Microstructure and nanomechanical properties of Mn-rich Ni–Mn–Ga thin films

We report the effect of post-annealing on the crystalline phase, grain growth, magnetic and mechanical properties of Ni–Mn–Ga thin films deposited at room temperature followed by post-annealing at different temperatures. The phase and microstructural analysis reveal that amorphous to crystalline transformation occurs in as-deposited films after post-annealing above 873 K. The transformation of disordered phase into nanocrystalline phase by the influence of annealing has been confirmed by transmission electron microscopy. The crystalline films exhibit soft magnetic behavior with the Curie temperature of 314 K, while the amorphous films exhibit the Pauli-paramagnetic behavior even down to 4 K. The mechanical properties like hardness and elastic modulus of the films also show a strong dependence on the annealing temperature with crystalline film exhibiting maximum values of 6 GPa and 103 GPa, respectively. The Ni–Mn–Ga film annealed at 873 K exhibits enhanced nanomechanical properties and room temperature ferromagnetism which make this a potential candidate for use in MEMS devices.     

Microstructural features and orientation correlations of non-modulated martensite in Ni–Mn–Ga epitaxial thin films

Epitaxially grown thin films with nominal composition Ni₅₀Mn₃₀Ga₂₀ and thickness 1.5 μm were prepared on MgO(1 0 0) substrate with a Cr buffer layer by DC magnetron sputtering. The surface layer microstructures of the as-deposited thin films consist of non-modulated (NM) martensite plates with tetragonal structure at ambient temperature, which can be classified into the low and high relative contrast zones of clustered plates (i.e. plate colonies) with parallel or near-parallel inter-plate interface traces in secondary electron images. Orientation analyses by electron backscatter diffraction revealed that individual NM plates are composed of alternately distributed thicker and thinner lamellar variants with (1 1 2)_Tetr compound twin relationship and coherent interlamellar interfaces. In each plate colony, there are four distinct plates in terms of the crystallographic orientation of the thicker lamellar variants and therefore, in total, eight orientation variants. For the low relative contrast zones, both thicker and thinner lamellar variants in adjacent plates are distributed symmetrically across their inter-plate interfaces (along the substrate edges). At the atomic level, there are no unbalanced interfacial misfits and height misfits, resulting in long and straight inter-plate interfaces with homogeneous contrast. However, in the high relative contrast zones, the thicker and thinner lamellar variants in adjacent plates are oriented asymmetrically across their inter-plate interfaces (at ～45° to the substrate edges). Significant atomic misfits appear in the vicinity of the inter-plate interfaces and in the film normal direction. The former result in bending of the inter-plate interfaces, and the latter give rise to the high relative contrast between adjacent plates.     

In situ studies of the martensitic transformation in epitaxial Ni–Mn–Ga films

The martensitic transformation of epitaxial Ni–Mn–Ga films is investigated with respect to changes of structure, microstructure, magnetic and electronic properties. For this, temperature dependent atomic force microscopy (AFM), X-ray, magnetization and resistivity measurements are performed in situ, during martensitic transformation of a 500 nm thick film. The combination of these methods gives a comprehensive understanding of the martensitic transformation and allows to identify differences of constrained epitaxial films compared to bulk. Experiments show the formation of a twinned, orthorhombic martensite with high uniaxial magnetocrystalline anisotropy from the austenite around room temperature. High resolution AFM micrographs directly reveal how martensite variants grow and show the converging of variants nucleated at different nucleation sites. While most features are in agreement with a first-order transformation, the transformation proceeds continuously to lower temperatures, an effect which can be explained by the constraint from the substrate.     

Probing structure and microstructure of epitaxial Ni–Mn–Ga films by reciprocal space mapping and pole figure measurements

The crystal structure and complex twinning microstructure of epitaxial Ni–Mn–Ga films on (1 0 0) MgO substrates was studied by X-ray diffraction using 2θ scans, pole figure measurements and reciprocal space mapping (RSM). The orientation distribution of all variants is visualized by RSM, which forms the basis for a better understanding of the crystallographic relation between variants and substrate. Above the martensitic transformation temperature the film consists of single austenite phase with lattice constant a = 5.81 Å at 419 K. At room temperature some epitaxially grown residual austenite with a = 5.79 Å remains at the interface with the substrate, followed by an intermediate layer exhibiting orthorhombic distortion, a_trans = 6.05 Å, b_trans = 5.87 Å, c_trans = 5.73 Å and a major fraction of 14M (7M) martensite, a = 6.16 Å b = 5.79 Å c = 5.48 Å. The seven-layered modulation of this metastable martensite structure is directly observed by RSM. The intermediate phase observed close to interface indicates the existence of an instable, pre-adaptive martensite phase with a short stacking period.     

Fabricating Ni–Mn–Ga microtubes by diffusion of Mn and Ga into Ni tubes

Tubes of the ferromagnetic shape-memory alloy Ni–Mn–Ga of composition near the Ni₂MnGa Heusler phase can be used, alone or combined in structures, in magnetic actuators or magnetic refrigerators. However, fabrication of Ni–Mn–Ga tubes with sub-millimeter diameter by classical cold or hot drawing methods is hampered by the brittleness of the alloy. Here, we demonstrate a new process, where Ni–Mn–Ga tubes are fabricated by interdiffusion of Mn and Ga into drawn, ductile Ni tubes with 500 and 760 μm inner and outer diameters. After interdiffusion and homogenization of Mn and Ga at 1000 °C for 24–36 h, Ni–Mn–Ga tubes with ∼300 and ∼900 μm inner and outer diameters were obtained with homogeneous radial composition distribution, independently of the diffusion sequences (i.e., Mn and Ga diffused sequentially or simultaneously). Longitudinal composition was uniform over lengths of ∼1 mm, but variable over longer length due to incomplete process control. For two of the three diffusion sequences, a sizeable (20–80 μm) region exhibiting Kirkendall pores formed at the outer surface of the tubes. Magnetization values as high as ∼60 emu/g were measured, which is comparable to the magnetization of the Ni₂MnGa Heusler phase. X-ray diffraction on the tube with the highest magnetization confirmed the room-temperature structure as cubic austenite.     

The ductility and shape-memory properties of Ni–Mn–Co–Ga high-temperature shape-memory alloys

Ni–Mn–Co–Ga alloys with Ni/Mn or Ni and Mn substituted by Co were investigated as candidates for high-temperature shape-memory alloys. Ni_56?xCo_xMn₂₅Ga₁₉ alloys with x < 8 consist of single phase martensite, whereas Ni_56?xCo_xMn₂₅Ga₁₉ (x ? 8), Ni₅₆Mn_25?yCo_yGa₁₉ (y = 4, 8) and Ni_56?z/2Mn_25?z/2Co_zGa₁₉ (z = 4, 6) alloys consist of a two-phase mixture of martensite and γ phase. The mechanical and shape-memory properties of Ni₅₆Mn_25?yCo_yGa₁₉ and Ni_56?z/2Mn_25?z/2Co_zGa₁₉ alloys, which were hot-rolled into 0.5 mm thin plates by conventional hot rolling process, were investigated. The ductility and hot-workability of Ni–Mn–Co–Ga alloys were greatly improved by increasing the amount of ductile γ phase. Dynamic tensile tests and scanning electron microscopy observations of fracture surfaces confirm that the existence of γ phase plays a key role in improving the ductility of Ni–Mn–Co–Ga alloys.     

Variation of atomic spacing and thermomechanical properties in Ni–Mn–Ga/alumina film composites

Ni_51.4Mn_28.3Ga_20.3 thin films deposited on alumina ceramics have been studied by X-ray powder diffraction and dynamic mechanical analysis. Substantial temperature vs. film thickness dependencies of interatomic spacing measured in the direction of the film normal are observed in the range of 25–200 °C and 0.1–5 μm, respectively. The coefficient of thermal expansion (CTE) of the film in the paramagnetic cubic phase has been determined to be equal to (15 ± 1) × 10⁻⁶ K⁻¹ for all the films, in agreement with the CTE of bulk material. The thickness dependent shrinkage of the pseudo-cubic lattice along the film normal direction is attributed to the thermally induced tensile stress in the film plane. The thickness dependence of the elastic modulus of submicron films is obtained. It is shown that the internal stresses result in both the thickness dependence of martensitic transformation temperature and the reversible, thermally induced change in shape of the Ni–Mn–Ga/alumina cantilever actuator.     

Microstructure,mechanical properties and shape memory effect of Ni–Mn–Ga–B high-temperature shape memory alloy

The effects of boron addition on the microstructure, transformation temperature, mechanical properties and shape memory effect of (Ni₅₄Mn₂₅Ga₂₁)_100−xB_x alloys were investigated. The results showed that the martensitic transformation start temperatures M_s decreased monotonically from 465 K for x = 0–278 K for x = 3. Boron addition refined the grain and significantly enhanced the mechanical properties. The compressive fracture strain of 22.3% and reversible strain of 6.8% were obtained in (Ni₅₄Mn₂₅Ga₂₁)_99.5B_0.5 alloy.     

Crystallization process and shape memory properties of Ti–Ni–Zr thin films

The crystallization process of as-deposited Ti–Ni–(10.8–29.5)Zr amorphous thin films was investigated. The Ti–Ni–Zr as-deposited films with a low Zr content exhibited a single exothermic peak due to the crystallization of (Ti,Zr)Ni with a B2 structure. In contrast, a two-step crystallization process was observed in the Ti–Ni–Zr thin films with a high Zr content. Shape memory behavior of Ti–Ni–Zr thin films heat treated at 873–1073 K was investigated by thermal cycling tests under various stresses. The martensitic transformation start temperature increased with increasing Zr content until reaching the maximum value, then decreased with further increasing Zr content. The inverse dependence of transformation temperature on Zr content in the thin films with a high Zr content is due to the formation of a NiZr phase during the crystallization heat treatment. The formation of the NiZr phase increased the critical stress for slip but decreased the recovery strain.     

Microstructure,phase transformation and mechanical property of Nb-doped Ni–Mn–Ga alloys

This study investigated the microstructure, phase transformation and mechanical property of (Ni_49.8Mn_28.5Ga_21.7)_100-xNb_x (x = 1, 3, 6, 9) alloys. The Nb1 alloy exhibited a single austenite phase at room temperature. With increasing Nb content for Nb3, Nb6 and Nb9, the alloy changed to a dual phase consisting of austenitic matrix and Nb-rich second phase with a hexagonal structure, and the amount of the second phase increased with the increase of Nb content. The martensitic transformation temperature and Curie temperature were changed and the transformation enthalpy was gradually reduced with increasing Nb content. The change of martensitic transformation temperature and Curie temperature was related to the introduction of Nb in the Ni–Mn–Ga structure that decreased valence electron concentration (e/a), increased unit cell volume and reduced magnetic exchange of the alloys. The decrease of transformation enthalpy was mainly attributed to the formation and increase of the Nb-rich second phase that reduced volume fraction of the matrix taking part in phase transformation. All the alloys presented a similar compression behavior with progressively fracturing characters (occurrence of several stress drops before complete fracturing). The fracture strength was slightly enhanced with increasing Nb content from Nb0 to Nb9, but the ductility has no apparent improvement.     

Temperature stability of martensite and magnetic field induced strain in Ni–Mn–Ga

In single crystal Ni₂MnGa that exhibits 4.6% magnetic field induced strain (MFIS) at 291 K, it is found that the effect lacks thermal stability. As the temperature rises, the MFIS decreases concomitantly with the lattice distortion. At the same time, the critical magnetic field necessary to activate twin boundary motion falls. A new intermediate martensitic phase is observed.     

Composition-dependent ground state of martensite in Ni–Mn–Ga alloys

For Ni–Mn–Ga alloys, giant magnetic-field-induced strains may be achieved in a modulated martensitic state, offering attractive chances for academic and practical exploration. However, the metastability of modulated martensite imposes a severe constraint on the capacity of these alloys as promising materials for sensors and actuators. In the present work, we conduct both experimental examinations and ab initio calculations to seek potential remedies of this critical problem through composition tuning. Results show that, for Group II alloys having modulated martensite at reasonable temperatures, the increase in Ni addition results in an enhanced tendency to the formation of non-modulated (NM) martensite, whereas the proper Mn addition leads to the stabilization of seven-layered modulated (7M) martensite, which serves as the structural ground state of martensite. By correlating the microstructural evolutions with the two-stage phase transformation (i.e. austenite → 7M martensite → NM martensite), it is demonstrated that the 7M martensite possesses lower energy barriers in terms of the lattice distortion of parent austenite and the interfacial energy of martensitic variants, which plays a vital role in bridging the austenite to NM martensite transformation. This result is expected to provide useful information for the design of these new functional materials.     

Double twinning in Ni–Mn–Ga–Co

Magnetic shape-memory alloys tend to deform via magnetic-field-induced and stress-induced twin-boundary motion. The rather low martensite transformation temperature of ternary Ni–Mn–Ga limits the operating temperature for potential applications. By alloying 5 at.% cobalt, the martensite transformation temperature and the Curie temperature was increased from 70 and 110 °C respectively up to 160 °C. In the single crystalline samples two non-modulated structures with tetragonal and orthorhombic lattices were found. The non-modulated orthorhombic structure has similar lattice parameters to the pseudo-orthorhombic 14M Ni–Mn–Ga phase. The single crystal specimen with the non-modulated orthorhombic structure exhibited a cyclic permutation of all three crystallographic axes in response to uniaxial loading. The parallelepiped-shaped sample was compressed repeatedly in all three directions. While maximizing work done by the load during deformation required three different martensite variants to result from deformation in three different directions, only two different martensite variants were found. The analysis of the sample shape revealed two variants mutually related through cyclic permutation of the lattice parameters, which cannot result from a single twinning event. The cyclic permutation is discussed in the light of Crocker’s double twinning mechanism.     

Microstructure evolution and mechanical properties of spark plasma sintered W–Ni–Mn alloy

Tungsten heavy alloys (90W–6Ni–4Mn) were prepared through spark plasma sintering (SPS) using micron-sized W, Ni, and Mn powders without ball milling as raw materials. The effects of sintering temperature on the microstructure and mechanical properties of the 90W–6Ni–4Mn alloys were investigated. SPS technology was used to prepare 90W–6Ni–4Mn alloys with relatively high density and excellent comprehensive performance at 1150–1250 °C for 3 min. The 90W–6Ni–4Mn alloys consisted of the W phase and the γ-(Ni, Mn, and W) binding phase, and the aγerage grain size was less than 10 µm. The Rockwell hardness and bending strength of alloys first increased and then decreased with increasing sintering temperature. The best comprehensiγe performance was obtained at 1200 °C, its hardness and bending strength were HRA 68.7 and 1162.72 MPa, respectiγely.     

Effects of surface roughness and training on the twinning stress of Ni–Mn–Ga single crystals

Spark eroding, which is commonly employed to cut samples out of magnetic shape-memory alloy single crystals, produces a rough surface layer. Directly after cutting, the single crystals exhibit a high twinning stress. After removal of a surface layer by electropolishing, the twinning stress reduces significantly and stress–strain curves become serrated. The reduction of twinning stress has previously been attributed to the removal of the defective surface layer. In this work, it is shown that different surface treatments in combination with repeated mechanical deformation experiments significantly reduce the twinning stress, regardless of whether or not electropolishing is used. The reduction of the twinning stress is due to softening that takes place as a mechanical training effect, which occurs with mechanical testing. In addition, the stress–strain curves of samples subjected to different surface treatments differed in so far as the curves of electropolished samples showed serrated flow, while the curves of unpolished samples and those of mechanically polished samples were smooth. Furthermore, the unpolished samples displayed significant hardening at higher strain. Following subsequent mechanical polishing, this hardening reduced to nearly zero, and the average twinning stress decreased another 30–50% to 1.6 MPa and below. For these samples, the twinning stress stayed at a very low level until twinning was complete.     

Internal structures and shape memory properties of sputter-deposited thin films of a Ti–Ni–Cu alloy

Low-temperature heat treatments of the sputter-deposited amorphous films, which were previously proved to be a new method to produce very good shape memory properties for Ti-rich Ti–Ni alloys, have been applied to a ternary Ti–43.0Ni–6.2Cu alloy (at.%). The basically same nanometric structures as in the binary alloy are formed, i.e. the nanometric structures consist of extremely thin plate precipitates of bct structure, which are formed on {100} planes of the parent B2 structure and have the c-axis normal to the habit planes. High-shape recovery stresses of about 500 MPa with recoverable shape strains of 5% are obtained without accompanying any permanent strains. A shape recovery stress of more than 870 MPa is attained if it is allowed to involve about 1% permanent strain. Although these bct precipitates have large tetragonalities, they are perfectly coherent with the parent bcc lattice. The maximum shape recovery stress is nearly twice that of the Ti-rich Ti–Ni binary alloy having a similar nanometric structure. It is suggested that this remarkable increase in recovery stress may be attributed to the change in Burgers vector of dislocations caused by partial disordering in Ti–Ni–Cu alloys. It is emphasized that the shape recovery stress in this ternary alloy is four times that of the Ti₂Ni containing samples and 10 times that of a bulk Ti–45Ni–5Cu alloy.     

The influence of saccharin on the electrodeposition and properties of Co–Ni alloy thin films

Abstract

Co–Ni alloys thin films were electrodeposited on Ru substrates from a chloride-saccharin bath at pH 3.8 and the effects of adding saccharin to the bath on the electrochemical deposition, corrosion resistance, chemical composition, physical and magnetic properties of the deposits were investigated. The analytical techniques of cyclic voltammetry (CV), potentiodynamic polarisation, electrochemical impedance spectroscopy (EIS), atomic absorption spectroscopy (AAS), atomic force microscopy (AFM), X-ray diffraction and hysteresis curves were applied to assess the codeposition process, and determine corrosion resistance, composition, morphology, nanocrystallinity and magnetic properties. Effectively, CV measurements revealed that the addition of saccharin in the electrolytic bath modifies the deposition process and an anomalous codeposition takes place; this enhanced the Co percentage in the Co–Ni deposits. Saccharin addition also increases the double layer capacitance and decreases the charge transfer resistance. On the other hand, the Tafel plots show a higher corrosion resistance for the deposits obtained from a bath with saccharin than those obtained from a bath without it. Furthermore, the presence of the saccharin in the bath also causes notable changes in the morphology and structure characteristics of deposits. In addition, it was found that the additive influences the magnetic properties of Co–Ni alloy thin films. The coercivity and magnetisation saturation are diminished for Co–Ni films prepared from electrolytes with addition of saccharin.