Thermal and structural characterization of Cu–Al–Mn–X (Ti,Ni) shape memory alloys

In this study, the Cu–Al–Mn–X (X = Ni, Ti) shape memory alloys at the range of 10–12 at.% of aluminum and 4–5 at.% manganese were produced by arc melting. We have investigated the effects of the alloying elements on the transformation temperatures, and the structural and the magnetic properties of the quaternary Cu–Al–Mn–X (X = Ni, Ti) shape memory alloys. The evolution of the transformation temperatures was studied by differential scanning calorimetry with different heating and cooling rates. The characteristic transformation temperatures and the thermodynamic parameters were highly sensitive to variations in the aluminum and manganese content, and it was observed that the nickel addition into the Cu–Al–Mn system decreased the transformation temperature although Ti addition caused an increase in the transformation temperatures. The effect of the nickel and the titanium on the thermodynamic parameters such as enthalpy and entropy values was investigated. The structural changes of the samples were studied by X-ray diffraction measurements and by optical microscope observations at room temperature. It is evaluated that the element Ni has been completely soluble in the matrix, and the main phase of the Cu–Al–Mn–Ni sample is martensite, and due to the low solubility of the Ti, the Cu–Al–Mn–Ti sample has precipitates, and a martensite phase at room temperature. The magnetic properties of the Cu–Al–Mn, Cu–Al–Mn–Ni and Cu–Al–Mn–Ti samples were investigated, and the effect of the nickel and the titanium on the magnetic properties was studied.     

Thermal and microstructural investigation of Cu–Al–Mn–Mg shape memory alloys

There are many studies to improve the properties of Cu–Al–Mn shape memory alloys, such as high transformation temperatures, ductility and workability. Most of them have been performed by adding a quaternary component to the alloy. In this study, the effect of trace Mg addition on transformation temperatures and microstructures of three different quaternary Cu–Al–Mn–Mg alloys has been investigated using thermal analysis, optical microscopy and XRD techniques. The transformation temperatures are within the range of 120–180 °C, and they have not changed significantly on decreasing the Mn content, replacing with Mg. The fine precipitates have been observed in the alloys with the Mg content up to 1.64 at%. Calculated entropy change and XRD analysis reveal that the alloys with high Al content have mainly 18R-type structure which could be responsible for good ductility and workability.     

A simple model to predict long-range atomic ordering temperatures in Cu-based shape memory alloys

The order–disorder and order–order phase transition temperatures in the austenitic phase of Cu-based shape memory alloys were used to obtain a set of first- and second-neighbour pair interchange energies. To this end, a mean field model was postulated. Then, the applicability to different alloys of this simple model was analysed. It was found that a good agreement with the experimental phase diagram is obtained for Cu–Zn–Al, Cu–Al–Ni and Cu–Al–Be alloys using composition-independent parameters. It was also found that for Cu–Al–Mn alloys, composition-dependent pair interchange energies need to be employed.     

Microstructural evolution in Al–Mn–Cu–(Be) alloys

This study investigates the effects of alloying elements on the microstructural evolution of Al-rich Al–Mn–Cu–(Be) alloys during solidification, and subsequent heating and annealing. The samples were characterised using scanning electron microscopy, energy dispersive X-ray spectroscopy, synchrotron X-ray diffraction, time-of-flight secondary-ion mass spectroscopy, and differential scanning calorimetry. In the ternary Al₉₄Mn₃Cu₃ (at%) alloy, the phases formed during slower cooling (≈1?K?s^?1) can be predicted by the known Al–Mn–Cu phase diagram. The addition of Be prevented the formation of Al₆Mn, decreased the fraction of τ₁-Al₂₉Mn₆Cu₄, and increased the fraction of Al₄Mn. During faster cooling (≈1000?K?s^?1), Al₄Mn predominantly formed in the ternary alloy, whereas, in the quaternary alloys, the icosahedral quasicrystalline phase dominated. Further heating and annealing of the alloys caused an increase in the volume fractions of τ₁ in all alloys and Be₄Al (Mn,Cu) in quaternary alloys, while fractions of all other intermetallic phases decreased. Solidification with a moderate cooling rate (≈1000?K?s^?1) caused considerable strengthening, which was reduced by annealing for up to 25% in the quaternary alloys, while hardness remained almost the same in the ternary alloy.     

Phase transformation of quasicrystals in aluminium-transition metal alloys

Quasicrystals in Al–Mn, Al–Cu–TM (TM = Fe, Cr, Mn and Ru) and Al–Cu–Fe–Cr alloys can undergo two different modes of phase transformation. Discontinuous transformations of quasicrystals are characterized by the existence of a definite reaction front separating the quasicrystalline phase from the resulting crystalline one; the kinetics are controlled by the migration of the reaction front. Continuous transitions, on the other hand, proceed by structural evolution such as modulation or chemical ordering inside the quasicrystalline phase without creating any high-energy interfaces. Both types of transformations are thermally activated and need atomic diffusion.     

Effect of alloying elements on room temperature tensile ductility in magnesium alloys

The impact of alloying elements on the room temperature tensile behaviour was investigated for a wide range of strain rates using eight types of extruded Mg-0.3 at.% X (X = Ag, Al, Li, Mn, Pb, Sn, Y and Zn) binary alloys with an average grain size of 2–3 μm. The solid solution alloying element affected not only tensile plasticity but also rate-controlling mechanism for these fine-grained magnesium alloys. Most of the alloys exhibited an elongation-to-failure of 20–50% , while the alloys with a high m-value exhibited large tensile plasticity, such as an elongation-to-failure of 140% in a strain rate of 1 × 10^?5 s^?1 for the Mg–Mn alloy. This elongation-to-failure is more than two times larger than that for pure magnesium. This is due to the major contribution of grain boundary sliding (GBS) on the deformation. Microstructural observations reveal that grain boundary segregation, which is likely to affect gain boundary energy, plays a role in the prevention or enhancement of GBS. The present results are clearly expected to open doors to the development of magnesium alloys with good secondary formability at room temperature through the control of alloying elements.     

Strain glass behaviour of Ni–Co–Mn–Sn ferromagnetic shape memory alloys

We report the direct experimental observations of the glassy behaviour in Ni–Co–Mn–Sn ferromagnetic shape memory alloys by doping sufficient substitutional point defect Co into the Ni sites (9 at%). The results showed that high level of Co doping had caused the complete suppression of the martensitic transformation and introduction of a strain glass transition in Ni–Co–Mn–Sn alloys. The strain glass transition was definitively characterized by the dynamic mechanical anomalies following the Vogel–Fulcher relationship and the signature nonergodicity of the frozen glass using a zero‐field‐cooled/field‐cooled heating measurement of static strain. The findings clarified the cause of vanishing of the martensitic transformation in Ni–Co–Mn–Sn alloy with high Co doping levels and the generality of glassy state in Ni–Mn based ferromagnetic shape memory alloys with high level of foreign elements doping. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Analysis of the mobility of migrating austenite–ferrite interfaces

Dilatometric studies assisted by high-temperature laser scanning confocal microscopy provide a comprehensive experimental picture with regard to cyclic austenite-to-ferrite transformations in Fe–C alloys. The validity range for the sharp interface and effective mobility approach is identified by comparing modelling results with calculations based on experiments. The interface velocity for the austenite-to-ferrite transformation in pure iron is exclusively controlled by the intrinsic interface mobility conforming to the upper boundary of mobilities. The austenite-to-ferrite transformation in Fe–C alloys under conventional cooling and heating conditions is primarily controlled by carbon diffusion in austenite. The lower boundary of the temperature-dependent interface mobility has been established for an Fe–C alloy over a wide range of temperatures during cycling transformation. Austenite-to-ferrite transformations in Fe–C–X alloys are characterized by still lower effective mobilities depending on both temperature and composition, because substitutional elements X give rise to a solute drag effect. An estimate for the effective mobility valid for the austenite-to-ferrite transformation in lean Fe–C–Mn alloys is provided.     

The nature of distribution of atoms,and its connection with electron structure in a number of ternary alloys on Ni3Mn basis

The influence of alloying the Ni₃Mn alloy with titanium, vanadium, or copper, on the superstructure of the alloy, was studied by the neutron diffraction method. It was shown that Ti, V, and Al stabilize the superstructure of Ni₃Mn, and Cu actively destroys it. The distribution of atoms of the alloying elements along the sites of fcc lattice and its connection with the electron structure of the alloy was analyzed. The different influence of alloying with a third element on the superstructure in alloys Ni₃Mn and Ni₃Fe is explained.     

63Cu NMR analysis of microstructure evolution in Al–Cu–Mg alloys

⁶³Cu NMR spectroscopy has been used to detect metastable Guinier–Preston–Bagaryatsky (GPB) zones and nanoscale precipitates of equilibrium S-phase (Al₂CuMg) in dilute alloys of aluminium containing copper and magnesium with compositions which lie in the α?+?S phase field. The GPB zones are observed to form rapidly at room temperature with a time development closely related to the Vickers hardness. The final development of S-phase in the alloy has been confirmed by the observation of a line shape in the alloy identical to that observed in a specimen prepared from stoichiometric Al₂CuMg. Analysis of the hyperfine structure of the ⁶³Cu line shape observed for S-phase shows clearly that two Cu sites are present with approximately equal population. This result suggests that possibly two crystallographically distinct Al₂CuMg phases are present. The addition of small amounts of silver to Al–Cu–Mg alloys in the α?+?θ phase field is known to induce the formation of Ω-phase: a slight distortion of tetragonal θ-phase Al₂Cu. A hyperfine-structured ⁶³Cu line shape assigned to Ω-phase, indicating one distinct Cu site, has been observed in two separate Al–1.7?at.%?Cu–0.33?at.%?Mg alloys containing 0.1 and 0.18?at.%?Ag, but not in the same Al–Cu–Mg alloy without Ag.     

High-temperature site preference and atomic short-range ordering characteristics of ternary alloying elements in γ’-Ni3Al intermetallics

Abstract

Remarkable high-temperature mechanical properties of nickel-based superalloys are correlated with the arrangement of ternary alloying elements in L1₂-type-ordered γ′-Ni₃Al intermetallics. In the current study, therefore, high-temperature site occupancy preference and energetic-structural characteristics of atomic short-range ordering (SRO) of ternary alloying X elements (X = Mo, W, Ta, Hf, Re, Ru, Pt or Co) in Ni₇₅Al_21.875X_3.125 alloy systems have been studied by combining the statistico-thermodynamical theory of ordering and electronic theory of alloys in the pseudopotential approximation. Temperature dependence of site occupancy tendencies of alloying X element atoms has been predicted by calculating partial ordering energies and SRO parameters of Ni-Al, Ni-X and Al-X atomic pairs. It is shown that, all ternary alloying element atoms (except Pt) tend to occupy Al, whereas Pt atoms prefer to substitute for Ni sub-lattice sites of Ni₃Al intermetallics. However, in contrast to other X elements, sub-lattice site occupancy characteristics of Re atoms appear to be both temperature- and composition-dependent. Theoretical calculations reveal that site occupancy preference of Re atoms switches from Al to both Ni and Al sites at critical temperatures, T_c, for Re > 2.35 at%. Distribution of Re atoms at both Ni and Al sub-lattice sites above T_c may lead to localised supersaturation of the parent Ni₃Al phase and makes possible the formation of topologically close-packed (TCP) phases. The results of the current theoretical and simulation study are consistent with other theoretical and experimental investigations published in the literature.     

Atomistic modeling of ternary additions to NiTi and quaternary additions to Ni–Ti–Pd,Ni–Ti–Pt and Ni–Ti–Hf shape memory alloys

The behavior of ternary and quaternary additions to NiTi shape memory alloys is investigated using a quantum approximate method for the energetics. Ternary additions X to NiTi and quaternary additions to Ni–Ti–Pd, Ni–Ti–Pt, and Ni–Ti–Hf alloys, for X=Au, Pt, Ir, Os, Re, W, Ta,Ag, Pd, Rh, Ru, Tc, Mo, Nb, Zr, Zn, Cu, Co, Fe, Mn, V, Sc, Si, Al and Mg are considered. Bulk properties such as lattice parameter, energy of formation, and bulk modulus of the B2 alloys are studied for variations due to the presence of one or two simultaneous additives.     

相场法研究Fe-Cu-Mn-Al合金富Cu相析出机制

基于Ginzburg-Landau理论采用连续相场法模拟了Fe-15%Cu-3%Mn-x Al(质量分数x=1%, 3%, 5%)合金在873 K等温时效时纳米富Cu析出相沉淀机制及Al含量对富Cu相析出的阻碍效应.通过计算成分场变量和结构序参数,研究了富Cu析出相的形貌、颗粒密度、平均颗粒半径、生长和粗化动力学.研究结果表明:在时效早期阶段,纳米富Cu相通过失稳分解机制析出,由于原子扩散速率存在差异,从而形成以富Cu相为核心的核壳结构.随着时效时间延长,富Cu相析出物结构由体心立方转变为面心立方.其中Al和Mn原子在富Cu核外偏析形成Al/Mn簇,可以将其视为阻碍富Cu析出相形成的缓冲层;在沉淀过程中,随着Al含量的增大, Al/Mn金属间相促进了缓冲层的生长,阻碍富Cu析出相的生长和粗化.     

New aspects of martensite stabilization in Ni–Mn–Ga high-temperature shape memory alloy

We report on new aspects of martensite stabilization in high-temperature shape memory alloys. We show that, due to the difference in activation energies among various structural defects, an incomplete stabilization of martensite can be realized. In material aged at high temperatures, this gives rise to a variety of unusual features which are found to occur in the martensitic transformation. Specifically, it is shown that both forward and reverse martensitic transformations in a Ni–Mn–Ga high-temperature shape memory alloy can occur in two steps. The observed abnormal behaviour is evidence that, in certain circumstances, thermoelastic martensitic transformation can be induced by diffusion.     

Influence of alloying elements on structure and some physical properties of quenched Sn–Sb alloy

We study the influence of ternary and quaternary alloying elements (Pb, Cd, Cu or Cu–Pb and Cu–Cd) on structural, electrical, hardness and other mechanical properties of Sn–Sb alloys (using an X-ray diffractometer and optical microscope, the double bridge method, Vickers hardness tester and the dynamic resonance method) to produce the best alloy for bearing applications. Adding Cu or Pb to Sn–Sb alloys improves their bearing properties, such as the mechanical properties (elastic modulus, internal friction, hardness and fracture strain) and thermal conductivity. Also, adding Cu, Pb or Cu–Pb to Sn–Sb alloys makes them excellent in their bearing applications and environmental hazards when compared with the Pb ₈₈Sn ₁₀Cu ₂ alloy for automotive applications (FIAT Normalizzazione) and the lead-based Babbitt bearing alloy.     

Mechanism of the shape memory effect in martensitic alloys: an assessment

The (one-way) shape memory effect is a phenomenon that when a martensitic alloy is deformed in a martensitic state it recovers its original shape upon heating to the parent phase. This is a universal effect for certain martensitic alloys. We will assess the mechanism of the effect critically and select the essential factors which govern the effect. We try to understand it from a unified view, invoking the group–subgroup symmetry relation between the parent and martensite phase, along with analysis of reversible twinning modes in martensite. By such an assessment, we will show why typical shape memory alloys, such as Ti–Ni, Cu–Al–Ni etc., exhibit good shape memory characteristics, while others, such as ferrous alloys, do not. Thus, we will show that most of the shape memory characteristics of various martensitic alloys can be understood consistently from such an approach.     

Shape memory alloys — characterization techniques

Shape memory alloys are the generic class of alloys that show both thermal and mechanical memory. The basic physics involved in the shape memory effect is the reversible thermoelastic martensitic transformation. In general, there exists two phases in shape memory alloys, viz., a high-temperature phase or austenitic phase (A) and a low-temperature phase or martensitic phase (M). In addition, an intermediate R phase exists in some special cases. The M↔A transformation is associated with a recoverable strain of about 6.5–8% and the R↔A transformation is associated with a recoverable strain of about 1%. The former transformation has been widely used in the applications like antenna deployment of satellite, aerospace couplings, orthodontic arch wires, medical guide wires for diagnostic and therapeutic catheters and other industrial applications. Our group has been giving emphasis to the characterization techniques for R phase, using differential scanning calorimetry (DSC), electrical resistivity probe (ER) and thermomechanical analyzer (TMA). R phase is found to have attractive features like stability against thermal cycling, a small thermal hysteresis and a negligible strain recovery fatigue. DSC has been used successfully to characterize the recoverable strain parameters, apart from the determination of transformation temperatures. ER is used, for the systematic study of the dependence of various phases on heat-treatment temperatures. TMA has been effectively employed for the study of the mixed phases. A space-rotating platform is designed and fabricated, using an actuator of shape memory spring, for obtaining controlled rotations. The efficiency and the reliability of this actuator has been tested, over a million thermal cycles.     

Effect of solute atoms on grain boundary sliding in magnesium alloys

The effect of solid-solution alloying on grain boundary sliding (GBS) was investigated using pure magnesium and six kinds of Mg–X (X?=?Ag, Al, Li, Pb, Y and Zn) dilute binary solid solutions with an average grain size of 10?µm. A sharp increase in damping capacity caused by GBS was observed above a certain temperature. The temperature at which a sharp increase in damping capacity occurred depended on the alloying element. The addition of Y and Ag markedly increased the onset temperature (more than 100?K) for a sharp increase in damping capacity, whereas the addition of Zn, Al and Li slightly increased the onset temperature (less than 50?K) as compared with that for pure magnesium. Tensile tests at a temperature of 423?K revealed that the higher the onset temperature, the lower the strain rate sensitivity of the flow stress. It is suggested that the former elements (Y and Ag) are more effective in suppressing GBS in magnesium alloys than the latter ones (Zn, Al and Li). The suppression of GBS was associated with low grain boundary energy, and the extent to which the energy is reduced depended on the alloying element. It was suggested that the change in the lattice parameter (the so-called c/a ratio) affects the grain boundary energy, and thus, the occurrence of GBS.     

Investigation of shape memory characteristics and production of HfZrTiFeMnSi high entropy alloy by mechanical alloying method

High entropy alloy (HEA) with shape memory effect (SME) has been the subject of great interest for the past few decades. However, with the increased demands for new materials for high thermal applications, the research activities on the multi elemental high entropy shape memory alloys (HESMA) have been increased by many folds recently. The nano crystalline HEA powder with shape memory effect developed in this study, HfZrTiFeMnSi, was produced by mechanical alloying (MA) for the first time. In this method equiatomic ratio of Hf, Zr, Ti, Fe, Mn, and Si were mixed together and milled by MA process for 100 h. The powder formed was of amorphous in nature. Elemental mapping of the powder from SEM-EDS revealed homogeneity of the alloying elements confirming successful fabrication of HfZrTiFeMnSi HEA powder. The DSC studies from ambient to 500 °C of the annealed alloy powders showed reversible austenitic to martensitic (A↔M) transformations. The A↔M transformation hysteresis seemed to vary with the milling time and annealing temperature. The enthalpy values, ΔH, for the transformation were calculated from the DSC plots using tangent method for peak area calculation. Regardless of the annealing temperature, the thermal analysis revealed that the ΔH, equilibrium temperature (T₀), and crystallization temperature values decreased with the increasing milling time.