Substructures of lenticular martensites with different martensite start temperatures in ferrous alloys

This study investigated the substructures of lenticular martensites with different martensite start temperatures (Ms) by transmission electron microscopy. Observation of Fe–33Ni revealed a substructural change from fine transformation twins in the midrib and twinned region to several sets of screw dislocations in the untwinned region during growth. Tangled and curved dislocations also appeared near the martensite–austenite interface of the untwinned region, as the martensite inherited the dislocations in the surrounding austenite. In contrast, curved and tangled dislocations appeared in the entire untwinned region in Fe–31Ni and in the whole martensite plate in Fe–20.5Ni–35Co, as the higher Ms temperatures facilitated the plastic deformation of the surrounding austenite. Thermally transformed thin plate martensite in Fe–31Ni–10Co–3Ti grew into a lenticular shape accompanied by a substructure with dislocations after deformation at temperatures above the Ms temperature. The change in the substructure of lenticular martensite presumably resulted from the local temperature rise in the martensite plate.     

Microstructure in the cubic to monoclinic transition in titanium–nickel shape memory alloys

Microstructure in the cubic to monoclinic transition in the technologically important Ti–Ni shape memory alloys is considered. Using a geometrically nonlinear theory of martensitic transformations, the twinned martensite, austenite–martensite, wedge, triangle, and diamond microstructures are studied. Specifically, compound, type I, and type II twins are possible for any choice of the lattice parameters; while, non-standard twins may exist with special lattice parameters only. In addition, 192 habit planes are found for a particular Ti–Ni alloy, but only 24 have been unambiguously observed in experiments. Further, the twinned wedge is possible in this alloy, but the triangle and diamond are not. These latter three are special microstructures, which provide a mechanism through which a specimen can easily transform and are possible only for alloys with specific lattice parameters. A complete enumeration of the various microstructures is given, and algorithms are presented so that the calculations can be repeated with different lattice parameters.     

Low-energy morphology of the interface layer between austenite and twinned martensite

A micromechanical scheme is developed for predicting the morphology and interfacial energy of the interface layer between the parent phase and internally twinned martensite. Low-energy morphologies are determined by minimizing, with respect to shape parameters, the elastic microstrain energy associated with local incompatibility of transformation strains. The computational scheme involves a finite element solution to a problem of non-linear elasticity with eigenstrains, shape sensitivity analysis with respect to general shape parametrization and minimization employing a gradient-based algorithm. As an application, low-energy morphologies are studied for the austenite–martensite interface in the cubic-to-orthorhombic transformation in a CuAlNi shape memory alloy. Discussion of the results of the analysis includes comparison to alternative simplified methods in terms of the predicted morphologies and the corresponding interfacial energies.     

A novel B19′ martensite in nickel titanium shape memory alloys

A new type of the B19′ (monoclinic) Ni–Ti martensite—one which is internally twinned by the (0 0 1)_m compound twinning mode, has been found in thermally cycled Ni–Ti shape memory alloys. This is an unexpected and remarkable martensite type on account of the fact that the (0 0 1)_m compound twinning mode does not qualify to occur as the fine structure in the B2–B19′ martensite transformation. On the basis of the good concurrence of the observed crystallographic parameters with those predicted by the phenomenological theory of martensite transformations, it has been determined that this martensite is a product of the R phase-B19′ martensite transformation. However, the (0 0 1)_m compound twinning mode can qualify to occur as the lattice invariant shear (LIS) only when the rhombohedral angle of the R phase is less than the critical value of 86.2°. The preference of this twinning mode as the LIS to the [0 1 1]_m Type II twinning mode, which is the normally observed substructure of the Ni–Ti martensites, has been rationalized to be due to the closer proximity of the orientation relationships to the lattice correspondence and the lower magnitudes of twinning shear, shape strain shear, twin interface energy and nucleation strain energy.     

Martensitic transformation and magnetic properties of Ti-doped NiCoMnSn shape memory alloy

Martensitic transformation, microstructure, and magnetic properties of Ti-doped Ni43-xTixCo7Mn43Sn7（at%）（x = 0, 0.5, 1.0, 2.0, and 4.0） shape memory alloys were investigated. The results show that transformation temperatures of Ni43Co7Mn43Sn7 can be efficiently adjusted by the substitution of Ti for Ni. For example, the martensitic transformation starting temperature（Ms） is reduced by about 278 K with 4 at% addition of Ti. Room temperature microstructure evolves from single tetragonal martensite for the Ti-free alloy to dual phases（tetragonal martensite ＋ second phase） with 0.5 at%, 1.0 at%, and2.0 at% addition of Ti to dual phases（cubic austenite ＋ second phase） for 4.0 at% Ti-doped alloy. The mechanical properties can be obviously improved by adding an appropriate amount of Ti. A noteworthy point is that magnetic-field-induced reverse transformation is observed in Ni39Ti4Co7Mn43Sn7 alloy.     

Size dependence of martensite transformation temperature in nanostructured Ni-Mn-Sn ferromagnetic shape memory alloy thin films

In the present study, we report the influence of grain size on structural and phase transformation behaviour of nanostructured Ni-Mn-Sn ferromagnetic shape memory alloy thin films synthesized by dc magnetron sputtering. With increase in substrate temperature, the structural phase changes from austenite with L2₁ cubic crystal structure to martensite with monoclinic structure. In addition, field-induced martensite-austenite transformation is observed in magnetization studies using superconducting quantum interference device magnetometer. The martensitic transformation behaviour of these films depends critically on the microstructure and dimensional constraint. Both, the martensite start temperature (M_s) and austenite finish temperature (A_f) of these nanostructured films decreases with decreasing grain size. The excess free volume associated with grain boundaries has been observed to increase with decrease in grain size which in turn leads to an increase in the number of grain boundaries. It has been proposed that the grain boundaries impose constraints on the growth of the martensite and confine the transformed volume fraction in nanocrystalline structure. A martensite phase nucleated within a grain will be stopped at the grain boundaries acting as obstacles for martensite growth. The investigations revealed that below a critical grain size of 10.8 nm, the austenite phase is observed to be more stable than the martensite phase which leads to the complete suppression of martensitic transformation in these films.     

Fabrication of mechanically alloyed Ti-Ni-Cu powders and damping properties of Al/Ti-Ni-cu sintered materials

The microstructure and phase transformation of mechanically alloyed Ti-(50-x)Ni-xCu powders added to an aluminium matrix to enhance their damping properties were studied. Four compositions between 5 and 20 at.%Cu intermetallic compounds were selected to control the fraction of the martensite phase of Ti-Ni-Cu. Mechanically alloyed Ti-Ni-Cu powders were heat-treated in a vacuum of 10⁶ torr for crystallization. Mechanically alloyed Ti-Ni-Cu powders were milled with Al, swaged at room temperature and rolled at 450°C. After mechanical alloying for 10 hours. The Ti, Ni and Cu elements were completely alloyed and an amorphous phase was formed. The amorphous phase was crystallized to martensite (B19’) and austenite (B2) after heat treatment for 1 hour at a temperature of 850°C, and a Fe₂Ti intermetallic compound was partially formed. As the Cu contents increased the austenite phase fraction increased. The specific damping capacity (SDC) of Al/TiNiCu composite was higher than that of the Al/TiNi composite or native aluminium.     

Deformation-induced martensitic transformation behavior in cold-rolled and cold-drawn type 316 stainless steels

We investigate deformation-induced martensitic transformation behavior in cold-rolled and cold-drawn specimens of type 316 stainless steel. Deformation-induced martensite preferentially nucleates at the twin boundary between the austenite matrix and a deformation twin. In the cold-rolled specimen, martensite formed at the twin boundary has a Kurdjumov–Sachs (K–S) relationship with both the austenite matrix and the deformation twin (“double K–S relationship”). In the cold-drawn specimen, two kinds of deformation twins with different twin planes are typically formed, and therefore deformation-induced martensites are formed where the deformation twin boundaries intersect: martensite thus has an imperfect “triple K–S relationship” with the austenite matrix and the two deformation twins. The complicated crystallographic orientation relationship between austenite and martensite grains strongly restricts the formation of some variants of deformation-induced martensites. Because of the difference in number of nucleation sites in the cold-drawn and cold-rolled specimens, martensitic transformation is more enhanced in the former than in the latter.     

Martensitic phase transformations in Ni–Ti-based shape memory alloys: The Landau theory

We present a simple Landau free energy functional for cubic-to-orthorhombic and cubic-to-monoclinic martensitic phase transformations. The functional is derived following group–subgroup relations between different martensitic phases – tetragonal, trigonal, orthorhombic and monoclinic – in order to fully capture the symmetry properties of the free energy of the austenite and martensite phases. The derived free energy functional is fitted to the elastic and thermodynamic properties of NiTi and NiTiCu shape memory alloys which exhibit cubic-to-monoclinic and cubic-to-orthorhombic martensitic phase transformations, respectively.     

Effect of Si on the reversibility of stress-induced martensite in Fe–Mn–Si shape memory alloys

Fe–Mn–Si is a well-characterized ternary shape memory alloy. Research on this alloy has consistently shown that the addition of 5–6 wt.% Si is desirable to enhance the reversibility of stress-induced martensite vis-à-vis shape memory. This paper examines the effect of Si on the morphology and the crystallography of the martensite in the Fe–Mn–Si system. It is concluded that the addition of Si increases the c/a ratio of the martensite, reduces the transformation volume change and decreases the atomic spacing difference between the parallel close-packed directions in the austenite–martensite interface (habit) plane. It is proposed that, in addition to austenite strengthening, Si enhances reversibility by reducing the volume change and the interfacial atomic mismatch between the martensite and the austenite. Although shape memory is improved, transformation reversibility remains limited by the necessary misfit dislocations that accommodate the atomic spacing differences in the interface.     

Microstructural evolution during multiaxial deformation of pseudoelastic NiTi studied by first-principles-based micromechanical modeling

The deformation behavior of pseudoelastic NiTi shape memory alloys under multiaxial loading conditions is influenced by the evolution of anisotropic martensitic microstructures. We use structural data and elastic constants of B19’ martensite calculated from first principles in a micromechanical model to simulate uni- and biaxial experiments with complex strain paths. The microstructural evolution in terms of volume fractions of different martensite variants and the effect of their elastic anisotropy are investigated in detail. The calculated macroscopic stress–strain data are in good agreement with experimental results reported. The simulations elucidate the relative importance of elastic and inelastic deformation mechanisms (twinning, detwinning and reorientation) for the multiaxial mechanical properties of NiTi. They provide a clear picture of the interplay between phase transformation, evolution of martensitic microstructures and macroscopic mechanical behavior. It is demonstrated that apparently small changes of variant volume fractions in twinned microstructures can significantly affect macroscopic stress states.     

Crystallographic orientation and stress-amplitude dependence of damping in the martensite phase in textured Ti–Nb–Al shape memory alloy

The low-frequency damping (tanδ) of a strongly textured β-titanium shape memory alloy (SMA) was investigated by a dynamic mechanical analysis (DMA) in a tensile mode together with a tensile test and a crystallographic analysis of the transformation. In addition to the high background of tanδ in martensite, a broad tanδ peak with a relaxation-like character was found in the martensite phase similar to the Ti–Ni SMAs. There was a critical stress for the broad peak that corresponds to the stress to complete the martensite variant reorientation, whereas the high background of tanδ had no critical stress. This implies that the broad peak is generated through the long-range motion of twin boundaries. A guideline to estimate the orientation dependence of damping in textured SMAs is also proposed using the interaction energy between the external stress and the transformation.     

Atomic force microscope study of stress-induced martensite formation and its reverse transformation in a thermomechanically treated Fe–Mn–Si–Cr–Ni alloy

Consecutive observations of the stress-induced martensite formation and its reversion by atomic force microscopy have been carried out for the fcc/hcp transformation in the thermomechanically treated sample of an Fe–Mn–Si–Cr–Ni shape memory alloy. It is found that thin martensite plates of 0.1–0.2 μm thickness, which are the same martensite variant on the same habit plane, are formed one after another at the immediate neighbor of the existing martensite plate. These martensite plates make a group of several plates within the width of 1–2 μm. This formation mode of martensite is compared with those martensite plates observed by high resolution microscopy and optical microscopy and it is concluded that the basic mode of the stress-induced transformation is that each martensite plate is induced to relieve the shape strain of the existing martensite plate for all the observed magnifications ranging from several hundreds to several millions. The first martensite plate formation is presumed to occur at the pre-existing stacking fault in austenite. In the reverse transformation on heating, it is likely that each martensite plate is reverse-transformed one after another by reverse movement of the Shockley partial dislocations residing at the tip of the plate. This seems to be true for every range of the observable magnification from namometres to microns. Such a reverse transformation mode ensures a good shape memory effect in Fe–Mn–Si-based shape memory alloys.     

Isothermal and athermal martensitic transformations in Ni–Ti shape memory alloys

Ni–Ti shape memory alloys are known to demonstrate three possible transformation paths between B2 and B19′ phases, B2–R–B19′, B2–B19′ and B2–B19–B19′, depending on their composition and thermo-mechanical treatment. In this work the isothermal kinetics of accumulation of martensite/austenite for all types of martensitic transformations in Ni–Ti and Ni–Ti–X (X = Fe or Cu) has been studied by means of resistance measurements during interruption of cooling/heating scans. Experimental results show that all transformations to the B19′ phase (B2–B19′, R–B19′, B19–B19′) demonstrate a substantial isothermal accumulation of martensite during isothermal dwelling between the martensitic transformation start and finish temperatures. The reverse transformations B19′–R and B19′–B19 are also classified as isothermal. The isothermal accumulation of austenite detected during the reverse B19′–B2 transformation is much less intense, at least partially due to the low sensitivity of resistance to the martensite fraction variation during the reverse transformation, and remains comparable with the resolution of the experimental set-up. The transformations between the B2 and R as well as between the B2 and B19 phases are athermal. Analysis of the entire set of possible transformations in β Ni–Ti systems allows one to conclude that isothermal transformations possess a much broader hysteresis and transformation range compared with athermal ones. Since the hysteresis of the transformation is related to the friction forces acting on interfaces this fact, and also observation of the isothermal effects during reverse martensitic and intermartensitic transformations, strongly support the interpretation of the observed isothermal effects in Ni–Ti as due to the diffusionless but thermally activated motion of interfaces during transformation. The difference between the transformation to B19′ martensite (isothermal) and all others (athermal) is attributed to a distinction in strain accommodation.     

Microstructures and shape memory characteristics of dual-phase Co–Ni–Ga high-temperature shape memory alloys

The influence of microstructure on mechanical properties and shape memory characteristics of Co–Ni–Ga high-temperature shape memory alloys were investigated in this study. X-ray diffraction, scanning electron microscopy and transmission electron microscopy were employed to detect the microstructures. We found that these alloys were composed of dual phases, a non-modulated tetragonal L1₀ martensite and a face-centered cubic (fcc) γ phase. The martensite was twinned and well self-accommodated. The γ phase was a Co-based solid solution with 30% lower hardness than martensite. Although the fracture mode was intergranular, the strength and plasticity of the alloys increased markedly with the increasing volume fraction of the γ phase. The presence of the γ phase in grain boundaries rather than in the martensite is favorable to shape memory recovery. This was revealed by the maximum shape recovery strain over 5.0% that was obtained in the Co₄₆Ni₂₅Ga₂₉ alloy, with the γ phase formed mainly in grain boundaries.     

Microstructure and cavitation behaviour of alloyed austempered ductile irons

In this paper, the study of cavitation behaviour of austempered ductile iron (ADI) alloyed with copper, as well as copper and nickel with a fully ausferritic microstructure, is presented. The ADI materials used were austenitized at 900 °C and austempered at 350 °C having an ausferrite microstructure with 16 and 19% of austenite, respectively. The experimental investigations were conducted using the ultrasonically induced cavitation test method. The results show that the cavitation damage was initiated at graphite nodules, as well as in the interface between a graphite nodule and an ausferrite matrix. The cavitation rate revealed that the ADI material alloyed with Cu + Ni austempered at 350 °C/3 h has a higher cavitation resistance in water than ADI alloyed with Cu. An increased cavitation resistance of the ADI material alloyed with Cu and Ni is due to the matrix hardening by stress assisted phase transformation of austenite into the martensite (SATRAM) phenomenon.     

Composition-Dependent of 6 M Martensite Structure and Magnetism in Cu-Alloyed Ni-Mn-In-Co by First-Principles Calculations

The composition dependence of the crystal structure and magnetism of the 6 M martensite for the Cu-doped Ni_43.75Mn_37.5In_12.5Co_6.25 alloy at different site occupations (Cu substitution for Ni, Mn, In, and Co, respectively) is investigated in detail with the first-principles calculations. Results show that the austenite (A) phase exhibits a ferromagnetic (FM) state in all occupation manners, the 6 M martensite possesses an FM state except for the case of Cu substitution at the normal Mn (Mn1) site, and the non-modulated (NM) martensite displays a ferrimagnetic (FIM) state apart from the Cu substitution at the Ni, Mn1, or In sites. The Cu atom destabilizes the A, 6 M, and NM phases regardless of the occupation manner. The one-step martensitic transformation from the A to NM phase occurs in the case of Cu substituting for Mn1, excess Mn (Mn2), or Co; for Cu substituting Ni, a martensitic transformation including 6 M martensite happens, i.e., A → 6 M → NM; however, the martensitic transformation disappears when Cu replaces In site. From the equilibrium lattice constants, it can be speculated that the substitution of Cu for Ni can effectively reduce the thermal hysteresis (∆T_Hys). The magnetic properties are found to be greatly reduced by the substitution of the non-magnetic element Cu for the ferromagnetic Mn atom, whereas the effect is fewer in the remaining cases. It is predicted that the alloy has more favorable properties when Cu replaces Ni. The present results can lay a theoretical foundation for further development of multielement magnetic shape memory alloys.     

Strain–temperature behavior of NiTiCu shape memory single crystals

Single crystal specimens of NiTi10Cu alloys were subjected to temperature cycling conditions under constant tensile and compressive stresses and the transformation strains were monitored. The [111] orientation exhibited the highest experimental transformation strains (6.64%) in tension while the [001] provides the highest transformation strains in compression (5.34%). These transformation strain levels are significantly higher than previously reported values on NiTiCu alloys. The theoretical treatment includes both the calculation of the CVP (correspondent variant pair) formation strain incorporating the growth of monoclinic phase from the most favorably oriented orthorhombic variant, and the concomitant detwinning of the monoclinic martensite. The experimental transformation strain values are consistently below the theoretical levels due to two main reasons: the slip deformation in the austenite domains as confirmed with TEM studies, and the incomplete transformation resulting in a mixture of orthorhombic and monoclinic phases as determined from diffraction patterns. The experimental transformation strains are higher in tension compared to compression for most single crystal orientations due to two factors: the additional strain associated with the detwinning of the B19′phase in the final microstructure (such as in [111] case), and the partial completion of the second step of the transformation limiting the compression strains.     

Phase volume fractions and strain measurements in an ultrafine-grained NiTi shape-memory alloy during tensile loading

An ultrafine-grained pseudoelastic NiTi shape-memory alloy wire with 50.9 at.% Ni was examined using synchrotron X-ray diffraction during in situ uniaxial tensile loading (up to 1 GPa) and unloading. Both macroscopic stress–strain measurements and volume-averaged lattice strains are reported and discussed. The loading behavior is described in terms of elasto-plastic deformation of austenite, emergence of R phase, stress-induced martensitic transformation, and elasto-plastic deformation, grain reorientation and detwinning of martensite. The unloading behavior is described in terms of stress relaxation and reverse plasticity of martensite, reverse transformation of martensite to austenite due to stress relaxation, and stress relaxation of austenite. Microscopically, lattice strains in various crystallographic directions in the austenitic B2, martensitic R, and martensitic B19′ phases are examined during loading and unloading. It is shown that the phase transformation occurs in a localized manner along the gage length at the plateau stress. Phase volume fractions and lattice strains in various crystallographic reflections in the austenite and martensite phases are examined over two transition regions between austenite and martensite, which have a width on the order of the wire diameter. Anisotropic effects observed in various crystallographic reflections of the austenitic phase are also discussed. The results contribute to a better understanding of the tensile loading behavior, both macroscopically and microscopically, of NiTi shape-memory alloys.     

Segregation engineering enables nanoscale martensite to austenite phase transformation at grain boundaries: A pathway to ductile martensite

In an Fe–9 at.% Mn maraging alloy annealed at 450 °C reversed allotriomorphic austenite nanolayers appear on former Mn decorated lath martensite boundaries. The austenite films are 5–15 nm thick and form soft layers among the hard martensite crystals. We document the nanoscale segregation and associated martensite to austenite transformation mechanism using transmission electron microscopy and atom probe tomography. The phenomena are discussed in terms of the adsorption isotherm (interface segregation) in conjunction with classical heterogeneous nucleation theory (phase transformation) and a phase field model that predicts the kinetics of phase transformation at segregation decorated grain boundaries. The analysis shows that strong interface segregation of austenite stabilizing elements (here Mn) and the release of elastic stresses from the host martensite can generally promote phase transformation at martensite grain boundaries. The phenomenon enables the design of ductile and tough martensite.