Comparing properties of substrate-constrained and freestanding epitaxial Ni–Mn–Ga films

In order to use the magnetic shape memory alloy Ni–Mn–Ga with its high achievable strain of up to 10% for microactuators, freestanding epitaxial films are required. Here we show that these conditions can be fulfilled when using chromium as a sacrificial layer. The low misfit towards Ni–Mn–Ga enables epitaxial growth. Furthermore, Cr can afterwards be removed selectively by wet-chemical etching and during deposition no significant interdiffusion is observed. The structure, microstructure and magnetic properties of micrometer thick films are not affected by the etching process. Films are ferromagnetic at room temperature and we observe the coexistence of non-modulated (NM) and seven layered modulated (14 M) martensite. Tensile stress–strain measurement of a freestanding bridge reveals a broad strain plateau of 12% at a twinning stress of 25 MPa, indicating reorientation of NM variants.     

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.     

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,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.     

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.     

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.     

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.     

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.     

Microstructure and properties of indium tin oxide thin films deposited by RF-magnetron sputtering

Tin-doped indium oxide （ITO） thin films were prepared using conventional radio frequency （RF） planar magnetron sputtering equipped with IR irradiation using a ceramic target of In2O3/SnO2 with a mass ratio of 1：1 at various IR irradiation temperatures T1 （from room temperature to 400℃）. The refractive index, deposited ratio, and resistivity are functions of the sputtering Ar gas pressure. The microstructure of ITO thin films is related to IR T1, the crystalline seeds appear at T1= 300℃, and the films are amorphous at the temperature ranging from 27℃ to 400℃. AFM investigation shows that the roughness value of peak-valley of ITO thin film （Rp-v） and the surface microstructure of rio thin films have a close relation with T1. The IR irradiation results in a widening value of band-gap energy due to Burstein-Moss effect and the maximum visible transmittance shifts toward a shorter wavelength along with a decrease in the film＇s refractive index. The plasma wavelength and the refractive index of ITO thin films are relative to the T1. XPS investigation shows that the photoelectrolytic properties can be deteriorated by the sub-oxides. The deterioration can be decreased by increasing the oxygen flow rote （fo2）, and the mole ratio of Sn/In in the samples reduces with an increase info2.     

Microstructure and magnetic properties of NiZn ferrite thin films prepared by sol-gel method

Ti^4＋ substitution for Fe^3＋ in Ni0.5Zn0.5Fe2O4 （NZF） ferrite thin films were realized by sol-gel method and annealing at 600℃for 30 min in the air. Crystal structure and lattice constant determination was performed by X-ray diffractometer （XRD）. Surface microstructure was observed by scanning electron microscope （SEM） and atomic force microscope （AFM）, and the magnetic properties were measured by vibrating sample magnetometer （VSM）. XRD analyses of the samples show that Ni0.5＋xZn0.5TixFe2-2xO4 （NZTF） films with x varing from 0 to 0.15 in steps of 0.05 are composed of single phase with spinel structure. And the lattice parameter, particle size and the diffraction intensity of the films increase with substitution of Ti as the result of the larger radius ions entering the lattice. SEM and AFM show homogeneous grain size of each sample, but there is a few differences in grain size with different Ti-substitution contents. As the nonmagnetic Ti^4＋ substitutes Fe^3＋, both the saturation magnetization and coercivity decrease.     

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.     

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.     

Microstructure,martensitic transformation and mechanical properties of Ni–Mn–Sn alloys by substituting Fe for Ni

The effects of partial substitution of Fe element for Ni element on the structure, martensitic transformation and mechanical properties of Ni_50–xFe_xMn₃₈Sn₁₂ (x=0 and 3%, molar fraction) ferromagnetic shape memory alloys were investigated. Experimental results indicate that by substitution of Fe for Ni, the microstructure and crystal structure of the alloys change at room temperature. Compared with Ni₅₀Mn₃₈Sn₁₂ alloy, the martensitic transformation starting temperature of Ni₄₇Fe₃Mn₃₈Sn₁₂ alloy is decreased by 32.5 K. It is also found that martensitic transformation occurs over a broad temperature window from 288.9 to 352.2 K. It is found that the mechanical properties of Ni–Mn–Sn alloy can be significantly improved by Fe addition. The Ni₄₇Fe₃Mn₃₈Sn₁₂ alloy achieves a maximum compressive strength of 855 MPa with a fracture strain of 11%. Moreover, the mechanism of the mechanical property improvement is clarified. Fe doping changes the fracture type from intergranular fracture of Ni₅₀Mn₃₈Sn₁₂ alloy to transgranular cleavage fracture of Ni₄₇Fe₃Mn₃₈Sn₁₂ alloys.     

Microstructure and properties of Cu–2.8Ni–0.6Si alloy

The phase transformation behavior and heat treatment response of Cu-2.8Ni-0.6Si (wt%) alloy subjected to different heat treatments were studied by X-ray diffraction, transmission electron microscopy observation, and measurement of hardness and electrical conductivity. The variation of hardness and electrical conductivity of the alloy was measured as a function of aging time. On aging at the temperature below TR (500-550°C) in Cu-2.8Ni-0.6Si alloy, the transformation undergoes spinodal decomposition, DO22 ordering, and d-Ni2Si phase. On aging at the temperature above TR (500-550 °C), the transformation products were precipitations of d-Ni2Si. The free energy versus composition curves were employed to explain the microstructure observations.     

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.     

Microstructure and optical properties of sprayed γ-CuI thin films for CuInS_2 solar cells

γ-CuI thin films were prepared by a spraying method using acetonitrile as a solvent,CuI and iodine as reagents.The influences of substrate temperature on the structure,topography,and optical properties of CuI films were investigated.Scanning electron microscope(SEM) photos revealed that the shape and grain size of CuI grains were related to substrate temperature.X-ray diffraction results showed that substrate temperature affected the crystalline quality of CuI films.When the substrate temperature was 110°C,...     

Microstructure and superelastic properties of free forged Ti–Ni shape-memory alloy

Elemental titanium (Ti) and nickel (Ni) powders were consolidated by spark plasma sintering (SPS) to fabricate Ti–51%Ni (mole fraction) shape-memory alloys (SMAs). The objective of this study is to enhance the superelasticity of SPS produced Ti–Ni alloy using free forging as a secondary process. Products from two processes (with and without free forging) were compared in terms of microstructure, transformation temperature and superelasticity. The results showed that, free forging effectively improved the tensile and shape-memory properties. Ductility increased from 6.8% to 9.2% after forging. The maximum strain during superelasticity increased from 5% to 7.5% and the strain recovery rate increased from 72% to 92%. The microstructure of produced Ti–51%Ni SMA consists of the cubic austenite (B2) matrix, monoclinic martensite (B19′), secondary phases (Ti₃Ni₄, Ti₂Ni and TiNi₃) and oxides (Ti₄Ni₂O and Ti₃O₅). There was a shift towards higher temperatures in the martensitic transformation of free forged specimen (aged at 500 °C) due to the decrease in Ni content of B2 matrix. This is related to the presence of Ti₃Ni₄ precipitates, which were observed using transmission electron microscope (TEM). In conclusion, free forging could improve superelasticity and mechanical properties of Ti–51%Ni SMA.     

Microstructure and properties of Mg-Li-Al alloys with Mn addition

M agnesium isone ofthe lowestdensity m aterialsand has high specific strength and rigidity and has widespread application (Fig.1).Itisaclose-packed hexagonalm etaland has poorform ability.H owever,itis wellknown thataddition of lithium to m agnesium can produce workable and body-centered cubicstructurealloys [1-5].M agnesium -lithium alloysexhibittwophasestructuresbetween 5.7 % and 10.3 % by wtLicontent,consisting ofthe α-M g (hcp)and β-Li (bcc) phases at room tem perature (Fig.2). The sin…