions by scanning electron microscopy using backscattered electron imaging (SEM-BEI) and quantitative analyses by optical metallography. Seven samples of 6.3-mm hot-rolled NiTi were evaluated. The coil samples were selected to exhibit a wide range of inclusion content. Each sample had a different Ni to Ti ratio corresponding to a different transformation temperature range (TTR) from A _s = ?25 °C (Ni = 50.79 a/o) to A _s = +95 °C (Ni = 49.63 a/o). Quantitative analyses by optical and by SEM-BEI are in reasonable good agreement for maximum particle size and maximum area fraction. Both methods of analysis show that carbide and intermetallic oxide inclusion populations in VIM-VAR hot-rolled coil vary significantly in the amount and size of inclusions with the alloy transformation temperature. Therefore, an analysis of a larger number of samples at each TTR is needed to develop statistically precise data. All carbide inclusions were less than 12.5 ??m and less than 1.0% area fraction in all the samples. Maximum size and area fraction of carbides decreased as TTR increased. Intermetallic oxide size and area fraction increased with increasing TTR Intermetallic oxides are fractured and separated from the matrix during hot working. However, stringering is very limited. The fracturing appears to happen in high TTR alloys but not in low TTR alloys. This dependence on TTR suggests that chemistry in or around the oxides affects their fracture behavior.     

Wear Properties of Porous NiTi Orthopedic Shape Memory Alloy

Porous NiTi shape memory alloy (SMA) scaffolds have great potential to be used as orthopedic implants because of their porous structure and superior physical properties. Its metallic nature provides it with better mechanical properties and Young??s modulus close to that of natural bones. Besides allowing tissue ingrowth and transfer of nutrients, porous SMA possesses unique pseudoelastic properties compatible to natural hard tissues like bones and tendons, thus expediting in vivo osseointegration. However, the nickel release from debris and the metal surface may cause osteocytic osteolysis at the interface between the artificial implants and bone tissues. Subsequent mobilization may finally lead to implant failure. In this study, the wear properties of porous NiTi with different porosities processed at different treatment temperatures are determined. The results of the study show that the porosity, phase transformation temperature, and annealing temperature are major factors influencing the wear characteristics of porous NiTi SMA.     

Embedding of Superelastic SMA Wires into Composite Structures: Evaluation of Impact Properties

Shape memory alloy (SMA) represents the most versatile way to realize smart materials with sensing, controlling, and actuating functions. Due to their unique mechanical and thermodynamic properties and to the possibility to obtain SMA wires with very small diameters, they are used as smart components embedded into the conventional resins or composites, obtaining active abilities, tunable properties, self-healing properties, and damping capacity. Moreover, superelastic SMAs are used to increase the impact resistance properties of composite materials. In this study, the influence of the integration of thin superelastic wires to suppress propagating damage of composite structures has been investigated. Superelastic SMAs have very high strain to failure and recoverable elastic strain, due to a stress-induced martensitic phase transition creating a plateau region in the stress-strain curve. NiTi superelastic wires (A _f = ?15 °C fully annealed) of 0.10 mm in diameter have been produced and characterized by SAES Getters. The straight annealed wire shows the typical flag stress-strain behavior. The measured loading plateau is about 450 MPa at ambient temperature with a recoverable elastic strain of more than 6%. For these reasons superelastic SMA fibers can absorb much more strain energy than other fibers before their failure, partly with a constant stress level. In this paper, the improvement of composite laminates impact properties by embedding SMA wires is evaluated and indications for design and manufacturing of SMA composites with high-impact properties are also given.     

High-Temperature Oxidation of Zircaloy-4 in Oxygen–Nitrogen Mixtures

Isothermal oxidation experiments with cladding tube segments of Zircaloy-4 (Zr-1.3%Sn) in oxygen–nitrogen model mixtures were performed at 800, 1000, and 1200 °C for 6, 1 h, and 15 min, respectively. The gas compositions varied between 0 and 100 vol% nitrogen including 1 and 99 vol%. A strong accelerating effect of nitrogen on the oxidation kinetics was seen for a wide range of boundary conditions. At 800 °C, oxidation in all mixtures with 1–99 % nitrogen resulted in higher reaction rates compared to the pure gases, especially after transition from protective to non-protective oxide scales. At 1000 and 1200 °C, only starvation of oxygen in mixtures with low oxygen contents resulted in lower rates compared to pure oxygen. The oxide scales formed in the mixtures were very porous due to the formation of zirconium nitride at the metal-oxide interface and its oxidation during continuing reaction. The extension of the oxide-nitride zone increased with temperature and with nitrogen content in the gas mixture. Nitrogen seems also to affect the pre-transition reaction kinetics. The mechanism of the faster oxidation kinetics of zirconium alloys in atmospheres containing nitrogen will be discussed in this paper.     

Functional Characterization of a Novel Shape Memory Alloy

A novel shape memory alloy (SMA) has been developed as an alternative to currently available alloys. This alloy, commercially known by its proprietary brand SMARQ, shows a higher working range of temperatures with respect to the SMA materials used until now in actuators, limited to environment temperatures below 90 °C. SMARQ is a high temperature SMA (HTSMA) based on a fully European material technology and production processes, which allows the manufacture of high quality products, with tuneable transformation temperatures up to 200 °C. Both, material and production processes have been evaluated for its use in space applications. A full characterization test campaign has been completed in order to obtain the material properties and check its suitability to be used as active material in space actuators. In order to perform the functional characterization of the material, it has been considered as the key element of a basic SMA actuator, consisting in the SMA wire and the mechanical and electrical interfaces. The functional tests presented in this work have been focused on the actuator behavior when heated by means of an electrical current. Alloy composition has been adjusted in order to match a transition temperature (As) of +145 °C, which satisfies the application requirements of operating temperatures in the range of ?70 and +125 °C. Details of the tests and results of the characterization test campaign, focused in the material unique properties for their use in actuators, will be presented in this work. Some application examples in the field of space mechanisms and actuators, currently under development, will be summarized as part of this work, demonstrating the technology suitability as active material for space actuators.     

The life of WC–Co cutting tools treated by plasma immersion ion implantation

In this study, the tool life of plasma immersion nitrogen-implanted cutting inserts while machining AISI 4140 steel has been investigated. The implantation time was 5 h and the temperature was in the range 320–520 °C. Implantation dose was 2×10¹⁸ ions cm⁻² for all treatments. Surface topography of the implanted surfaces was obtained from atomic force microscopy. Results of the turning tests are discussed in terms of tool life (flank wear) and surface roughness of the workpieces. The results show that plasma immersion nitrogen implantation increased tool life by about 85%.     

ToF-SIMS Study on the Initial Stages of the Halogen Effect in the Oxidation of TiAl Alloys

Intermetallic titanium aluminide samples implanted with fluorine using plasma immersion ion implantation were investigated after high-temperature exposure for short times at 500 and 900 °C in air by ToF-SIMS as a surface analytical method. The ToF-SIMS method was applied in order to obtain information regarding the location of fluorine with respect to the oxide layer formed and the substrate after ion implantation and after high-temperature exposure, respectively. The aim of the present work was to obtain further insight into the mechanisms active during the initial stages of oxidation. The scale structure in the initial oxidation phase consists of titanium and aluminum oxides/fluorides/oxyfluorides. The arrangement of their layered structure can be interpreted according to their thermodynamic stabilities in the partial pressure gradient of oxygen over the scale and according to the metal activities and the presence of fluorine at the metal/scale interface.     

Surface morphology and tribological behavior of AlSi10 alloys treated by plasma immersion ion implantation for automotive applications

Plasma immersion ion implantation (PIII) was used to implant nitrogen into Al at a temperature in the range of 320–520 °C. AlN phase was observed for temperatures above 450 °C, whereas no AIN detected by XRD diagnosis at temperatures below 380 °C. It was also observed that there was no effective increase in hardness of the material, but some wear resistance due to formation of AlN.     

Stability in Phase Transformation After Multiple Steps of Marforming in Ti-Rich Ni-Ti Shape Memory Alloy

Nickel-titanium (Ni-Ti) alloys are the most attractive among shape memory alloys (SMA) due to their good functionality properties coupled with high strength and ductility. The transformation temperatures in Ti-rich Ni-Ti SMA can be altered by subjecting them to suitable thermal and/or mechanical treatments to obtain martensitic transformation in one or more steps above 0 °C. The goal of the present work is to investigate the stability of phase transformation characteristics, such as, type of sequence (one, two, and multiple steps) and transformation temperatures in Ti-Rich Ni-Ti SMA (Ni-51 at.%Ti), after being subjected to an initial heat treatment at 500 °C for 30 min in air followed by multiple steps of marforming (cold rolling, 30% thickness reduction) intercalated with heat treatments at 500 °C for 30 min in air and a final heat treatment at four different temperatures (400, 450, 500, and 600 °C) for 30 min in air atmosphere. Differential scanning calorimetry (DSC) and electrical resistivity (ER) were used to identify the phase transformation sequences and the stability of transformation temperatures during initial 10 thermal cycles for each sample with distinct thermo-mechanical treatment.     

Effect of alloyed molybdenum on corrosion behavior of plasma immersion nitrogen ion implanted austenitic stainless steel

Plasma immersion ion implantation (PIII) of nitrogen has been performed on two austenitic stainless steels (with and without Mo addition) at three different temperatures namely, 250, 380 and 500 °C for 3 h. Grazing angle X-ray diffraction (GXRD) was carried out on the surface of the steels (both PIII treated and untreated). GXRD results suggest that PIII is more effective in Mo containing stainless steel (SS). The electrochemical corrosion studies examined through both by DC polarization and EIS technique in 3.5 wt.% NaCl reveals that, 3 h N-implantation at 250 and 380 °C improves the corrosion and pitting resistance of both the austenitic stainless steels under investigation. The effect N implantation on pitting resistance is seen more in the presence of Mo, than when it is not present in the SS. It is further emphasized that the pitting resistance of the alloys significantly deteriorates, when they are implanted at 500 °C.