Sn buffered by shape memory effect of NiTi alloys as high-performance anodes for lithium ion batteries

By applying the shape memory effect of the NiTi alloys to buffer the Sn anodes, we demonstrate a simple approach to overcome a long-standing challenge of Sn anode in the applications of Li-ion batteries – the capacity decay. By supporting the Sn anodes with NiTi shape memory alloys, the large volume change of Sn anodes due to lithiation and delithiation can be effectively accommodated, based on the stress-induced martensitic transformation and superelastic recovery of the NiTi matrix respectively, which leads to a decrease in the internal stress and closing of cracks in Sn anodes. Accordingly, stable cycleability (630 mA h g^?1 after 100 cycles at 0.7C) and excellent high-rate capabilities (478 mA h g^?1 at 6.7C) were attained with the NiTi/Sn/NiTi film electrode. These shape memory alloys can also combine with other high-capacity metallic anodes, such as Si, Sb, Al, and improve their cycle performance.     

Atomistic characterization of pseudoelasticity and shape memory in NiTi nanopillars

Molecular dynamics simulations are performed to study the atomistic mechanisms governing the pseudoelasticity and shape memory in nickel–titanium (NiTi) nanostructures. For a 〈1 1 0〉 – oriented nanopillar subjected to compressive loading–unloading, we observe either a pseudoelastic or shape memory response, depending on the applied strain and temperature that control the reversibility of phase transformation and deformation twinning. We show that irreversible twinning arises owing to the dislocation pinning of twin boundaries, while hierarchically twinned microstructures facilitate the reversible twinning. The nanoscale size effects are manifested as the load serration, stress plateau and large hysteresis loop in stress–strain curves that result from the high stresses required to drive the nucleation-controlled phase transformation and deformation twinning in nanosized volumes. Our results underscore the importance of atomistically resolved modeling for understanding the phase and deformation reversibilities that dictate the pseudoelasticity and shape memory behavior in nanostructured shape memory alloys.     

Influence of carbon on martensitic phase transformations in NiTi shape memory alloys

In the present paper we show how carbon affects martensitic transformations in Ni-rich NiTi shape memory alloys. During vacuum induction melting in graphite crucibles, NiTi melts dissolve carbon and TiC particles form during solidification. Differential scanning calorimetry (DSC) shows that this is associated with a decrease in the phase transition temperatures. We provide new experimental evidence for increasing temperature intervals between the start and the end of the martensitic transformations (from B2 to B19′) with increasing C content in as-cast and solution-annealed (850 °C) microstructures. The nucleation and growth of TiC particles in intercellular/interdendritic regions causes variations in the local Ni/Ti ratios. This results in wider transformation temperature intervals (DSC peak broadening) in as-cast and solution-annealed microstructures. Subsequent intense heat treatments (1000 °C) homogenize the alloy and re-establish sharp DSC peaks during martensitic transformations.     

Shape memory behavior of Ti–Ta and its potential as a high-temperature shape memory alloy

In this study, the effect of Ta content on shape memory behavior of Ti–Ta alloys was investigated. The shape memory effect was confirmed in Ti–(30–40)Ta alloys. The martensitic transformation start temperature (M_s) decreased by 30 K per 1 at.% Ta. The amount of ω phase formed during aging decreased with increasing Ta. A stable high-temperature shape memory effect was confirmed for Ti–32Ta (M_s = 440 K) during thermal cycling between 173 and 513 K. On the other hand, the high-temperature shape memory effect of Ti–22Nb, which has a similar M_s to Ti–32Ta, exhibited poor stability due to the large amount of ω phase formed during thermal cycling. It is suggested that Ti–Ta is an attractive candidate for the development of novel high-temperature shape memory alloys.     

High-temperature strength and deformation of γ/γ′ two-phase Co–Al–W-base alloys

The high-temperature strength and deformation behavior of γ/γ′ two-phase Co–Al–W-base alloys have been studied with polycrystalline and single-crystal materials. The ternary, quaternary and higher-order alloys containing Ta, Cr and/or Re exhibit flow stress anomalies above 873 K due to slip of pairs of 1/2〈1 1 0〉 superpartial dislocations on {0 0 1} planes, in addition to {1 1 1} planes, in the γ′ precipitates. Compression tests on the single-crystal specimens reveal a true anomalous peak temperature of 1073 K for both ternary and Ta-containing quaternary alloys. Above the peak, the ternary alloy exhibits a rapid decrease in strength with temperature, as 1/2〈1 1 0〉 dislocations bypass the γ′ precipitates without significant shearing. Conversely, the Ta-containing quaternary alloy sustains strength to higher temperatures due to the activation of 1/3〈1 1 2〉 partial dislocation slip that introduces a high density of stacking faults in the γ′ precipitates.     

On the crystallographic anisotropy of nanoindentation in pseudoelastic NiTi

We use a nanoindenter with a Berkovich tip to study local mechanical properties of two polycrystalline intermetallics with a B2 crystal structure, NiAl and NiTi. We use orientation imaging scanning electron microscopy to select a relevant number of grains with appropriate sizes and surface normals parallel to 〈0 0 1〉, 〈1 0 1〉 and 〈1 1 1〉. As a striking new result, we find a strong crystallographic orientation dependence for NiTi. This anisotropy is less pronounced in the case of NiAl. For NiTi, the indentation force required to impose a specific indentation depth is highest for indentation experiments performed in the 〈0 0 1〉 direction and lowest along the 〈1 1 1〉 direction. We consider transmission electron microscopy results from cross-sections below the indents and use molecular dynamics simulations and resolved shear stress calculations to discuss how this difference can be accounted for in terms of elementary deformation and transformation processes, related to dislocation plasticity (NiAl and NiTi), and in terms of the stress-induced formation and growth of martensite (NiTi). Our results show that the crystallographic anisotropy during nanoindentation of NiTi is governed by the orientation dependence of the martensitic transformation; dislocation plasticity appears to be less important.     

New modelling of the B2 phase and its associated martensitic transformation in the Ti–Ni system

A symmetric two-sublattice model (Ni, Ti, Va)_0.5(Ni, Ti, Va)_0.5 is applied to describe the intermediate B2 compound in order to cope with the order–disorder transition in the Ti–Ni system. Using this model, the ordered B2 and the disordered Ti-rich b.c.c. are described by a single Gibbs free energy function. The B2 phase is the parent phase of the martensitic transformation in the TiNi shape memory alloys (SMAs), and its thermodynamic properties are then reassessed with emphasis on its composition range that is critical for SMAs. The low temperature B19′ phase is also evaluated on the basis of the selected experimental data from the martensitic transformation. Properties related to the transformation are studied in comparison with experimental data. The magnetic contribution is examined for the martensitic transformation. All calculations are in satisfactory agreement with experimental phenomena.     

Mechanism of deformation and crystal lattice reorientation in strain localization bands and deformation twins of the B2 phase of titanium nickelide

Optical metallography and transmission electron microscopy were used to investigate the formation and microstructure of strain localization bands and deformation twins in single crystals of a TiNi alloy deformed by rolling. On the basis of these investigations, with the use of the theory of martensitic transformations based on the concept of cooperative thermal vibrations of coherent objects (close-packed planes) in crystals, a new mechanism of twinning in these alloys is suggested, namely, through the forward plus reverse (B2 → B19 → B2) martensitic transformations with the reverse transformation developing via an alternative transformation system. It is shown that using this mechanism one can describe on the same grounds the twinning in the crystal lattice of the B2 phase with twin planes of different ({1 1 2}, {1 1 3}, and {3 3 2}) Miller indices and the formation of strain localization bands with low-angle misorientations.     

Determination of the interface energies of spherical,cuboidal and octahedral face-centered cubic precipitates in Cu–Co,Cu–Co–Fe and Cu–Fe alloys

The coarsening theory of a spherical particle in a ternary alloy developed by Kuehmann and Voorhees (KV) has been generalized to any centro-symmetric particle. A classical thermodynamic analysis reveals that the generalized KV theory enables us to estimate the interface energy of a particle with a fixed shape, even if the shape of the particle is not controlled by minimization of the interface energy. Data on the coarsening of spherical, {0 0 1}-faceted cuboidal and {1 1 1}-faceted octahedral precipitates in a Cu–Co alloy, a Cu–Fe alloy, and three Cu–Co–Fe alloys with different Co and Fe contents during aging at 873–973 K have been collected by transmission electron microscopy and electrical resistivity. By applying the generalized KV theory to the experimental data, the energies of sphere, {0 0 1} and {1 1 1} interfaces have been determined. Their energies increase with increasing the Fe composition in the alloys.     

Pseudoelastic deformation and size effects during in situ transmission electron microscopy tensile testing of NiTi

The stress-induced B2–B19′ transformation in aged 51 at.% NiTi was investigated using in situ straining transmission electron microscopy (TEM). Increased applied strain along [1 1 0]_B2 transforms B2 into plates containing B19′ variants that are related by a (1 1 0)_B2 compound twin plane. This atypical twin plane is explained by relaxing the invariant plane constraint in the crystallographic theory of martensite (CTM) to an invariant line constraint. The relaxation is rationalized from the thin foil geometry. The relaxed CTM approach, coupled with conditions to maximize transformation strain along the loading axis and minimize elastic energy, predicts the observed twin interface, diffraction patterns, and interface with the B2 austenite. These results demonstrate subtleties in interpreting thin foil TEM results regarding martensitic transformations, and translating those results to bulk response.     

Effect of ternary alloying elements on the shape memory behavior of Ti–Ta alloys

The effect of ternary alloying elements (X = V, Cr, Fe, Zr, Hf, Mo, Sn, Al) on the shape memory behavior of Ti–30Ta–X alloys was investigated. All the alloying elements decreased the martensitic transformation temperatures. The decrease in the martensitic transformation start (M_s) temperature due to alloying was affected by the atomic size and number of valence electrons of the alloying element. A larger number of valence electrons and a smaller atomic radius of an alloying element decreased the M_s more strongly. The effect of the alloying elements on suppressing the aging effect on the shape memory behavior was also investigated. It was found that the additions of Sn and Al to Ti–Ta were effective in suppressing the effect of aging on the shape memory behavior, since they strongly suppress the formation of ω phase during aging treatment. For this reason the Ti–30Ta–1Al and Ti–30Ta–1Sn alloys exhibited a stable high-temperature shape memory effect during thermal cycling.     

Enhancing magnetocrystalline anisotropy of the Fe70Pd30 magnetic shape memory alloy by adding Cu

Fe–Pd–Cu thin films are of great interest for applications in magnetic shape memory microsystems due to their increased martensitic transformation temperature. Here we analyse the consequences of Cu addition to Fe–Pd on the binding energy and magnetic properties by a combination of thin film experiments and first-principles calculations. Strained epitaxial growth of Fe₇₀Pd_30-xCu_x with x = 0, 3, 7 is used to freeze intermediate stages during the martensitic transformation. This makes a large range of tetragonal distortion susceptible for analysis, ranging from body-centred cubic to beyond face-centred cubic (1.07 < c/a_bct < 1.57). We find that Cu enhances the quality of epitaxial growth, while spontaneous polarization and Curie temperature are reduced only moderately, in agreement with our calculations. Beyond c/a_bct > 1.41 the samples undergo structural relaxations through adaptive nanotwinning. Cu enhances the magnetocrystalline anisotropy constant K₁ at room temperature, which reaches a maximum of ?2.4 × 10⁵ J m^?3 around c/a_bct = 1.33. This value exceeds those of binary Fe₇₀Pd₃₀ and the prototype Ni–Mn–Ga magnetic shape memory system. Since K₁ represents the maximum driving energy for variant reorientation in magnetic shape memory systems, we conclude that Fe–Pd–Cu alloys offer a promising route towards microactuator applications with significantly improved work output.     

Deformation mechanisms in a Ru–Ni–Al ternary B2 intermetallic alloy

Deformation mechanisms in a B2 Al50Ni5Ru45 alloy have been studied in compression over the temperature range 298–1323 K. The alloy exhibited a low temperature sensitivity of the flow stress over the temperature range 298–973 K. The strain rate sensitivity below 973 K was relatively low, similar to binary RuAl-based alloys. Dislocation analyses after room temperature compression indicate the presence of 〈1 0 0〉 and 〈1 1 0〉 dislocations on {1 1 0} planes, with the 〈1 0 0〉 dislocations present with slightly higher densities. Compression creep tests at stress levels between 300 MPa and 500 MPa revealed exceptional creep strength in the temperature range investigated. The predominant dislocation substructure after creep deformation consisted of uniformly distributed, cusped 〈1 0 0〉-type screw dislocations on {1 1 0} planes. The deformation behavior and creep mechanisms are discussed in comparison with other high melting temperature B2 intermetallics.     

Study of the fracture behavior in soft and hard oriented NiAl single crystals by AFM

In order to understand the fracture behavior and room temperature brittleness of NiAl single crystals, atomic force microscopy (AFM) investigations were performed on in-situ loaded 4-point-bend specimens of hard and soft oriented crystals. A significant amount of dislocations are emitted from the crack tip on different slip systems. {1 0 0} slip planes are activated in soft crystals, whereas in hard crystals also slip planes, which are identified as {1 1 2} or {1 2 3} are observed. From evaluations of the AFM images, dislocation distributions ahead of crack tips and the plastic crack opening displacement (COD) from blunted crack tips are examined. The fracture toughness is calculated from the measured plastic COD and compared with the results obtained from load-displacement curves. First in-situ experiments on NiAl specimens heated up to 400 K are described, where a significant increase in plasticity is observed.     

Correlation between composition and phase transformation temperatures in Ni–Mn–Ga–Co ferromagnetic shape memory alloys

The effect of Co addition on the phase transformation temperatures (martensitic and Curie point) and crystal structure of Ni–Mn–Ga–Co shape memory alloys has been investigated on (Ni_50.26Mn_27.30Ga_22.44)_100−xCo_x (x = 0, 2, 4, 6) alloys as well as on alloys having different Ni/Mn/Ga ratios and a fixed amount of Co. Alloying by Co affects the martensitic transformation temperature and the transformation enthalpy change mainly through the change on the valence electron concentration (e/a), but the transformation entropy is almost unaffected. On the other hand, the composition (analyzed through the e/a ratio) shows a different influence on the Curie temperature depending on the crystallographic phase (austenite or martensite) in which the magnetic ordering takes place. It is also reported that in Ni–Mn–Ga–Co alloys the Curie temperature of the martensitic phase is lower than that of the austenitic phase, opposite to what occurs in ternary Ni–Mn–Ga alloys.     

Transformation-induced plasticity during pseudoelastic deformation in Ni–Ti microcrystals

[1 1 0]-oriented microcrystals of solutionized 50.7 at.% Ni–Ti were prepared by focused ion beam machining and then tested in compression to investigate the stress-induced B2-to-B19′ transformation in the pseudoelastic regime. The compression results indicate a sharp onset of the transformation, consistent with little prior plasticity. Post-mortem scanning transmission electron microscopy reveals no apparent retained martensite but rather a macroscopic band of dislocation activity within which are planar arrays of ～100 nm dislocation loops involving a single a〈0 1 0〉{1 0 1} slip system. Micromechanics analyses show that the angle of the band is consistent with activation of a favored martensite plate. Further, the stress from the individual variants within the plate is shown to favor activation of the observed slip system. The work done by the applied stress during the B2-to-B19′ transformation is estimated to be ～34 MJ m^?3 at ambient temperature.     

Size effects in the superelastic response of Ni54Fe19Ga27 shape memory alloy pillars with a two stage martensitic transformation

The superelastic behavior of Ni₅₄Fe₁₉Ga₂₇ shape memory alloy (SMA) single crystalline pillars was studied under compression as a function of pillar diameter. Multiple pillars with diameters between 10 μm and 200 nm were cut on a single crystalline bulk sample oriented along the [1 1 0] direction as the compression axis and that had undergone fully reversible two stage martensitic transformation, i.e. L2₁ austenite to 10M/14M modulated martensite and then to L1_o martensite. The results revealed an increase in the critical stress for stress-induced martensitic transformation and the yield strength of martensite with decreasing pillar size. The stress hysteresis also increased with the reduction in pillar size and the superelastic response started to diminish below 500 nm pillar diameter. Two-stage martensitic transformation was suppressed for pillar sizes of 1 μm and below, which were shown to exhibit a direct austenite to L1_o transformation. Such a change in the transformation pathway, i.e. from a two stage to one stage transformation, was also observed in bulk single crystals with increasing temperature. We demonstrated the absence of two stage transformation in bulk at high temperatures. This finding suggests that decreasing the sample size and increasing the temperature have similar effects on the superelastic response of NiFeGa SMAs that had undergone two-stage transformation and indicates that a reduction in pillar diameter decreases the transformation temperature due to the difficulty of martensite nucleation on small scales. The damping coefficients of the pillars were also calculated and the results highlighted that damping capacities higher than those of bulk metallic alloys can be achieved using submicron sized pillars.     

Void growth in metals: Atomistic calculations

Molecular dynamics simulations in monocrystalline and bicrystalline copper were carried out with LAMMPS (Large-scale Atomic/Molecular Massively Parallel Simulator) to reveal void growth mechanisms. The specimens were subjected to tensile uniaxial strains; the results confirm that the emission of (shear) loops is the primary mechanism of void growth. It is observed that many of these shear loops develop along two slip planes (and not one, as previously thought), in a heretofore unidentified mechanism of cooperative growth. The emission of dislocations from voids is the first stage, and their reaction and interaction is the second stage. These loops, forming initially on different {1 1 1} planes, join at the intersection, if the Burgers vector of the dislocations is parallel to the intersection of two {1 1 1} planes: a 〈1 1 0〉 direction. Thus, the two dislocations cancel at the intersection and a biplanar shear loop is formed. The expansion of the loops and their cross slip leads to the severely work-hardened region surrounding a growing void. Calculations were carried out on voids with different sizes, and a size dependence of the stress threshold to emit dislocations was obtained by MD, in disagreement with the Gurson model which is scale independent. This disagreement is most marked for the nanometer sized voids. The scale dependence of the stress required to grow voids is interpreted in terms of the decreasing availability of optimally oriented shear planes and increased stress required to nucleate shear loops as the void size is reduced. The growth of voids simulated by MD is compared with the Cocks–Ashby constitutive model and significant agreement is found. The density of geometrically necessary dislocations as a function of void size is calculated based on the emission of shear loops and their outward propagation. Calculations are also carried out for a void at the interface between two grains to simulate polycrystalline response. The dislocation emission pattern is qualitatively similar to microscope observations.     

Effect of deformation and annealing on the formation and reversion of ε-martensite in an Fe–Mn–C alloy

Microstructure and texture evolution during cold rolling and subsequent annealing were studied in an Fe–22 wt.% Mn–0.376 wt.% C alloy. During rolling the deformation mechanisms were found to be dislocation slip, mechanical twinning, deformation-induced ε-martensite transformation and shear banding. At higher strains, the brass-type texture with a spread towards the Goss-type texture dominated. A decrease in the Cu- and S- components was attributed to the preferential transformation to ε-martensite in Cu- and S-oriented grains. The texture of ε-martensite was sharp and could be described as {1 1 2 9}〈3 3 6 2〉. The orientation relationship {1 1 1}^γ//{0 0 0 1}^ε and 〈110〉^γ//〈1 1 –2 0〉^ε between ε-martensite and austenite was observed but only certain variants were selected. On subsequent annealing, the ε-martensite transformed reversely to austenite by a diffusionless mechanism. Changes in length along rolling, normal and transverse directions on heating were anisotropic due to a combination of volume expansion and shape memory effects. The S-texture component increased significantly due to transformation from the ε-martensite.     

Mechanisms of martensitic phase transformations in body-centered cubic structural metals and alloys: Molecular dynamics simulations

Two different mechanisms of the stress-induced martensitic phase transformation at the crack tip in body-centered cubic (bcc) structural metals and alloys have been studied by molecular dynamics simulations. For cracks with 〈1 0 0〉 crack fronts, the bcc (B2) to face-centered cubic (fcc) (L1₀) phase transformation along the Bain stretch occurs. Whereas for cracks with 〈1 1 0〉 crack fronts, either the bcc (B2) to fcc (L1₀) or the bcc (B2) to hexagonal close-packed (hcp) transformation is the candidate. We have found that the combination of local stress and crystal orientation plays an important role in the mechanism of the martensitic transformation. Thus a simple way to determine the mechanism of the martensitic transformation is developed. The complicated deformation behaviors at the crack tip in bcc iron and B2 NiAl are discussed in terms of this method.