Ni-rich Alloys Research Articles

Mechanical and elastocaloric effect of aged Ni-rich TiNi shape memory alloy under load-controlled deformation

This study investigated the elastocaloric effect of Ni-rich Ti49.6Ni50.4 shape memory rods under compression. As-received rods, rods aged at 300 °C for 1 h, and rods aged at 275 °C for 125 h were investigated to reveal the effects of aging on the elastocaloric properties. These samples were first trained under constant stress of 1200 MPa or 1500 MPa, which decreased the B19′ transformation temperature and stabilized the R-phase transformation. Associated with the changes in transformation temperatures, the pseudoelasticity performance and elastocaloric effect of the samples decayed with increasing training times and then became stable when the training time exceeded a certain value. The sample aged at 275 °C for 125 h, which was most hardened by the precipitation hardening effect, exhibited better stability during the training process due to less plastic deformation and thus retained an obvious elastocaloric cooling effect. Because the precipitation treatment broadened the transformation range of the sample aged at 275 °C for 125 h by introducing a two-stage B19’→R→B2 reverse transformation, the elastocaloric cooling effect of 7 °C could be utilized at a relatively large temperature range of −20 °C to 100 °C.

Conventional and Inverse Magnetocaloric Effect in Ni-Rich Ni-Mn-Ga and Ni-Mn-Sn Heusler Alloy: A Comparison

Magnetic and magnetocaloric effect of Ni-rich Ni52Mn34Sn14 (Ni-Mn-Sn) and Ni54Mn17Ga29 (Ni-Mn-Ga) Heusler alloys have been investigated up to a magnetic field of 5T and within a temperature range of 4.2 – 325 K. In this study, we report a systematic comparison between Ni-rich Ni52Mn34Sn14 and Ni54Mn17Ga29 alloys in the light of their magnetocaloric effect (MCE). In both the samples, a large magnetic entropy change was observed (~96 J kg-1 K-1 for Ni-Mn-Ga), but for the alloy Ni-Mn-Sn the MCE becomes negative/inverse. From various magnetic measurements it have been observed that in Ni-Mn-Sn alloy the martensite to austenite transition accompanied by lower to higher magnetization whereas for Ni-Mn-Ga alloy reverse situation occurred. The different type of magnetocaloric effect, i.e. inverse and direct can be explained by considering magneto-crystalline anisotropy and different state of magnetization of the martensite and austenite phase of the alloys.

Effects of Ni and Cr addition on the wear performance of NiTi alloy

Development of hard materials for structural and bearing applications is a challenging task due to complexities in materials processing. Nickel-based intermetallics are a choice for the wear resistance applications. In this study, in order to examine the effects of Ni and Cr addition on the wear performance of Ni-rich alloys, 60Ni, 55Ni-5Cr, 50Ni-5Cr, and 50Ni-10Cr (at.%) alloys were developed through arc melting technique. The aim was to conduct a microstructural and phase analysis study and their effects on hardness and wear behavior. Samples were solution treated at 900 °C for 5 h under vacuum followed by equilibrium cooling. Microstructural and phase analysis revealed the presence of B2 cubic NiTi austenite along with Ni-rich hexagonal Ni3Ti and Cr-rich tetragonal Cr3Ni2 phases throughout the microstructure of alloys. The Cr developed phase was not present in binary composition because of Cr absence. Ternary compositions possessed higher hardness and wear resistance than the binary alloy. Hardness and wear resistance of 50Ni-5Cr and 50Ni-10Cr were comparable with tool steels and conventional 440C martensitic stainless steel bearing material; this high hardness and wear resistance was attributed to the strong solid solution strengthening and precipitation hardening effects of Cr along with the combined effect of Ni-rich Ni3Ti and NiTi austenite phases. Improvement in hardness and wear resistance were correlated with the Cr addition in the developed alloys.

Evolution of crystallographic orientation, precipitation, phase transformation and mechanical properties realized by enhancing deposition current for dual-wire arc additive manufactured Ni-rich NiTi alloy

Ni-rich NiTi alloys were deposited using the in-situ alloying wire arc additive manufacturing (WAAM) method, with varying deposition currents from 80 A to 120 A. The effects of deposition current on the crystal orientation, precipitation, phase transformation and mechanical properties of the WAAM-deposited NiTi alloys were investigated. The results show that increasing the deposition current during the WAAM process would result in noticeable coarsening of B2 grain and an increased volume fraction of high angle grain boundaries (HAGBs). Also, the texture intensity gradually decreased with increasing deposition current. The fabricated components are dominated by the B2 phase with quantities of Ni4Ti3 precipitates in all samples. When increasing the deposition current during the WAAM process, the size of Ni4Ti3 precipitates generally increased and gradually decomposed into a stable Ni3Ti phase which could be detected in the sample produced at 120 A. Furthermore, all of the characteristic phase transformation temperatures increased with the deposition current while the ultimate tensile strength dropped from 927.9 MPa to 613.8 MPa and elongation reduced from 8.7 % to 5.6 %. The cyclic loading-unloading tests revealed that similar trends for the evolution of irreversible strain (εir), recoverable strain (εre), recovery ratio, and elastic energy storage efficiency (η) during cycling were obtained in all samples processed with different deposition currents. The highest εre of 3.2 % and the highest recovery ratio of 53.9 % were obtained in the sample processed with 80 A at an applied stress of 700 MPa for ten cycles. The change of mechanical properties with varying deposition current is due to a combination of factors including precipitation hardening effect, grain refinement effect, and crystal orientation. These results can be useful for optimizing WAAM process parameters to fabricate NiTi components with acceptable structural properties.

Effect of low-energy proton on the microstructure, martensitic transformation and mechanical properties of irradiated Ni-rich TiNi alloy thin films

Effect of low-energy proton on the microstructure, martensitic transformation and mechanical properties of irradiated Ni-rich TiNi alloy thin films

Electrodeposited Ni-Cu alloy coatings on mild steel for enhanced corrosion properties

Ni rich single-phase Ni-Cu alloy coatings were obtained on mild steel substrates by electrodeposition from stable alkaline citrate baths. Three different baths were prepared with varying Cu2+ concentration. Electrodeposition experiments were performed in the galvanostatic mode at three different current densities of 10, 20 and 30 mA cm−2. The coating compositions calculated from EDAX analysis showed that copper content in the coating increased with an increase in copper content of the bath, but decreased with an increase in current density. It was observed that the morphology of the deposits changed from globular to cauliflower with an increase in current density. Deposits from baths containing lower copper content showed more separated and localised cauliflower structures. The roughness of the deposits was also observed to increase with an increase in current density and to some extent with increase in deposition time. The corrosion potential for all coatings was less negative compared to mild steel, indicating barrier protection properties. Corrosion rate was largely affected by the morphology and roughness of the coatings. At higher current densities and higher deposition time, rougher surfaces and gaps and separations between the cauliflower structures were responsible for higher corrosion rate.

Effect of Hf solute addition on the phase transformation behavior and hardness of a Ni-rich NiTi alloy

Hf substituted NiTi alloys are crucial for high temperature shape memory applications owing to their martensitic phase transformation temperatures around 100°C. For further high temperature applications above this limit, a balanced combination of high phase transformation temperatures, high strength and low thermal hysteresis is the foremost criterion. Here, we show that substitution of an array of Hf concentrations (5–25 at.%) to Ni50.3Ti49.7 alloy leads to a wide range of phase transformation temperatures from sub-zero to 280°C. Our studies establish complete solid solution solubility of Hf in the Ni50.3Ti49.7 alloy up to 25 at.% Hf. As a result, the hardness Ni50.3Ti49.7 alloy increases linearly with Hf concentration on account of solid solution strengthening effect. We further show that the Ni50.3Ti29.7Hf20 alloy exhibits least thermal hysteresis combined with high phase transformation temperatures and hardness amongst the compositions investigated. Our study paves the way for designing Ni-rich NiTiHf high temperature shape memory alloys, with operating temperatures up to 250°C and thermal hysteresis as low as 30°C.

Fabrication of step functionally graded NiTi by laser heating

This paper investigates the application of localized laser heating to produce a step pseudoelastic behavior of a cold worked Ni-rich Ti-50.9 at%Ni alloy. The localized heating was done using a custom-made laser heating apparatus. The aim is to create step graded martensitic phase transformation plateaus with large stress window and good recoverability. A cold-worked NiTi wire was locally heated using laser at 400 °C for 10 min, 475 °C for 30 min and 525 °C for 20 min along its length. These temperature and duration settings were carefully chosen based on isothermal heat treatment of the same Ti-50.9 at%Ni wire. Under tensile load, the wire exhibited deformation in a sequence of stress plateaus (step deformation), starting from the segment heated at the highest temperature and ending at the segment heated at the lowest temperature. The step gradient stress plateau produced 310 MPa and 270 MPa stress windows on the forward and reverse transformations, respectively. The residual strain on the recovery was about 1%. This novel heat treatment technique provides the possibility to produce a step pseudoelastic behavior of Ni-rich NiTi alloys to improve the mechanical responses of this smart material in actuator applications.

Martensite stabilisation effect in Ni-rich NiTi shape memory alloy with different structure and martensitic transformations

The aim of the present work was to study the martensite stabilisation effect in Ni51Ti49 alloy with different structures and martensitic transformations. The quenched Ni51Ti49 alloy underwent the B2→B19’ transformation, whereas the B2→R→B19’ transformation occurred in the annealed sample. The martensite stabilisation effect was studied after deformation in the B19’ state in both samples, and in the R state in the annealed sample. It was found that despite the sample structure, no plastic strain appeared during deformation up to 7%, however, the martensite stabilisation effect was observed in both the quenched and annealed samples. If deformation occurred due to the reorientation of the R phase, the martensite stabilisation effect was negligible and did not exceed 1 °C. If the stress induced B19’ phase appeared during deformation in the R state, the martensite stabilisation effect occurred. It was found that the shift in the reverse transformation temperatures on heating of the pre-deformed sample, depended on the structure of the B19’ phase. It was assumed that the damage to the interface coherency resulted in the appearance of an additional energy barrier that influenced the finish temperature of the reverse transformation. Furthermore, it was believed that the martensite reorientation during deformation changed the stored elastic energy, and the shift in the start temperature of the reverse transformation was due to the change in the stored elastic energy and loss in the interface coherency.

Magnetic properties of metastable bcc phase in Fe64Ni36 alloy synthesized through polyol process

The equilibrium FeNi alloy exhibits the bcc phase in a narrow composition less than 5 at.% Ni. Fe64Ni36 was obtained through instant chemical reduction employing polyol process and compared with Fe5Ni95 alloy. X-ray diffraction revealed bcc and fcc phases for the Fe-rich and Ni-rich FeNi compositions, respectively. The metastable bcc FeNi transformed to the fcc phase on annealing at 700 °C, whereas the Ni-rich alloy retained its fcc phase. Electron microscopic examination revealed spherical morphology for Fe64Ni36 alloy with an average size of 72 nm compared with flake-like morphology for the Fe5Ni95. The thermomagnetic analysis revealed a Curie temperature of 567 and 359 °C for the as-synthesized Fe and Ni-rich phases, respectively. An increase in Curie temperature by 30 °C was observed in both the compositions on annealing. Room temperature hysteresis loop measurements showed a saturation magnetization of 117 emu/g for bcc Fe64Ni36 alloy which increased to 165 emu/g for the fcc Fe64Ni36. The reaction kinetics involved in polyol process has enabled us to synthesis and investigate the magnetic properties of metastable bcc phase in the Fe64Ni36 composition.

Wire and arc additive manufacturing of a Ni-rich NiTi shape memory alloy: Microstructure and mechanical properties

Wire and Arc Additive Manufacturing (WAAM) was used for fabrication of NiTi parts using a commercialy available Ni-rich NiTi wire as the feedstock material. The as-built parts are near fully austenitic at room temperature as confirmed by differential scanning calorimetry, X-ray diffraction and superelastic cycling. The as-built microstructure changed from collumnar, in the first deposited layers, to equiaxed in the last deposited ones as a result of the different thermal cycle conditions. This is the first work where WAAM NiTi parts exhibit superelastic behavior under tensile conditions, highlighting the potential use of the technique for the creation of parts shaped in a complex manner based on this material and process. The potential to use WAAM for deposition of advanced functional materials is demonstrated.

Shape memory alloy reinforced magnesium matrix composite fabricated via friction stir processing

Shape memory alloys (SMAs) are the new generation functional material and being recognized as a smart or intelligent material. In this research, a novel Ni-rich NiTip shape memory alloy (SMA) reinforced magnesium matrix composites were prepared using a recent solid-state friction stir processing (FSP) technique. High speed steel was selected as tool material. A flat shouldered plain cylindrical tool pin profile was selected for experiment. The FSP was performed on a fixed value of 560 tool rpm, 100 mm/min traversing speed and 3° tool tilt. The particle distribution in processed zone was analyzed using optical micrography while micro-hardness were evaluated by Vickers indentation test. The results revealed that the FSP was successful in fabrication of surface composite on magnesium matrix. The processed zone indicates good bonding of reinforcement particles with the substrate. However, some accumulation of reinforcement was observed in the processed region. The micro-hardness of the reinforced zone shows significant improvement.

Surface Integrity of Ni-Rich NiTi Shape Memory Alloy at Optimized Level of Wire Electric Discharge Machining Parameters

The concern of this experimental work is to study the surface integrity aspects such as surface morphology, three-dimensional surface topography, recast layer, phase analysis, and micro-hardness for Ni55.95Ti44.05 shape memory alloy at the optimized level of wire electric discharge machining parameters. A mathematical model was developed for surface roughness and material removal rate considering servo voltage, pulse on time, wire tension, wire feed rate, and pulse off time using response surface methodology technique. In order to obtain the optimized parameters, multi-objective optimization technique grey relation analysis was utilized. The adequacy of the developed model was also checked by analysis of variance. At optimal parameters setting, i.e., pulse on time 123 µs, pulse off time 58 µs, servo voltage 50 V, wire tension 3 N, and wire feed rate 5 m/min, maximum material removal rate (8.223 mm3/min) and minimum surface roughness (1.93 µm) were achieved. Surface characteristics of machined surface divulge the presence of discharge craters, debris, molten droplets, micro-voids, spherical nodules, and cracks. A recast layer of thickness 19 µm with approximately 21% of foreign elements was deposited on the machined surface at optimized parameters, whereas the micro-hardness of the outer machined surface was found to be increased approximately 1.98 times as compared to micro-hardness of bulk material. X-ray diffraction analysis shows the presence of the following compounds on the machined surface NiTi, Ni4Ti3, Ti4O3, Cu5Zn8, Ni(TiO3), and NiZn.

Microstructural effect on the thermomechanical behavior of aged Ni-rich NiTi SMA

In this study, we investigate the microstructural effect on the thermomechanical behavior of an aged 50.6 at% Ni NiTi shape memory alloy. The thermal and structural characterizations at zero-stress were performed by means of Differential Scanning Calorimetry (DSC) and x-ray Diffraction (XRD) analyzes, supported by Scanning Electron Microscopy (SEM) observations. It was reported that increasing the aging temperature induces a significant change in microstructural features and thermal properties such as transformation process, transformation temperatures and transformation rate. The precipitation phase kinetic as function of aging temperature was also discussed. In order to understand the influence of the observed microstructural changes on the NiTi mechanical behavior, the stress-induced martensitic transformation was studied through an isothermal compression tests. The hardness and the superelastic stress-strain loops were strongly affected by the microstructural behavior. The correlation between thermal and mechanical behaviors was carried out by the construction of the critical stress-temperature diagram. Two different transformation processes were selected to study the effect of the Ti3Ni4 precipitation phase on the global NiTi thermomechanical behavior. The obtained results can be very useful to predict the occurrence of the shape memory and superelastic properties for an aged Ni-rich NiTi alloy.

Microstructural characterization and quantitative phase analysis of Ni-rich NiTi after stress assisted aging for long times using the Rietveld method

The present work was aimed to quantitatively analyze the phases in the Ni-rich NiTi shape memory alloy which was aged at different temperatures of 470, 500 and 530 °C for 11, 38, 196 and 536 h. The aging treatment was done while applying various stress values. The phase transformation behavior of prepared specimens was analyzed using differential scanning calorimetry (DSC) and X-ray diffraction (XRD) at ambient temperature and 75 °C. The weight percent of the different phases was measured by the Rietveld refinement method using MAUD software. The quantitative phase analysis and transmission electron microscopy (TEM) images show that the amount of Ni4Ti3 precipitates is increased in the specimens aged under stress. Furthermore, the Ni4Ti3 metastable precipitates are transformed to Ni3Ti2 and Ni3Ti stable phases after a long period aging under 120 MPa for 536 h and the various variants of precipitates are not affected by applied stress after long periods of aging.

Effects of thermo-mechanical processing on precipitate evolution in Ni-rich high temperature shape memory alloys

NiTiHf-based high temperature shape memory alloys have attracted considerable attention for their high temperature (>115 °C) reversible phase transformations. Additionally, the shape memory response of the material can be tailored based on microstructure. In the case of Ni-rich NiTiHf shape memory alloys, this response can be tuned with the formation of a nano-phase that can increase the transformation temperature as well as improve mechanical properties. However, NiTiHf-based shape memory alloys are not without their drawbacks, such as difficulty in processing and controlling of nano-precipitation. In this study, the thermo-mechanical processability of a Ni-rich NiTiHf high temperature shape memory alloy, Ni50.5Ti34.5Hf15, is presented. Samples are hot-rolled to 25% and 50% reductions and then further heat treated at 550 and 750 °C to examine the formation of H-phase nano-precipitates. The size and morphology of the nano-precipitates is examined using synchrotron radiation X-ray diffraction during in situ heat treatments and compared with high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) results from ex situ heat treated samples. Changes in transformation temperatures due to the thermo-mechanical processing are determined from differential scanning calorimetry measurements. Results from this study show that SR-XRD can be used to estimate the size and observe the growth and coarsening behavior of H-phase nano-precipitates.

Role of short- and long-range ordering on diffusion in Ni-Al alloys

The varying degrees of short- and long-range order exhibited by multicomponent solids complicates a first-principles calculation of nondilute diffusion coefficients. Temporal and spatial variations in the local degree of order affect the migration barriers of individual hops and can result in strong correlations between successive hops that ultimately affect macroscopic transport coefficients. Here we report on a first-principles study of diffusion in Ni-rich Ni-Al alloys. We used cluster expansion Hamiltonians to describe the energies of the end states and migration barriers of each hop. Kinetic Monte Carlo simulations were performed to calculate macroscopic transport coefficients. Variations in the degree of ordering are shown to play a significant role in affecting diffusion coefficients. While Al has a higher mobility than Ni in the disordered Ni-rich fcc solid solution, it becomes significantly less mobile in the ordered $L{1}_{2}\phantom{\rule{4pt}{0ex}}{\ensuremath{\gamma}}^{\ensuremath{'}}$ phase due to strong thermodynamic tendencies that keep Al trapped to disconnected sublattice sites.

Tribologically induced amorphization in the subsurface of aged Ni-rich TiNi alloy during dry sliding

The microstructure modification due to friction energy transformation in near-surface zone is crucial to the tribological performance of materials. To study the surface and subsurface response of materials exhibiting stress-induced martensitic transformation to repeated sliding, we have investigated the quite novel microstructure changes induced during the dry sliding of an aged Ti-51.5 at.% Ni alloy against the GCr15 spheres. In the process of reciprocating sliding, the B2 austenite primarily transforms into amorphous phase in the worn subsurface area. Remarkably, B2 clusters of nanocrystals below 10 nm are randomly embedded in the amorphous ribbon in the topmost region whereas the medium-range-ordered debris in the order of 3–5 nm are retained in the deeper layer. More importantly, it can be found that large number of nanocrystalline phase and amorphous structure coexist in the strip at a depth about 2.5 μm. Additionally, XRD patterns of the worn tracks show the appearance of B19’, being different from the B2 in the original microstructure. The martensitic transformation therefore plays a crucial role in accommodating associated plastic deformation for the formation of an amorphous layer. The distinctive elementary mechanisms identified here will be essential for the future modeling of the tribologically deformed layer of the alloys.

Effect of Ni content and Hf addition on the unlubricated wear performance of Ni-rich NiTi alloys

Due to the combination of high hardness, high strength, excellent corrosion resistance, superelasticity and low elastic modulus, Ni-rich NiTi alloys have recently been considered as a promising alloy system for using in bearing and related applications. In this study, in order to examine the effects of the Ni content and Hf addition on the unlubricated wear performance of the Ni-rich NiTi alloys, both 52Ni, 55Ni, 52Ni-5Hf and 55Ni-5Hf (at%) alloys were fabricated. The microhardness test results indicate that 55Ni and 55Ni-5Hf samples exhibited higher hardness than the 52Ni and 52Ni-5Hf samples, respectively, this is attributed to the higher volume of the Ni4Ti3 phases in the higher Ni-rich alloys. In addition, the Hf addition further improves the hardness of the alloys. The wear test results also confirm the superior wear performance of the 55Ni-5Hf alloys than that of the 55Ni and 52Ni-5Hf alloys. The SEM observations from the worn surfaces demonstrated the same wear mechanisms of these tested alloys, which are mainly abrasive wear. Hence, it can be deduced that both the higher Ni content and Hf addition are beneficial to obtain better wear performance.

Extraction Effect of Ni-Zn By Electrodeposition from Aqueous Acid Solutions

The electrodeposition of Zn-Ni is classified by Brenner (1) as anomalous codeposition, because zinc, the less noble metal, is preferentially deposited to nickel the more noble metal. The inhibition of H+ reduction occurs with increasing Zn ions concentration in solution (2). Anomalous codeposition is favored in chloride medium and inhibited in boric acid (3). The reaction kinetic of Zn-Ni codéposition was investigated in acid solutions .The effects of solution composition and pH were analyzed. The inhibition of H+ reduction occurs with increasing Zn ions concentration in solution. Increasing pH values causes Zn deposition during Ni-Zn codeposition. Anomalous codeposition is favored in chloride medium and inhibited in boric acid. When alloy deposition becomes the main process, the interfacial pH is governed by the individual metal deposition that controls the kinetic behavior. The interfacial pH increases during separate Ni deposition, meaning that it occurs with simultaneous consumption of H+. Anomalous codeposition process is not due to a saturation of species at the electrode surface. Results show that it is possible to obtain alloys rich in either nickel or zinc , from an acidic solution,depending on the Ni/Zn concentration ration. For Ni/Zn concentration ratios in the range of 1-5, zinc rich alloys are obtained despite Zn is the less noble metal and even when it is present lower concentrations than nickel. For the highest Ni/Zn concentrations ratio ≥100, the formation of the alloy occurs by a normal deposition, resulting in Ni-rich alloys. Boric acid extends the proton discharge potential to more cathodic values. Thus it can reduce anomalous codeposition since the presence of 0,8M of acid reduces the intensity of the peak corresponding to δ phase that is rich in zinc and enhances the intensity of γ phase containing more nickel than the δ phase.