Ni-Mn-Ga films in the austenite and the martensite structures at room temperature have been obtained using the DC magnetron sputtering technique. Two elaboration processes were studied. A first batch of samples was deposited using a resist sacrificial layer in order to release the film from the substrate before vacuum annealing. This process leads to polycrystalline films with a strong (022) fiber texture. The martensitic phase transformation of such polycrystalline freestanding films has been studied by optical and scanning electron microscopy. A second batch of samples was grown epitaxially on (100)MgO substrates using different deposition temperatures. The texture has been analyzed with four-circle X-ray diffraction. Epitaxial films crystallized both in the austenite and the martensite structures at room temperature have been studied.
Partitioning at phase boundaries of complex steels is important for their properties. We present atom probe tomography results across martensite / austenite interfaces in a precipitation-hardened maraging TRIP steel (12.2 Mn, 1.9 Ni, 0.6 Mo, 1.2 Ti, 0.3 Al; at.%). The system reveals compositional changes at the phase boundaries: Mn and Ni are enriched while Ti, Al, Mo, and Fe are depleted. More specific, we observe up to 27 at.% Mn in a 20 nm layer at the phase boundary. This is explained by the large difference in diffusivity between martensite and austenite. The high diffusivity in martensit…
Tailoring the phase stability and magnetic structure by combining the antiferromagnetic MnNiGe martensite with ferromagnetic MnFeGe austenite, a magnetic-field-induced martensitic transformation has been achieved in MnNi1-xFexGe system. The doped Fe enables the isolated structural and magnetic transitions of MnNiGe to coincide at room temperature and also establishes ferromagnetic couplings in six-Mn-centering-one-Fe-atom clusters. The ferromagnetic clusters transit the antiferromagnetic state in martensite to a ferromagnetic state and the alloys are further induced to a stronger ferromagnetic…
Austenite reversion during tempering of a Fe-13.6Cr-0.44C (wt.%) martensite results in an ultrahigh strength ferritic stainless steel with excellent ductility. The austenite reversion mechanism is coupled to the kinetic freezing of carbon during low-temperature partitioning at the interfaces between martensite and retained austenite and to carbon segregation at martensite-martensite grain boundaries. An advantage of austenite reversion is its scalability, i.e., changing tempering time and temperature tailors the desired strength-ductility profiles (e.g. tempering at 400°C for 1 min. produces a…
A three-dimensional phase-field model is proposed for simulating the magnetic martensitic phase transformation. The model considers a paramagnetic cubic austenite to ferromagnetic tetragonal martensite transition, as it occurs in magnetic Heusler alloys like Ni2 MnGa, and is based on a Landau 2-3-4 polynomial with temperature dependent coefficients. The paramagnetic-ferromagnetic transition is recaptured by interpolating the micromagnetic energy as a function of the order parameter for the ferroelastic domains. The model is numerically implemented in real space by finite element (FE) method. F…
Neutron diffraction measurements, performed in presence of an external magnetic field, have been used to show structural evidence for the kinetic arrest of the first-order phase transition from the high temperature austenite phase to the low temperature martensite phase in the magnetic shape memory alloy Ni37Co11Mn42.5Sn9.5 and the formation of a glass-like arrested state (GLAS). The CHUF (cooling and heating under unequal fields) protocol has been used to establish phase coexistence of metastable and equilibrium states of GLAS in the neutron diffraction patterns. We also explore the field-tem…
Besides permitting an accurate determination of the ferromagnetic-to-paramagnetic phase transition temperature and the characteristic temperatures for the beginning and end of the growth of martensite (austenite) phase at the expense of austenite (martensite) phase while cooling (heating), the results of an extensive ac susceptibility, sound velocity and internal friction investigation of the thermoelastic martensitic transformation in melt-quenched (site-disordered) Ni55Fe20Al25 alloy provide a clear experimental evidence for the following. Irreversible thermoelastic changes (thermal hysteres…
The nucleation of bcc austenite in a single crystal of a mechanically stabilized 2H-martensite of Cu-Al-Ni shape-memory alloy is studied. The nucleation process is induced by localized heating and observed by optical microscopy. It is observed that nucleation occurs after a time delay and that the nucleation points are always located at one of the corners of the sample (a rectangular bar in the austenite), regardless of where the localized heating is applied. Using a simplified nonlinear elasticity model, we propose an explanation for the location of the nucleation points, by showing that the …
We have studied the phase volume fraction related magnetoresistance (MR) across the first order martensite transformation (MT) of Ni44Cu2Mn43In11 alloy. Within the metastability of MT, an isothermal application of magnetic field converts the martensite into austenite. The field induced austenite phase fraction (fIA) at any temperature depends on the availability and instability of martensite phase fraction (fM ) at that temperature. This fIA is found to contribute most significantly to the observed giant MR while the contribution from pure martensite and austenite phase fraction is negligible.…
We consider a recently introduced 2-D square-to-rectangle martensite model that explains several unusual features of martensites to study ferromagnetic martensites. The strain order parameter is coupled to the magnetic order parameter through a 4-state clock model. Studies are carried out for several combinations of the ordering of the Curie temperatures of the austenite and martensite phases and, the martensite transformation temperature. We find that the orientation of the magnetic order which generally points along the short axis of the rectangular variant, changes as one crosses the twin o…
Stabilization of Martensite and Austenite Phases and Realization of Two-way Martensitic Transition in Co-Ni-Ga Ferromagnetic Shape Memory Alloy Nanoparticles
Understanding the mechanism of martensitic transformation is of great importance in developing advanced high strength steels, especially TRansformation-Induced Plasticity (TRIP) steels. The TRIP effect leads to enhanced work-hardening rate, postponed onset of necking and excellent formability. In-situ transmission electron microscopy has been performed to systematically investigate the dynamic interactions between dislocations and alpha martensite at microscale. Local stress concentrations, e.g. from notches or dislocation pile-ups, render free edges and grain boundaries favorable nucleation s…
NiTi is the most used shape-memory alloy, nonetheless, a lack of understanding remains regarding the associated structures and transitions, including their barriers. Using a generalized solid-state nudge elastic band (GSSNEB) method implemented via density-functional theory, we detail the structural transformations in NiTi relevant to shape memory: those between body-centered orthorhombic (BCO) groundstate and a newly identified stable austenite ("glassy" B2-like) structure, including energy barriers (hysteresis) and intermediate structures (observed as a kinetically limited R-phase), and betw…
The martensitic start temperature ($M_{\text{s}}$) is a technologically fundamental characteristic of high-temperature shape memory alloys. We have recently shown [Phys. Rev. B 94, 224104 (2016)] that the two key features in describing the composition dependence of $M_\text{s}$ are the $T=0$ K phase stability and the difference in vibrational entropy which, within the Debye model, is directly linked to the elastic properties. Here, we use density functional theory together with special quasi-random structures to study the elastic properties of disordered martensite and austenite Ti-Ta alloys a…
We carried out magneto-optical Kerr effect (MOKE) and magnetization measurements on a single crystal of Ni2.00Mn1.16Ga0.84 in a longitudinal geometry. While there had been reports of polar geometry measurements so far, we show that - against earlier predictions - surface magnetic states of the martensite and the austenite can be also probed efficiently via longitudinal MOKE. A single variant magnetic state, which occurs at room temperature, is characterized by ferromagnetic hysteresis loops similar to standard ferromagnets. Temperature dependencies of Kerr rotation were found to be linearly pr…
7M orthorhombic modulated structure in the martensite phase of Ni1.8Pt0.2MnGa is reported by powder neutron diffraction study, which indicates that it is likely to exhibit magnetic field induced strain. The change in the unit cell volume is less than 0.5% between the austenite and martensite phases, as expected for a volume conserving martensite transformation. The magnetic structure analysis shows that the magnetic moment in the martensite phase is higher compared to Ni2MnGa, which is in good agreement with magnetization measurement.
The irreversibility of the martensite transition in magnetic shape memory alloys (MSMAs) with respect to external magnetic field is one of the biggest challenges that limits their application as giant caloric materials. This transition is a magneto-structural transition that is accompanied with a steep drop in magnetization (i.e., 'delta M') around the martensite start temperature (Ms) due to the lower magnetization of the martensite phase. In this communication, we show that 'delta M' around Ms in Mn rich Ni-Mn based MSMAs gets suppressed by two orders of magnitude in crushed powders due to t…
An effective scheme of isostructural alloying was applied to establish a Curie-temperature window in isostructural MnNiGe-CoNiGe system. With the simultaneous accomplishment of decreasing structural-transition temperature and converting antiferromagnetic martensite to ferromagnetic state, a 200 K Curie-temperature window was established between Curie temperatures of austenite and martensite phases. In the window, a first-order magnetostructural transition between paramagnetic austenite and ferromagnetic martensite occurs with a sharp jump in magnetization, showing a magnetic entropy change as …
In this paper, we present temperature and field dependent neutron diffraction (ND) study to unravel the structural and the magnetic properties in Ni50Mn38Sb12 Heusler system. This alloy shows martensitic transition from high temperature austenite cubic phase to low temperature martensite orthorhombic phase on cooling. At 3 K, the lattice parameters and magnetic moments are found to be almost insensitive to field. Just below the martensitic transition temperature, the martensite phase fraction is found to be 85%. Upon applying the field, the austenite phase becomes dominant, and the field induc…
A systematic study of magnetic properties of Ni2+xMn1-xGa (0 \le x \le 0.19) Heusler alloys undergoing structural martensite-austenite transformations while in ferromagnetic state has been performed. From measurements of spontaneous magnetization, Ms(T), jumps ΔM at structural phase transitions were determined. Virtual Curie temperatures of the martensite were estimated from the comparison of magnetization in martensitic and austenitic phases. Both saturation magnetic moments in ferromagnetic state and effective magnetic moments in paramagnetic state of Mn and Ni atoms were estimated and the i…
The crystal structure and magnetoresponsive properties of Fe-doped MnCoGe alloys have been investigated using x-ray diffraction (XRD) and magnetic measurements. By alloying the Fe-containing isostructure compounds into MnCoGe, a magnetostructural transition from paramagnetic austenite to ferromagnetic martensite with large magnetization difference can be realized in a temperature window between the Curie temperatures of the austenite and martensite, resulting in magnetic-field-induced martensitic transformations and large magnetic-entropy changes. A structural and magnetic phase diagram of Fe-…
The microstructure of a CoNiAl FSMA was determined by conventional transmission electron microscopy, electron diffraction studies together with advanced microscopy techniques and in-situ Lorentz microscopy. 10 to 60 nm sized rod-like precipitates of hcp $ε$-Co were confirmed to be present by HRTEM. The orientation relationship between the precipitates and B2 matrix is described by the Burgers orientation relationship. The crystal structure of the martensite obtained after cooling is tetragonal L10 with a (1-11) twinning plane. The magnetic domain structure was determined during an in-situ cool…
Materials which can undergo extremely fast displacive transformations as well as very slow diffusive transformations are studied using a Ginzburg-Landau framework to understand the physics behind microstructure formation and time-temperature-transformation (TTT) diagrams. This simple model captures the essential features of alloys such as steels and predicts the formation of mixed microstructures by an interplay between diffusive and displacive mechanisms. The intrinsic volume changes associated with the transformations stabilize mixed microstructures such as martensite-retained austenite (res…
In order to obtain Ni-Mn-Ga epitaxial films crystallized in martensite structures showing Magnetic-Induced Rearrangement (MIR) of martensite variants, a fine control of the composition is required. Here we present how the co-sputtering process might be helpful in the development of Ni-Mn-Ga epitaxial films. A batch of epitaxial Ni-Mn-Ga films deposited by co-sputtering of a Ni-Mn-Ga ternary target and a pure manganese target has been studied. The co-sputtering process allows a precise control of the film compositions and enables keeping the epitaxial growth of Ni-Mn-Ga austenite during deposit…
It is shown that a temperature window between the Curie temperatures of martensite and austenite phases around the room temperature can be obtained by a vacancy-tuning strategy in Mn-poor Mn1-xCoGe alloys (0 <= x <= 0.050). Based on this, a martensitic transformation from paramagnetic austenite to ferromagnetic martensite with a large magnetization difference can be realized in this window. This gives rise to a magnetic-field-induced martensitic transformation and a large magnetocaloric effect in the Mn1-xCoGe system. The decrease of the transformation temperature and of the thermal hysteresis…
Stress induced martensitic transformation in NiTi at elevated temperatures: martensite variant microstructures, recoverable strains and plastic strains
In the present work, the aspects of magnetic and structural properties of Ni-Mn-Ga alloys are described in the framework of fist-principles approach and mapped into ternary composition diagrams. The stable atomic arrangement and magnetic alignment for compositions with cubic austenite and tetragonal martensite structures across phase diagrams are predicted. It is shown that Ni- and Ga-rich compositions possess the regular Heusler structure in contrast to Mn-rich compositions with inverse Heusler structure as favorable one. Compositions with unstable austenite structure are concentrated in the …
Entropy barriers and ageing states appear in martensitic structural-transition models, slowly re-equilibrating after temperature quenches, under Monte Carlo dynamics. Concepts from protein folding and ageing harmonic oscillators turn out to be useful in understanding these nonequilibrium evolutions. We show how the athermal, non-activated delay time for seeded parent-phase austenite to convert to product-phase martensite, arises from an identified entropy barrier in Fourier space. In an ageing state of low Monte Carlo acceptances, the strain structure factor makes constant-energy searches for …
Influence of disorder, antisite defects, martensite transition and compositional variation on the magnetic properties and electronic structure of Mn$_2$NiGa and Mn$_{1+x}$Ni$_{2-x}$Ga magnetic shape memory alloys have been studied by using full potential spin-polarized scalar relativistic Korringa-Kohn-Rostocker (FP-SPRKKR) method. Mn$_2$NiGa is ferrimagnetic and its total spin moment increases when disorder in the occupancy of Mn$_{\rm Ni}$ (Mn atom in Ni position) is considered. The moment further increases when Mn-Ga antisite defect[1] is included in the calculation. A reasonable estimate o…
Anomalous thermal and elastic properties of an epitaxial NiTi film exhibiting R-phase
Czech Technical University in Prague（布拉格捷克理工大学）；Institute of Thermomechanics, Czech Academy of Sciences（捷克科学院热力学研究所）；FZU – Institute of Physics, Czech Academy of Sciences（捷克科学院物理研究所）；Helmholtz-Zentrum Dresden-Rossendorf（德累斯顿-罗斯多夫亥姆霍兹中心）；Universität Duisburg-Essen（杜伊斯堡-埃森大学）；Research Center Future Energy Materials and Systems (RC FEMS), Research Alliance Ruhr（鲁尔研究联盟未来能源材料与系统研究中心）
For the first time, cyclic re-austenitization is carried out for additively manufactured high-strength low-alloy (HSLA) steels in order to refine the microstructure by reducing the prior austenite grain (PAG) size. In this work, HSLA-100 steels processed using laser powder bed fusion (LPBF) technique are subjected to several cycles of re-austenitization using quenching dilatometry. Microstructure characterization for every cycle revealed the presence of bainite, martensite and martensite/austenite (M/A) islands. From the analysis of the dilatometry curves and extensive microstructure character…
We present here results of temperature dependent high resolution synchrotron x-ray powder diffraction study of sequence of phase transitions in Ni2MnGa. Our results show that the incommensurate martensite phase results from the incommensurate premartensite phase, and not from the austenite phase assumed in the adaptive phase model. The premartensite phase transforms to the martensite phase through a first order phase transition with coexistence of the two phases in a broad temperature interval (~40K), discontinuous change in the unit cell volume as also in the modulation wave vector across the…
The magnetic and thermodynamic properties of a Ni2.19Mn0.81Ga alloy with coupled magnetic and structural (martensitic) phase transitions were studied experimentally and theoretically. The magnetocaloric effect was measured by a direct method in magnetic fields 0-26 kOe at temperatures close to the magnetostructural transition temperature. For theoretical description of the alloy properties near the magnetostructural transition a statistical model is suggested, that takes into account the coexistence of martensite and austenite domains in the vicinity of martensite transformation point.
Homogeneous freestanding films have been obtained by the direct current (DC) magnetron sputtering technique using a sacrificial layer. After annealing, the films are crystallized with a strong out-of-plane texture along the (022) direction. The stoichiometry of the annealed films is close to the target composition and leads to a martensitic transformation around 255K. The annealed films demonstrate ferromagnetic behavior with a Curie temperature of about 362K. The magnetization process has been studied on the both states and during the martensitic transition. The saturation magnetizations have…
Using a variational model based on non-linear elasticity we investigate whether in a cubic-to-tetragonal phase transformation it is energetically preferable to nucleate martensite within austenite. Under minimal growth assumptions on the free energy density $W$ away from the wells, we derive explicit upper bounds on $W^{qc}({\mathbb{I}})$, i.e. on the macroscopic free energy density of a region that has been macroscopically deformed by the identity map. The bounds only depend on material parameters, the temperature difference and the growth of $W$ away from the wells. By comparing $W^{qc}({\ma…
The thermodynamic stability of the premartensite (PM) phase has been a topic of extensive investigation in shape memory alloys as it affects the main martensite phase transition and the related physical properties. In general, the PM phase is stable over a rather narrow temperature-composition range. We present here evidence for chemical pressure induced suppression of the main martensite transition and stabilization of the PM phase over a very wide temperature range from 300 K to around 5 K in a magnetic shape memory alloy (MSMA) Ni50Mn34In16 using magnetic susceptibility, synchrotron X-ray p…
The reverse martensitic ("austenitic") transformation upon heating of equiatomic nickel-titanium nanoparticles with diameters between 4 and 17 nm is analyzed by means of molecular-dynamics simulations with a semi-empirical model potential. After constructing an appropriate order parameter to distinguish locally between the monoclinic B19' at low and the cubic B2 structure at high temperatures, the process of the phase transition is visualized. This shows a heterogeneous nucleation of austenite at the surface of the particles, which propagates to the interior by plane sliding, explaining a diff…
Using first-principles calculations based on density functional theory, we have studied the mechanical, electronic, and magnetic properties of Heusler alloys, namely, Ni$_{2}BC$ and Co$_{2}BC$ ($B$ = Sc, Ti, V, Cr and Mn as well as Y, Zr, Nb, Mo and Tc; $C$ = Ga and Sn). On the basis of electronic structure (density of states) and mechanical properties (tetragonal shear constant), as well as magnetic interactions (Heisenberg exchange coupling parameters), we probe the properties of these materials in detail. We calculate the formation energy of these alloys in the (face-centered) cubic austeni…
The lattice dynamics in the polycrystalline shape-memory Heusler alloy Ni$_{50}$Mn$_{35}$In$_{15}$ has been studied by means of resonant ultrasound spectroscopy (RUS). RUS spectra were collected in a frequency range $100-1200$ kHz between 10 and 350 K. Ni$_{50}$Mn$_{35}$In$_{15}$ exhibits a ferromagnetic transition at 313 K in the austenite and a martensitic transition at 248 K accompanied by a change of the magnetic state. Furthermore it displays a antiferromagnetic to ferromagnetic transition within the martensitic phase. We determined the temperature dependence of the shear modulus and the …
Electrical- and magneto-transport across the thermo-elastic martensitic transformation in anti-site-disordered off-stoichiometric Co-Fe-Ti-Si Heusler alloy thin films
The corrosion property of Nickel-titanium (NiTi) shape memory alloy is investigated during forward martensitic transformation between 40C and 0C. The Differential Scanning Calorimetry technique is used to find the forward and reverse martensitic transformation temperatures. NiTi shows the present of martensitic phase at near room temperature by cooling from 80C. The change in corrosion behavior is monitored by electrochemical Open Circuit Potential (OCP) during phase transformation. Cyclic potentiodynamic polarization method is used to identify the corrosion compound of NiTi. Corrosion rate at…
We describe the microstructure, shape and dynamics of growth of a droplet of martensite nucleating in a parent austenite during a solid-solid transformation, using a Landau theory written in terms of conventional affine, elastic deformations and {\em non-affine} degrees of freedom. Non-affineness, $ϕ$, serves as a source of strain incompatibility and screens long-ranged elastic interactions. It is produced wherever the local stress exceeds a threshold and anneals diffusively thereafter. A description in terms of $ϕ$ is inevitable when the separation between defect pairs, possibly generated dur…
The structural, magnetic, and magnetocaloric properties of epitaxial Ni-Co-Mn-Al thin films with different compositions have been studied. The films were deposited on MgO(001) substrates by co-sputtering on heated substrates. All films show a martensitic transformation, where the transformation temperatures are strongly dependent on the composition. The structure of the martensite phase is shown to be 14M. The metamagnetic martensitic transformation occurs from strongly ferromagnetic austenite to weakly magnetic martensite. The structural properties of the films were investigated by atomic for…
Effect of the temperature and magnetic field induced martensitic transformation (MT) on the electronic structure and some physical properties of bulk Fe$_{45.2}$Mn$_{25.9}$Ga$_{28.9}$ Heusler alloy has been investigated. {According to the experimental results of DSC, magnetic and transport measurements direct and reverse martensitic transformation without external magnetic field takes place within 194 $\leq T \leq$ 328 K temperature range with a hysteresis up to $ΔT \approx$ 100 K defined as $ΔT$ = $A_{f,s}$ - $M_{s,f}$, where $A_{f,s}$ and $M_{s,f}$ are the critical temperatures of direct and…
Twin boundaries play an essential role in the use of magnetic shape memory alloy Ni-Mn-Ga as active material. Only if twin boundaries can be moved by an external magnetic field, high strain values of up to 10 % can be obtained. Therefore, understanding the observed twin microstructure of thin films is crucial for future application. We exemplarily present two different microstructural pattern, type X and type Y microstructure, using the example of two Ni-Mn-Ga films with similar film thickness and composition. The analysis of microstructure and structure of the thin films shows that both, type…
