First-order Structural Transition Research Articles

Controlling phase transitions in MnNiGe using thermal quenching and hydrostatic pressure

Abstract The phase transitions in MnNiGe compounds were explored by manipulating the heat treatment conditions and through hydrostatic pressure application. As the quenching temperature increased, both the first-order martensitic structural transition temperatures and magnetic transition temperatures decreased relative to those in the slowly-cooled samples. When the samples were quenched from 1200 ℃, the first-order martensitic structural transition temperature lowered by more than 200 K. The structural transitions also shifted to lower temperature with the application of hydrostatic pressure during measurement. Temperature-dependent X-ray diffraction results reveal
that the changes of the cell parameters resulting from the structural transitions are nearly identical for all samples regardless of the extensive variation in their structural transition temperatures. In addition, neutron scattering measurements confirm the magnetic structure transition between simple and cycloidal spiral magnetic structures.

Strong enhancement of magnetic ordering temperature and structural/valence transitions in EuPd3S4 under high pressure.

We present a comprehensive study of the inhomogeneous mixed-valence compound, EuPd3S4, by electrical transport, X-ray diffraction, time-domain 151Eu synchrotron Mössbauer spectroscopy, and X-ray absorption spectroscopy measurements under high pressure. Electrical transport measurements show that the antiferromagnetic ordering temperature, TN, increases rapidly from 2.8 K at ambient pressure to 23.5 K at ~19 GPa and plateaus between ~19 and ~29 GPa after which no anomaly associated with TN is detected. A pressure-induced first-order structural transition from cubic to tetragonal is observed, with a rather broad coexistence region (~20 GPa to ~30 GPa) that corresponds to the TN plateau. Mössbauer spectroscopy measurements show a clear valence transition from approximately 50:50 Eu2+:Eu3+ to fully Eu3+ at ~28 GPa, consistent with the vanishing of the magnetic order at the same pressure. X-ray absorption data show a transition to a fully trivalent state at a similar pressure. Our results show that pressure first greatly enhances TN, most likely via enhanced hybridization between the Eu 4f states and the conduction band, and then, second, causes a structural phase transition that coincides with the conversion of the europium to a fully trivalent state.

Itinerant ferromagnetism and room temperature giant magnetocaloric effect in (Mn0.6Fe0.4) (Ni0.5Co0.5) Si shape memory alloy

In this article, the feasibility of obtaining a magneto-structural coupling over a wide working temperature range of about 127 K (from 206.5 K to 333.5 K) with negligible thermal hysteresis in combination with the structural, microstructural, magnetic, and magnetocaloric properties of a 50 % Co-doped (at the Ni site) polycrystalline (Mn0.6Fe0.4) (Ni0.5Co0.5) Si (MFNCS-0.5) magnetic shape memory alloy (MSMA) has been thoroughly investigated. Along with leaf-like microstructure, at room temperature, the system shows a mixed phase of TiNiSi type low-temperature high-magnetic (ferromagnetic) orthorhombic martensite and Ni2In type high-temperature low-magnetic (paramagnetic) hexagonal austenite, with the dominance of the second one. To estimate the magnetocaloric effect (MCE) across the phase transition, the isothermal magnetic measurement technique has been employed. The merging of heating and cooling iso-field thermo-magnetization (M-T) curves, the presence of negligible thermal hysteresis in the MH curves, universal magnetic entropy curves, a proposed phenomenological model (across the Curie temperature), and the positive slopes of the Arrott plot (Banerjee criterion) show that the first-order structural and magnetic transition are coupled along with a second-order ferromagnetic to paramagnetic (FM → PM) phase transition (SOPT). By extrapolating the Arrott plot to the H/M = 0 axis the spontaneous magnetization value very close to 0 K, Ms(0), is found to be 71.92 emu/g (∼1.83 µB/f.u.). The linear dependency of MS2T on T2 below SOPT and the RWR (Rhodes–Wolhfarth ratio) = 4.29 > 1 indicate the long-range itinerant ferromagnetism in this alloy. A giant magnetic entropy change (ΔSm) of 25.77 J kg−1 K−1 and a refrigerant capacity (RC) of 472.83 J kg−1 are obtained at 6 T field. This observed magnetic refrigerant's key characteristics, including a giant magnetocaloric effect (MCE) near room temperature (RT), negligible thermal hysteresis loss, a wide operating temperature range of 127 K, and the use of cost-effective, non-toxic constituent elements, make it a suitable and very promising member for applications in solid-state refrigeration technology near RT.

Cu3As: Uncommon Crystallographic Features, Low-Temperature Phase Transitions, Thermodynamic and Physical Properties

The formation and crystal structure of the binary Cu3As phase have been re-investigated. Some physical properties were then measured on both single crystal and polycrystalline bulk. Cu3As melts congruently at 835 °C. At room temperature (RT), this compound has been found to crystallize in the hexagonal Cu3P prototype (hP24, P63cm) with lattice parameters: a = 7.1393(1) Å and c = 7.3113(1) Å, rather than in the anti HoH3-type (hP24, P-3c1) as indicated in literature. A small compositional range of 74.0-75.5 at.% Cu (26.0-24.5 at.% As) was found for samples synthesized at 300 and 400 °C; a corresponding slight understoichiometry is found in one out of the four Cu atomic sites, leading to the final refined composition Cu2.882(1)As. The present results disprove a change in the crystal structure above RT actually reported in the phase diagram (from γ' to γ on heating). Instead, below RT, at T = 243 K (-30 °C), a first-order structural transition to a trigonal low-temperature superstructure, LT-Cu3-xAs (hP72, P-3c1) has been found. The LT polymorph is metrically related to the RT one, having the c lattice parameter three times larger: a = 7.110(2) Å and c = 21.879(4) Å. Both the high- and low-temperature polymorphs are characterized by the presence of a tridimensional (3D) uncommon and rigid Cu sublattice of the lonsdaleite type (Cu atoms tetrahedrally bonded), which remains almost unaffected by the structural change(s), and characteristic layers of triangular 'Cu3As'-units (each hosting one As atom at the center, interconnected each other by sharing the three vertices). The first-order transition is then followed by an additional structural change when lowering the temperature, which induces doubling of also the lattice parameter a. Differential scanning calorimetry nicely detects the first low-temperature structural change occurring at T = 243 K, with an associated enthalpy difference, ΔH(TR), of approximately 2 J/g (0.53 kJ/mol). Low-temperature electrical resistivity shows a typical metallic behavior; clear anomalies are detected in correspondence to the solid-state transformations. The Seebeck coefficient, measured as a function of temperature, highlights a conduction of n-type. The temperature dependence of the magnetic susceptibility displays an overall constant diamagnetic response.

Polyhedral Distortions and Unusual Magnetic Order in Spinel FeMn2O4.

Spinel compounds AB2X4 consist of both tetrahedral (AX4) and octahedral (BX6) environments with the former forming a diamond lattice and the latter a geometrically frustrated pyrochlore lattice. Exploring the fascinating physical properties and their correlations with structural features is critical in understanding these materials. FeMn2O4 has been reported to exhibit one structural transition and two successive magnetic transitions. Here, we report the polyhedral distortions and their correlations to the structural and two magnetic transitions in FeMn2O4 by employing the high-resolution neutron powder diffraction. The cation distribution is found to be (Mn0.92+Fe0.13+)A(Mn3+Fe0.93+Mn0.12+)BO4. While large trigonal distortion is found even in the high-temperature cubic phase, the first-order cubic-tetragonal structural transition associated with the elongation of both tetrahedra and octahedra with shared oxygen atoms along the c axis occurs at TS ≈ 750 K, driven by the Jahn-Teller effect of the orbital active B-site Mn3+ cation. Strong magnetoelastic coupling is unveiled at TN1 ≈ 400 K as manifested by the appearance of Néel-type collinear ferrimagnetic order, an anomaly in both tetrahedral and octahedral distortions, as well as an anomalous decrease of the lattice constants c and a weak anomaly of a. Upon cooling to TN2 ≈ 65 K, it evolves to a noncollinear ferrimagnetic order accompanied by the different moments at the split magnetic sites B1 and B2. Only one-half of the B-site Mn3+/Fe3+ spins, i.e., the B2-site spins in the pyrochlore lattice, are canted, which is a unique magnetic order among spinels. The canting angle between A-site and B2-site moments is ∼25°, but the B1-site moment stays antiparallel to the A-site moment even at 10 K. This noncollinear order is accompanied by a modification of the O-B-O bond angles in the octahedra without significant change in lattice constants or tetrahedral/octahedral distortion parameters, indicating a distinct magnetoelastic coupling. We demonstrate distinct roles of the A-site and B-site magnetic cations in the structural and magnetic properties of FeMn2O4. Our study indicates that FeMn2O4 is a wonderful platform to unveil interesting magnetic order and to investigate their correlations with polyhedral distortions and lattice.

Structural, magnetic and magnetocaloric properties of hexagonal MnCoGe-based thin films

The characteristic size of the magnetocaloric materials in magnetic refrigerators, thermomagnetic regenerators and energy harvesters is usually down to micrometer and nanometer length scales, which provides the largest possible contact surface area to the heat transfer liquid. Therefore, it is pivotal to investigate the structural, magnetic and magnetocaloric properties of magnetocaloric materials at micrometer and nanometer length scales. In the present study, we have successfully fabricated MnCoGe-based thin films using the pulsed laser deposition (PLD) technique. The as-deposited film shows a dense surface, homogeneous chemical distribution and a preferred orientation along the c-axis of the hexagonal Ni2In-type structure. In-situ temperature-dependent X-ray diffraction measurements on the as-deposited films reveal an irreversible structural degradation above 300 °C due to the considerable evaporation of the Mn atoms, which causes the formation of microscale pores in the films. The thermomagnetic behavior of the film annealed at 250 °C displays a reversible second-order ferromagnetic transition of the hexagonal phase at Curie temperature TC = 275 K, and a first-order hexagonal-orthorhombic structural transition below 200 K. The decoupling of the magnetic and structural transitions brings reversible magnetocaloric effect with the entropy change ΔS values of 2.5 J/(kgK) and the refrigeration capacity reaching 89 J/kg in Δμ0H = 5 T, which are comparable to other reported magnetocaloric thin films. Moreover, antiferromagnetic coupling in the low-temperature orthorhombic phase was observed, which has rarely been reported in the MnCoGe-based bulk alloys. The different magnetic ground states between the thin film and the bulk alloys may be originated from the strain effect imposed by the Al2O3 substrate. Consequently, this work not only provides insights into the structural, magnetic and magnetocaloric properties of the MnCoGe-based alloys at a nanometer length scale, but also offers a new idea for tailoring the multifunctional properties for this material family.

The first-order structural transition in NiO at high pressure

Insulator-metal transition in NiO and concomitant collapse of spin and magnetism in the material are important subjects in studies of strong electronic correlations and as such they generate multiple theoretical and experimental efforts aimed at understanding the complicated physics of strongly correlated electronic systems. We report here the iso-structural transition in NiO accompanying the previously observed by us transition to the metallic state. These findings resolve some experimental controversies regarding the transition. We also discuss the latest theoretical results in detail and show that our data confirm some recent theoretical models. Given the simplicity of the material and its fundamental importance to the understanding of strongly correlated electronic systems, our findings should stimulate further experimental and theoretical efforts to understand this prototype Mott insulator.

Large magnetocaloric effect near room-temperature by tuning the magneto-structural transition in (Mn, Fe)(Ni, Fe)Si alloy

The observation of near room-temperature coupling of both magnetic and structural transitions in Fe substituted Mn-Ni-Si alloy leads to an interesting magneto-structural transition (MST) phenomenon which intensifies the required magnetocaloric parameters for magnetic cooling applications. The crystal structure analysis reveals that temperature as well as Fe substitution work as the driving forces for deforming the orthorhombic unit cell and to stabilize the hexagonal phase. The correlation between the unit cell parameters of both phases confirms that a large change in unit cell volume (∼2.9%) is mainly responsible for the structural transition. The simultaneous substitution of Fe across Ni and Mn sites helps to tune the MST temperature. Both magnetization and calorimetric studies confirm the existence of first-order type structural transition across MST. The [Mn0.64 Ni0.64 Fe0.72 Si] alloy exhibits a large isothermal magnetic entropy change (ΔS M ) of −19.2 0.4 J kg−1 K−1 accompanied by a large value of effective refrigerant capacity (RC effe ) of 181.8 3.7 J kg−1 due to a magnetic field change of 0–30 kOe. The estimated total entropy change associated with the complete structural transition from the calorimetric studies sets an upper limit for the entropy change of the system. The low cost and non-toxic nature of constituent elements, composition-dependent tunability of the transition temperature, and near room-temperature large magnetocaloric parameters make this alloy potentially suitable to be used as a refrigerant in solid-state magnetic cooling technology.

Acoustic phonon dispersion of α−RuCl3

Acoustic phonons have recently been posited as playing an integral role in explaining the half-quantized thermal Hall effect in $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{RuCl}}_{3}$. Therefore, we present much needed inelastic x-ray scattering measurements of its acoustic phonon dispersion, along with calculations using the frozen-phonon method. We also discuss a temperature study which conclusively shows a first-order structural transition to a non-$C2/m$ space group at low temperature. Together these results are an important backbone for future theoretical and experimental studies of $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{RuCl}}_{3}$.

Aurivillius Phase Bi4V3O12 with d1 Magnetic Cations, Anisotropic and Negative Thermal Expansion, Multiple Structural Transitions, and Low-Dimensional Magnetism.

Aurivillius phases are an important class of inorganic compounds as they often show ferroelectric properties, and some members of this family are used in nonvolatile ferroelectric memories. The majority of Aurivillius phases have nonmagnetic d0 cations in the perovskite block. Bi4Ti3O12 is the best-known and extensively studied compound within this family. Here, using a high-pressure, high-temperature synthesis method, we could successfully prepare a full magnetic analogue, Bi4V3O12, with d1 cations. Bi4V3O12 is unstable in air above about 520 K. However, in an inert atmosphere, Bi4V3O12 demonstrates two first-order reversible structural transitions near 525 and 760 K. The high-temperature prototypical phase is the same in both Bi4V3O12 and Bi4Ti3O12 with tetragonal (T) I4/mmm symmetry and aT = 3.85608(5) Å and cT = 32.6920(8) Å (at 850 K) for Bi4V3O12, while the low-temperature phases are different. Bi4V3O12 shows anisotropic thermal expansion above 300 K and negative volumetric thermal expansion above about 700 K. Magnetic measurements showed a broad maximum near 70 K on magnetic susceptibility, indicating the presence of low-dimensional magnetism with strong antiferromagnetic interactions between V4+ ions with the Curie-Weiss temperature of about -370 K. But no long-range magnetic ordering was found in Bi4V3O12 down to 2 K.

Orbital ordering and fluctuations in a kagome superconductor CsV3Sb5

Recently, competing electronic instabilities, including superconductivity and density-wave-like order, have been discovered in vanadium-based kagome metals AV3Sb5 (A = K, Rb, Cs) with a nontrivial band topology. This finding stimulates considerable interest to study the interplay of these competing electronic orders and possible exotic excitations in the superconducting state. Here, we performed 51V and 133Cs nuclear magnetic resonance (NMR) measurements on a CsV3Sb5 single crystal to clarify the nature of density-wave-like transition in these kagome superconductors. A first-order structural transition is unambiguously revealed below Ts ∼ 94 K by observing the sudden splitting of Knight shift in 51V NMR spectrum. Moreover, combined with 133Cs NMR spectrum, the present result confirms a three-dimensional structural modulation. By further analyzing the anisotropy of Knight shift and 1/T1T at 51V nuclei, we proposed that the orbital order is the primary electronic order induced by the first-order structural transition, which is supported by further analysis on electric field gradient at 51V nuclei. In addition, the evidence for possible orbital fluctuations is also revealed above Ts. The present work sheds light on a rich orbital physics in kagome superconductors AV3Sb5.

Elastocaloric and Magnetocaloric Effects Linked to the Martensitic Transformation in Bulk Ni55Fe11Mn7Ga27 Alloys Produced by Arc Melting and Spark Plasma Sintering

The investigation of caloric effects linked to first-order structural transitions in Heusler-type alloys has become a subject of considerable current interest due to their potential utilization as refrigerants in solid-state cooling devices. This study is mainly motivated by the possibility of developing refrigeration devices of improved energy efficiency with a reduced environmental impact. We produced partially textured and isotropic bulk samples of the Heusler-type magnetic shape memory alloy Ni55Fe11Mn7Ga27 by arc melting and spark plasma sintering (SPS), respectively. Their structural, microstructural, and phase transition characteristics and magnetocaloric and elastocaloric effects, associated with first-order martensitic transformation (MT), were studied. The elemental chemical compositions of both samples were close to nominal, and a martensitic-like structural transformation appeared around room temperature with similar starting and finishing structural transition temperatures. At room temperature, austenite exhibited a highly ordered L21-type crystal structure. The partial grain orientation and isotropic nature of the arc-melted and SPS samples, respectively, were revealed by X-ray diffraction and SEM observations of the microstructure. For the arc-melted sample, austenite grains preferentially grew in the (100) direction parallel to the thermal gradient during solidification. The favorable effect of the texture on the elastocaloric response was demonstrated. Finally, due to its partial grain orientation, the arc-melted bulk sample showed superior values of maximum magnetic entropy change (|ΔSM|max = 18.6 Jkg−1K−1 at 5 T) and elastocaloric adiabatic temperature change (|ΔTadme|max = 2.4 K at 120 MPa) to those measured for the SPS sample (|ΔSM|max = 8.5 Jkg−1K−1 and (|ΔTadme|max = 0.8 K).

Solid-state phase transition in n-alkanes of different parity

The kinetics of the first-order solid-state structural transition in monodisperse n-alkanes samples of tricosane C23H48 and tetracosane C24H50 was studied by DSC and FTIR spectroscopy. The initial nuclei location of the new phase was revealed. The process of crystal structure rearrangement is initiated in the interlayers between neighboring lamellar for odd tricosane, while the nanonuclei in even tetracosane arise in the crystalline lamella cores. Thus, the influence of the number evenness of carbon atoms in the n-alkanes chains on the first-order structural phase transition has been proved.

The influence of conformational defects on the development of structural phase transition in tetracosane C24H50

The kinetics of the first-order solid-state structural transition in monodisperse n-alkanes samples of even tetracosane C24H50 was studied by FTIR spectroscopy. The existence of many irregular conformers in solid phases of tetracosane, the concentration of which reaches a maximum when approaching the melting temperature, has been demonstrated. The existence of these defective molecules promotes transitions between different rotator phases in the solid state.

The correlation between the covalent bonds and magnetocaloric properties of the Mn2−xFexPyGe1−yMz compounds

In recent years, MnFePGe magnetocaloric materials have been widely studied as promising candidates for magnetic refrigeration materials. The Curie temperature of MnFePGe can be adjusted to around room temperature by changing the element ratio or doping with other elements. Due to its first-order magnetic and structural transition, it engenders a large entropy change but unfortunately also exhibits a large thermal hysteresis during the phase transition, which leads to energy loss and lower refrigeration capability. In this paper, we establish a correlation between the in-plane covalent bonding and Curie temperature (TC), thermal hysteresis (ΔThys), two-phase coexistence zone (ΔTcoex), and entropy change (ΔSDSC) using 54 Mn2−xFexPyGe1−yMz (where M is a metallic or nonmetallic doped element) samples with different components. Neutron diffraction and XRD diffraction data and refinements have been employed to allow a detailed electron density reconstruction of six typical samples with the maximum entropy method. We find that the length of the in-plane bonding is closely correlated with the TC and ΔThys, while the TC, ΔThys, ΔTcoex, and ΔSDSC have no significant correlation with the length of the interlayer covalent bond. Moreover, we find that the ΔThys correlates most strongly with the change in the bond length when undergoing the paramagnetic-to-ferromagnetic phase transition rather than the absolute value of the bond length. These results provide an understanding of how to control the properties, enabling effective ways to tune the composition of magnetic refrigeration materials to tailor magnetocaloric properties for optimal performance.

Determination of the Crystal Structures in the A-Site-Ordered YBaMn2O6 Perovskite

We present a complete structural study of the successive phase transitions observed in the YBaMn2O6 compound with the layered ordering of cations on the perovskite A-site. We have combined synchrotron radiation X-ray powder diffraction and symmetry-adapted mode analysis to describe the distorted structures as pseudosymmetric with respect to the parent tetragonal structure. The YBaMn2O6 compound shows three consecutive phase transitions on cooling from 603 K down to 100 K. It undergoes a first-order structural transition at T1 ≈ 512 K from a C2/m cell with a single Mn site to a P21/c cell with two nonequivalent Mn sites. No checkerboard ordering of the two types of MnO6 octahedra is revealed, and there is no significant charge segregation. A second transition is observed below T2 ≈ 460 K giving rise to a duplication of the c-axis and the occurrence of four nonequivalent Mn sites. These sites are grouped in two pairs, producing, in this case, a checkerboard arrangement in the ab-plane with an average charge segregation of Δq ≈ 0.4 e–. The observed distortions in this phase disagree with the formation of an orbital-ordered phase. Finally, another structural transition is observed coupled to the magnetic transition at TN ≈ 200 K and the c-axis is no longer duplicated. The low-temperature phase is polar with SG P21. It also contains four nonequivalent Mn sites grouped in two pairs. The charge difference between these pairs is increased, achieving a value of Δq ≈ 0.7 e–. In this phase, an asymmetric stretching mode favors a Jahn–Teller-like distortion in the expanded MnO6 octahedra that could be associated with an ordering of eg (3dx2–z2/3dy2–z2) orbitals. Our refinements disclose that this phase is ferroelectric with significant polar displacements of the Mn and Obasal atoms along the b-axis. The simultaneous occurrence of ferroelectricity and magnetic ordering indicates that YBaMn2O6 can be considered as a type II multiferroic compound and can present magnetoelectric coupling.

Hybridization-Gap Formation and Superconductivity in the Pressure-Induced Semimetallic Phase of the Excitonic Insulator Ta2NiSe5

The excitonic insulator Ta$_2$NiSe$_5$ experiences a first-order structural transition under pressure from rippled to flat layer-structure at Ps = 3 GPa, which drives the system from an almost zero-gap semiconductor to a semimetal. The pressure-induced semimetal, with lowering temperature, experiences a transition to another semimetal with a partial-gap of 0.1-0.2 eV, accompanied with a monoclinic distortion analogous to that occurs at the excitonic transition below Ps. We argue that the partial-gap originates primarily from a symmetry-allowed hybridization of Ta-conduction and Ni-valence bands due to the lattice distortion, indicative of the importance of electron-lattice coupling. The transition is suppressed with increasing pressure to Pc = 8 GPa. Superconductivity with a maximum Tsc = 1.2 K emerges around Pc, likely mediated by strongly electron-coupled soft phonons. The electron-lattice coupling is as important ingredient as the excitonic instability in Ta2NiSe5.

Quantum billiards with correlated electrons confined in triangular transition metal dichalcogenide monolayer nanostructures

Forcing systems through fast non-equilibrium phase transitions offers the opportunity to study new states of quantum matter that self-assemble in their wake. Here we study the quantum interference effects of correlated electrons confined in monolayer quantum nanostructures, created by femtosecond laser-induced quench through a first-order polytype structural transition in a layered transition-metal dichalcogenide material. Scanning tunnelling microscopy of the electrons confined within equilateral triangles, whose dimensions are a few crystal unit cells on the side, reveals that the trajectories are strongly modified from free-electron states both by electronic correlations and confinement. Comparison of experiments with theoretical predictions of strongly correlated electron behaviour reveals that the confining geometry destabilizes the Wigner/Mott crystal ground state, resulting in mixed itinerant and correlation-localized states intertwined on a length scale of 1 nm. The work opens the path toward understanding the quantum transport of electrons confined in atomic-scale monolayer structures based on correlated-electron-materials.

The influence of hydrostatic pressure and annealing conditions on the magnetostructural transitions in MnCoGe

In this work, the phase transitions of stoichiometric MnCoGe alloys were studied by systematically varying the annealing conditions and applying hydrostatic pressure. First-order martensitic structural transitions from the Ni2In-type hexagonal austenite phase to the TiNiSi-type orthorhombic martensite phase spanned a wide temperature window (>200 K) as a result of quenching the samples at temperatures ranging from the solid phase at 700 °C to the liquid phase at 1150°C. Despite the large variation in their structural transition temperatures, the changes in cell parameters across the structural transitions and the Curie–Weiss temperatures of the martensite/austenite phase were relatively small. For the sample quenched from 800°C, coupled magnetostructural transitions were observed, and the largest maximum magnetic entropy change was found to be −ΔSmax=33.6 J/kg K for a 7-T field change. The coupled magnetostructural transitions and the corresponding magnetic entropy enhancements were found to also be achievable by applying hydrostatic pressures. Meanwhile, as the quenching temperatures or hydrostatic pressures increased, the first-order martensitic structural transition shifted toward lower temperature until it was ultimately absent, in which case only the crystal structure and magnetic transition of the Ni2In-type hexagonal austenite phase were present.

Elastic Properties and Energy Dissipation Related to the Disorder-Order Ferroelectric Transition in a Multiferroic Metal-Organic Framework [(CH3)2NH2][Fe(HCOO)3] with a Perovskite-Like Structure.

The elastic properties and the coupling of ferroelasticity with ferromagnetism and ferroelectricy are crucial for the development of multiferroic metal-organic frameworks (MOFs) with strong magnetoelectric coupling. Elastic properties and energy dissipation related to the disorder-order ferroelectric transition in [(CH3)2NH2][Fe(HCOO)3] were studied by differential scanning calorimetry (DSC), low temperature X-ray diffraction (XRD) and dynamic mechanical analysis (DMA). DSC result indicated the transition near 164 K. XRD showed the first-order structural transition from rhombohedral Rc to monoclinic Cc at ~145 K, accompanied by the disorder-order transition of proton ordering in the N–H…O hydrogen bonds in [(CH3)2NH2]+ as well as the distortion of the framework. For single crystals, the storage modulus was ~1.1 GPa and the loss modulus was ~0.02 GPa at 298 K. DMA of single crystals showed quick drop of storage modulus and peaks of loss modulus and loss factor near the ferroelectric transition temperature ~164 K. DMA of pellets showed the minimum of the normalized storage modulus and the peaks of loss factor at ~164 K with weak frequency dependences. The normalized loss modulus reached the maximum near 145 K, with higher peak temperature at higher frequency. The elastic anomalies and energy dissipation near the ferroelectric transition temperature are caused by the coupling of the movements of dimethylammonium cations and twin walls.