Magnetic and transport properties in the Heusler series Ni2−xMn1+xSn affected by chemical disorder

Crystal structure, magnetic and transport characteristics of Ni_2−x Mn_1+x Sn Heusler series have been studied with the emphasis on chemical disorder effects. It is shown that the structure and the disorder character in these series can be predicted by using simple rules. Ni₂ MnSn is a ferromagnetic, congruent melting phase, which crystallizes cubic in the L2₁ structure type. By increasing x, Ni and Mn atoms randomly mix and occupy the heterocubic sites of the regular Heusler structure, and the magnetic structure becomes ferrimagnetic. The total magnetic moment m_sat decreases linearly in the range 0.2 ≤ x ≤ 1, while the Curie temperature T_C increases. At low Mn content (x < 0.2), the unit cell volume shows anomalous behavior, characterized by constant m_sat and T_C. Electrical resistivity, Seebeck coefficient, and thermal conductivity strongly depend on the amount of disorder, which increases with the Mn content. Results of first-principle calculations based on the coherent potential approximation (CPA) alloy theory for the magnetic and electrical properties are in reasonable agreement with the simple rules and all experimental data.     

Effect of Co addition on the martensitic transformation and magnetocaloric effect of Ni–Mn–Al ferromagnetic shape memory alloys

A series of Ni_50−xCo_xMn₃₂Al₁₈ (x = 3, 4, 5, 6, 7, and 8) alloys were prepared by the arc melting method. The martensitic transformation (MT) shifts to a lower temperature with increasing Co concentration and can be tuned to occur from a ferromagnetic austenite to a weak-magnetic martensite in the range of 6 ≤ x ≤ 8. The field-induced metamagnetic behavior was realized in Ni₄₂Co₈Mn₃₂Al₁₈ sample in which a large magnetic entropy change of 7.7 J/kg K and an effective refrigerant capacity value of 112 J/kg were obtained under the field of 60 kOe. The large magnetocaloric effect and adjustable MT temperature suggest that Ni–Co–Mn–Al alloys should have promising potential as magnetic refrigerants.     

Microstructure and shape memory behavior of Ti55.5Ni44.5−xCux (x = 11.8–23.5) thin films

The microstructure and shape memory behavior of Ti_55.5Ni_45.5−xCu_x (x = 11.8–23.5) thin films annealed at 773, 873, and 973 K for 1 h were investigated. None of the films except the Ti_55.4Ni_32.8Cu_11.8 film annealed at 773 K for 1 h had any precipitates in the B2 grain interiors and their grain sizes were small (less than 1 μm). Increasing the annealing temperature caused grain growth and thus a decrease in the critical stress for slip and an increase in the martensitic transformation start temperature (Ms). The grain size was also controlled by the growth of a second phase. In the three-phase equilibrium region of Ti₂Ni, Ti₂Cu and TiNi, Ti₂Cu grains grew faster than Ti₂Ni grains, leading to a decrease in the critical stress for slip and an increase in the Ms temperature with increasing Cu content.     

Crystal structure and thermoelectric properties of Cu2Cd1−xZnxSnSe4 solid solutions

Cu₂Cd_1–xZn_xSnSe₄ solid solutions were synthesized, and their phase constitutions and thermoelectric properties were investigated. The solid solutions crystallized in the stannite-type structure for Zn contents x up to 0.65 and in the kesterite-type structure for 0.7 ≤ x ≤ 1.0. The lattice parameter a and cell volume V of the compounds decreased linearly with increasing x for both the stannite-type (0 ≤ x ≤ 0.65) and the kesterite-type (0.7 ≤ x ≤ 1) structures. The lattice parameter c decreased with increasing x for the compounds with the kesterite-type structure but increased for the compounds with the stannite-type structure. The c/a ratio increased with increasing Zn content, which indicated an weakening of the lattice distortion. The Seebeck coefficient tended to decrease with increasing Zn content, whereas the electrical conductivity and thermal conductivity increased. The figure of merit ZT increased with increasing x over the composition range of 0 ≤ x ≤ 0.60 and then fluctuated with a further increase in x. A maximum ZT of 0.23 was achieved for Cu₂Cd_0.4Zn_0.6SnSe₄ at 720 K.     

Phases and thermoelectric properties of Ge1−x(Pb0.9Yb0.1)xTe alloys

A series of Ge_1−x(Pb_0.9Yb_0.1)_xTe alloys with x = 0.05, 0.10, 0.15, 0.20 and 0.30 were prepared by a conventional melting and a spark plasma sintering (SPS) techniques. The phases and thermoelectric properties for the alloys were investigated. The alloys consist of the GeTe-based rhombohedral single phase for x = 0.05, while both GeTe-based rhombohedral and PbTe-based rock-salt phases due to spinodal decomposition for the higher Pb content (x ≥ 0.10). The amount of the PbTe-based phase increases with the Pb content x increasing. All samples show p-type conduction. As Pb content x increases, the thermal conductivity reduces obviously, while the Seebeck coefficient and the electrical resistivity increases slightly. The maximum ZT of 1.4 at 723 K was eventually achieved in the sample with x = 0.15 due to its rather low thermal conductivity, from 3.7 W m⁻¹K⁻¹ at room temperature to 1.4 W m⁻¹K⁻¹ at 723 K (3.7–1.4 W m⁻¹K⁻¹), relative high Seebeck coefficient (46.5–141 μV K⁻¹) and relative low electrical resistivity (3.0–7.36 μΩ m).     

High strength Ni–Zr–(Al) nanoeutectic composites with large plasticity

Micrometer-sized γ−Ni dendrite reinforced nanoeutectic matrix composites have been developed in (Ni_0.92Zr_0.08)_100–xAl_x (0 ≤ x ≤ 4) by arc melting. The eutectic matrix is composed of alternate nano-lamellae of intermetallic Ni₅Zr and fcc–Ni solid solution phases. All these composites exhibit very high strength, large compressive plasticity ∼25% and strain-hardening up to 1780 MPa. Al dissolves in γ−Ni(Zr) solid solution phase, decreases its hardness/strength, and increases the volume % of γ−Ni dendrite from 20% (x = 0) to 29% (x = 4). Whereas, refinement of the eutectic lamellae thickness from 275 nm (x = 0) to 160 nm (x = 4) increases the matrix hardness and retains the global strength of the composites. The effect of Al addition on the microstructure formation, volume fraction as well as the length scale of the constituent phases, and mechanical properties, have been discussed using an analytical model.     

Microstructure and martensitic transformation of TiNiNbB shape memory alloys

In present work, microstructure, martensitic transformation and mechanical properties of Ti₄₄Ni_47−xNb₉B_x (x = 0, 0.5, 1, 5 at.%) alloys were investigated as a function of B content. The results show that the addition of B significantly influences the microstructure of the alloys. The microstructure of Ti₄₄Ni₄₇Nb₉ alloy consists of B2 parent phase matrix and β-Nb phase. When the B content is 0.5 at.%, Nb₃B₂ phase presents. With further increasing B content to above 1 at.%, TiB and NbB phases present instead of Nb₃B₂ phase. With increasing B content, the transformation temperatures increase due to the reduced Ni/Ti ratio and Nb content in the matrix. The mechanical properties can be optimized by the addition of 1 at.% B.     

Multi-stage martensitic transformations induced by repeated thermal cycling of equiatomic TiNi alloy

Usually a multi-stage martensitic transformation is observed in Ni-rich TiNi alloys after heat treatment at 350–500 °C. It is due to the internal stresses created by the Ni₄Ti₃ participate. In the present work it was found that the multi-stage martensitic transformation appeared in Ti–50.0 at.% Ni alloy after thermal cycles through the temperature range of the phase transitions. Annealed sample undergoing one-stage phase transition was subjected to 32 thermal cycles in the DSC apparatus. The results had shown that three-stage forward martensitic transformation observed after 32 thermal cycle was due to the B2 → R, B2 → B19′ and R → B19′ phase transitions. It was found that the B19′ phase obtained from the B2 phase underwent the reverse transformation at higher temperatures than the B19′ phase obtained from the R phase. After annealing the cycled sample at 400 °C the transformation behavior was similar to the non-thermal cycled alloy. It was concluded that the main reason for the multi-stage phase transition induced by the thermal cycles was the phase hardening.     

An investigation on the crystal structures of Ti50Ni50−xCux shape memory alloys based on density functional theory calculations

The present research has investigated the martensite crystal structures and electronic structures of Ti₅₀Ni_50−xCu_x (x = 0, 5, 12.5, 15, 18.75, 20, 25) shape memory alloys using density functional theory (DFT). The computational results are compared with the reported data and it is found that the equilibrium lattice constants are in good agreement with reported values. It is also found that with Cu addition to NiTi, the lattice parameters (a and c) and the monoclinic angle decrease, whereas the lattice parameter b increases. With increasing Cu content, fewer electrons were transferred from Ti to Ni in comparison with that in binary NiTi alloys, and the NiTi monoclinic structure becomes unstable. When Cu content is increased to around 20 at%, an orthorhombic crystal structure is formed which agrees well with reported experimental observations.     

Effect of minor Cu content on microstructure and mechanical property of NiTiCu bulk alloys fabricated by crystallization of metallic glass powder

Ultrafine-grained Ni_50.2−xTi_49.8Cu_x (x = 0, 2.5, 5, and 7.5) bulk shape memory alloys were fabricated by sintering of metallic glass (MG) powder and crystallization of amorphous phase. Non-isothermal crystallization kinetic analysis reveals that the crystallization mechanism of the synthesized x = 5 MG powder is typical interface-controlled two dimensional growth of nuclei followed by volume diffusion-controlled three dimensional growth of nuclei. In contrast, the crystallization mechanism of the synthesized x = 7.5 MG powder is typical volume diffusion-controlled three dimensional growth of nuclei in whole crystallization process. Correspondingly to different crystallization mechanisms, the two sintered and crystallized (SCed) bulk alloys have the same crystallized phases of bcc B2, fcc NiTi₂ phases, and monoclinic B19′, but these phases display different morphologies and distributions. The SCed x = 5 bulk alloy has a microstructure of bcc B2 matrix surrounding fcc NiTi₂ phase region, while the SCed x = 7.5 bulk alloy possesses discontinuous bcc B2 phase region. Consequently, the different crystallization mechanisms and microstructures causes extreme high yield strength and large plasticity for the SCed x = 5 bulk alloy and low strength and no plasticity for the SCed x = 7.5 bulk alloy. Especially, the yield strength of the SCed x = 5 bulk alloy is at least two times of that of the counterpart alloy prepared by melt solidification. The results provide a method fabricating high performance bulk alloys by tailoring crystallization mechanism using powder metallurgy.     

Thermal conductivity of Ni3V–Ni3Al pseudo-binary alloys

The effect of changes in the composition and microstructure of the Ni₃V–Ni₃Al pseudo-binary alloys on their thermal conductivity has been investigated. For Ni₃V and Ni₃Al-based single-phase alloys, the thermal conductivity shows a maximum value at the stoichiometric compositions, and it decreases as the V (or Al) content of the Ni₃Al (or Ni₃V) alloy increases, following the Nordheim rule. For Ni₃V–Ni₃Al two-phase alloys, the thermal conductivity of the constituent Ni₃Al phase exhibits a smaller value than that of the Ni₃V phase. Eventually, the thermal conductivity of the two-phase alloys decreases as the Al content increases because of the increase in the volume fraction of the Ni₃Al phase with low conductivity. As the temperature increases from 293 K to 1073 K, the conductivity increases for all of the alloys but not for stoichiometric Ni₃V. However, the dependence of the thermal conductivity on the alloy composition between 293 K and 1073 K is similar. Hence, it is confirmed that the thermal conductivity of the Ni₃V–Ni₃Al pseudo-binary alloys is controlled by the composition and volume fraction of the constituent phase.     

Reassessment of Ni-Al and Ni-Fe-Al solidus temperatures

Solidus temperatures of the B2 NiAl phase have been determined by high-temperature differential thermal analysis for binary melt compositions Ni_xAl_100?x (45<x<57) and for ternary alloys Fe_yNi_50?yAl₅₀ (0≤y≤50). It was shown that the melting temperature of the stoichiometric Ni₅₀Al₅₀ phase is 1681 °C, which is 43 K higher than some literature data. The solidus line at the Ni-rich side of the Ni-Al phase diagram exhibits a steeper slope than that reported previously. Substituting Fe for Ni, the decrease of solidus temperature along the isoplethal section with 50 at.% Al of the ternary Ni-Fe-Al phase diagram exhibits a steep initial slope of ?13 K/at.% Fe for small Fe-fractions, which changes into a nearly linear decrease with an average slope of ?8.5 K/at.% Fe.     

Strain glass in doped Ti50(Ni50−xDx) (D = Co,Cr, Mn) alloys: Implication for the generality of strain glass in defect-containing ferroelastic systems

Strain glass is a new glassy state discovered recently in Ni-rich Ti–Ni ferroelastic alloys. However, it remains unclear whether or not strain glass can be found in a wide range of ferroelastic systems. Here, we investigated the transition behavior of three different defect-doped systems Ti₅₀(Ni_50?xD_x) (D = Co, Cr, Mn) and found a striking similarity in their transition behavior as a function of defect concentration x. In all these systems, there exists a critical doping level x_c at which the transition behavior shows an interesting crossover. At x < x_c, these materials undergo a martensitic transition and the transition temperature decreases with increasing x. However, at x > x_c, the martensitic transition is suppressed and a strain glass transition occurs. These results imply that strain glass may be quite general in defect-containing ferroelastic systems. An analysis with a modified Landau-type free energy landscape suggests that although point defects always favor the formation of strain glass, to actually form a strain glass they need to destabilize the martensite of the system.     

Influence of Sc addition on microstructure and transformation behaviour of Ni24.7Ti50.3Pd25.0 high temperature shape memory alloy

Vacuum-arc melted Ni_24.7Ti_50.3Pd_25.0 and Ni_24.7Ti_49.3Pd_25.0Sc_1.0 (at.%) alloys were investigated to study effect of Sc micro-addition on microstructure and transformation behaviour of NiTiPd alloy. Study showed that microstructure of homogenized NiTiPd alloy consisted of NiTiPd matrix interspersed with Ti₂(Ni,Pd) precipitates. In contrast, NiTiPdSc alloy showed a single phase NiTiPdSc matrix with a few scandium oxide particles at isolated places. TEM and X-ray diffraction studies confirmed matrix phase of the alloys to be of orthorhombic B19 structure. TEM observations showed that NiTiPdSc alloy had relatively larger martensite plates with a smaller twin ratio compared to that of NiTiPd alloy. Also, APB (anti-phase boundary) like regions with twinless martensites was observed in both the alloys, area fraction of APB-like regions being more in NiTiPdSc alloy. Thermal analysis showed that transformation temperatures (TTs) of NiTiPd alloy decreased significantly with addition of Sc. The martensite finish temperature (M_f) of 181 °C for NiTiPd alloy lowered to 139 °C upon 1.0 at.% Sc addition. The transformation hysteresis of Ni_24.7Ti_49.3Pd_25.0Sc_1.0 (at.%) alloy was measured to be 7 °C, significantly lower than that of 15 °C for Ni_24.5Ti_50.0Pd_25.0Sc_0.5 alloy, reported in literature. Alloy purity, lower volume fraction of second phase and presence of twinless/small twin ratio martensite in microstructure is believed to be the reasons for such low transformation hysteresis. The transformation behaviour of the alloys upon stress-free thermal cycling was found stable, variation in TTs being within 1–2 °C.     

Magnetic and magnetocaloric properties in Cu-doped high Mn content Mn50Ni40−xCuxSn10 Heusler alloys

The effects of Cu substitution on the phase transitions and magnetocaloric effect of Mn₅₀Ni_40−xCu_xSn₁₀ Heusler alloys were investigated. With the increase of Cu content, the martensitic transformation (MT) temperature shifts substantially towards lower temperature, while the Curie temperature of austenite remains almost unchanged. The reverse MT temperature decreases from 180 to 171 K for Mn₅₀Ni₃₉Cu₁Sn₁₀ alloy as the magnetic field increases from 1 to 30 kOe. Under an applied magnetic field of 30 kOe, the maximum values of magnetic field induced entropy changes are 19.6, 28.9, and 14.2 J/kg K for x = 0, 1, and 2, respectively. The effective refrigerant capacities and hysteresis losses for these alloys were discussed in this paper.     

Comparative study of R-phase martensitic transformations in TiNi-based shape memory alloys induced by point defects and precipitates

We studied the influence of point defects (Fe) and precipitates (Ti₃Ni₄) on the characteristics of R-phase martensitic transformation by comparing the transport and thermal properties of as-quenched Ti₅₀Ni₄₆Fe₄ and annealed Ti_48.7Ni_51.3 shape memory alloys. Both alloys undergo a weak first-order R-phase transformation with a small thermal hysteresis (less than 7 K) and non-zero transformation strain, suggesting the introduction of point defects and precipitates lead to a stable R-phase in these alloys due to the defects induced local lattice deformations. Furthermore, our study revealed that the transition temperature, transformation width, and transformation strain of the investigated R-phase TiNi-based alloys are strongly affected by the induced defects. As a result, the annealed Ti_48.7Ni_51.3 has a higher transition temperature than that of Ti₅₀Ni₄₆Fe₄, as expected.     

The influence of Gd/Ce substitution on the magnetic properties,electronic structure and the valence of cerium in the solid solution CexGd1−xNi3

The polycrystalline compounds Ce_xGd_1−xNi₃ with a rhombohedral PuNi₃ (x ≤ 0.2) and hexagonal CeNi₃ (x ≥ 0.8) – type of crystal structures have been obtained. The change of the lattice parameters may suggest an unstable valence of cerium in the studied system. The effect of partial substitution of Gd by Ce is reflected in a change of the cell volume V(x), the Curie temperature T_C(x) and in the temperature dependence of the magnetic susceptibility and electrical resistivity. Thus, T_C(x) decreases from 115 K (x = 0) to ∼6.8 K (x = 0.8). The XPS spectra have been measured at room temperature. The valence band spectra (VB) as well as the core level lines have been analysed as influence of the Gd/Ce substitution on the electronic structure. The VB near the Fermi level (E_F) is dominated by Ni3d states. In the VB region some slight effects of hybridization and changes of intensity of states on E_F have been noticed. The analysis of Ce core level lines reveals the occurrence of possible intermediate valence. The values of the Ce4f - state occupation parameter (n_f) and the hybridization energy (Δ) have been estimated. The gradual filling of the Ni3d band is revealed by a reduction of the 6 eV satellite intensities in the Ni2p core level spectrum. All these effects can modify the magnetic properties of the investigated compounds.     

Thermoelectric properties of Indium doped Cu2GeSe3

Cu₂Ge_1−xIn_xSe₃ (x = 0, 0.05, 0.1, 0.15) compounds were prepared by a solid state synthesis. The powder X-ray diffraction pattern of the undoped sample revealed an orthorhombic phase. The increase in doping content led to the appearance of additional peaks related to cubic and tetragonal phases along with the orthorhombic phase. This may be due to the substitutional disorder created by Indium doping. Scanning Electron Microscopy micrographs showed a continuous large grain growth with low porosity, which confirms the compaction of the samples after hot pressing. Elemental composition was measured by Electron Probe Micro Analyzer and confirmed that all the samples are in the stoichiometric ratio. The electrical resistivity (ρ) systematically decreased with an increase in doping content, but increased with the temperature indicating a heavily doped semiconductor behavior. A positive Seebeck coefficient (S) of all samples in the entire temperature range reveal holes as predominant charge carriers. Positive Hall coefficient data for the compounds Cu₂In_xGe_1−xSe₃ (x = 0, 0.1) at room temperature (RT) confirm the sign of Seebeck coefficient. The trend of ρ as a function of doping content for the samples Cu₂In_xGe_1−xSe₃ with x = 0 and 0.1 agrees with the measured charge carrier density calculated from Hall data. The total thermal conductivity increased with rising doping content, attributed to an increase in carrier thermal conductivity. The thermal conductivity revealed 1/T dependence, which indicates the dominance of Umklapp phonon scattering at elevated temperatures. The maximum thermoelectric figure of merit (ZT) = 0.23 at 723 K was obtained for Cu₂In_0.1Ge_0.9Se₃.     

Order–disorder transition of vacancies from the full- to the half-Heusler structure in Ni2−xMnSb alloys

The thermal transformations and crystal structures in the ordered bcc phases appearing in Ni_2−xMnSb alloys have been investigated. Thermo-analyses on NiMnSb(x = 1) show three λ-shaped peaks suggesting a magnetic and chemical ordering transitions at approximately 450, 865 and 965 °C. With decreasing x, the first and second peak temperatures gradually decrease, while the third one increases. By Z-contrast imaging technique, it was confirmed that the second peak corresponds to the order-disorder transition of vacancies from the L2₁ to the C1_b structure.     

Effects of equal channel angular extrusion and aging treatment on R phase transformation behaviors and Ti3Ni4 precipitates of Ni-rich TiNi alloys

Ni-rich TiNi alloys were subjected to the effect of multiple equal channel angular extrusion (ECAE) treatments by B_C path at 500 °C. The characteristics of R phase transformation in aging treatment were dissimilar in the appearance and the temperature range to those counterparts induced by ECAE treatments. The fine lens-like shape Ti₃Ni₄ particles precipitated mainly in the regions of near grain boundaries and on the tangled grain boundaries after ECAE treatments. The effects and mechanisms of aging treatments and ECAE treatments on R phase transformation behaviors and Ti₃Ni₄ precipitates were investigated and discussed.