Search Results (31)

In this study, we comparatively analyzed the variable-temperature crystal structures for two isomorphous salts, [1-benzyl-4-aminopyridinium][M(mnt)₂] (M = Ni or Cu; mnt²⁻ = maleonitriledithiolate; labeled as APy-Ni or APy-Cu). Both salts crystallize in the triclinic P–1 space group at 296 K, comprising linear [M(mnt)₂]⁻ (M = Ni or Cu) tetramers. A magnetostructural phase transition occurs at T_C~190 K in S = ½ APy-Ni at ambient pressure, with a conversion of paramagnetic tetramers into nonmagnetic spin-paired dimers. The discontinuous alteration of cell parameters at T_C signifies the characteristic of first-order phase transition in APy-Ni. No such transition appears in the nonmagnetic APy-Cu within the same temperature vicinity, demonstrating the magnetic interactions promoting the structural phase transition in APy-Ni, which is further reinforced through a comparison of the lattice formation energy between APy-Ni and APy-Cu. The phase transition may bear a resemblance to the mechanisms typically observed in spin-Peierls systems. We further explored the magnetic and phase transition properties of APy-Ni under varying pressures. Significantly, T_C shows a linear increase with rising pressure within the range of 0.003–0.88 GPa, with a rate of 90 K GPa⁻¹, manifesting that the applied pressure promotes the transition from tetramer to dimer. Full article

In order to improve the magnetocaloric properties of MnNiSi-based alloys, a new type of high-entropy magnetocaloric alloy was constructed. In this work, Mn_0.6Ni_1−xSi_0.62Fe_0.4Co_xGe_0.38 (x = 0.4, 0.45, and 0.5) are found to exhibit magnetostructural first-order phase transitions from high-temperature Ni₂In-type phases to low-temperature TiNiSi-type phases so that the alloys can achieve giant magnetocaloric effects. We investigate why c_hexagonal/a_hexagonal (c_hexa/a_hexa) gradually increases upon Co substitution, while phase transition temperature (T_tr) and isothermal magnetic entropy change (ΔS_M) tend to gradually decrease. In particular, the x = 0.4 alloy with remarkable magnetocaloric properties is obtained by tuning Co/Ni, which shows a giant entropy change of 48.5 J∙kg⁻¹K⁻¹ at 309 K for 5 T and an adiabatic temperature change (ΔT_ad) of 8.6 K at 306.5 K. Moreover, the x = 0.55 HEA shows great hardness and compressive strength with values of 552 HV2 and 267 MPa, respectively, indicating that the mechanical properties undergo an effective enhancement. The large ΔS_M and ΔT_ad may enable the MnNiSi-based HEAs to become a potential commercialized magnetocaloric material. Full article

Chromium nitride is an important transition metal nitride for studying fundamental properties and for advanced technological applications. It is considered a model system for exploring structural, electronic, and magnetic transitions. These transitions occur at 275 ± 10 K and appear to be coupled; however, many discrepant studies on these transitions can be found in the published literature. The underlying reasons for these controversies are suspected to be the CrN nanoparticles preparation methods, strains, impurities, stoichiometry, nanoparticle size, characterization methods, and ambient conditions for characterizing them. This article is focused on the review of the nanoparticle synthesis methods and the use of these nanoparticles for studying structural, electronic, and magnetic transitions. The focus is mainly on the experimental methods, while theoretical simulations are briefly reviewed at the end of the article. Full article

The reaction of Mn(II) salts in the air with different R-salicylaldehyde oximes and the sodium or cesium salts of 9-anthracenecarboxylato (9-AC) allows for the isolation of new six polynuclear compounds: [Mn₃NaO(salox)₃(9-AC)₂(EtOH)₃H₂O]_n·2EtOH (1), [Mn₃NaO(3-Me-salox)₃(9-AC)₂(EtOH)₃H₂O]_n·EtOH (2), [Mn₆O₂(salox)₆(9-AC)₂(EtOH)₂(H₂O)₂]·3EtOH (3), [Mn₃O(3-Me-salox)₃(9-AC)(EtOH)₃(H₂O)]·1.8EtOH·3H₂O (4), [Mn₆O₂(Me-salox)₆(9-AC)₂(EtOH)₄(H₂O)₂]·0.5H₂O (5), and [Mn₆O₂(Et-salox)₆(9-AC)₂(EtOH)₄(H₂O)₂]·3EtOH (6). H₂salox is a salicylaldehyde oxime, H₂(3-Me-salox) is a 3-methyl-salicylaldehyde oxime, H₂Me-salox is a 1-(2-hydroxyphenyl)ethan-1-one oxime and a H₂-Et-salox is 1-(2-hydroxyphenyl)propan-1-one oxime. Structurally, compounds 1 and 2 consist of chains of trinuclear {Mn^III₃(μ₃-O)(salox)₃}⁺ units connected by Na⁺ ions. Compounds 3, 5, and 6 are hexanuclear units formed by two parallel trinuclear units {Mn^III₃(μ₃-O)(salox)₃}⁺ or {Mn^III₃(μ₃-O)(Me-salox)₃}⁺ planes related through an inversion center. Compound 4 consists of two isolated [Mn₃O(3-Me-salox)₃(9-AC)(EtOH)₃(H₂O)] trinuclear molecules in the unit cell showing crystallographic differences. Magnetic studies reveal a set of antiferromagnetic interactions in compounds 1 and 2 and a combination of antiferromagnetic and ferromagnetic interactions in compounds 3, 5, and 6. In all cases, the magneto-structural correlation between the intramolecular Mn^III-N-O-Mn^III torsion angle and the magnetic exchange within these units have been confirmed. For compounds 5 and 6, ac magnetic measurements reveal the slow relaxation of magnetization with moderate energy barriers of 19.9 cm⁻¹ and 31.1 cm⁻¹, respectively. Absorbance and fluorescence measurements in solution show the transitions of the 9-anthracenecarboxylate chromophore for all the compounds. Full article

Direct measurements of the magnetocaloric effect were performed in a Heusler Ni_44.4Mn_36.2Sn_14.9Cu_4.5 alloy at cryogenic temperatures in magnetic fields up to 10 T. The maximum value of the inverse magnetocaloric effect in a 10 T field was ∆T_ad = –2.7 K in the vicinity of the first-order magnetostructural phase transition at T₀ = 117 K. Ab initio and Monte Carlo calculations were performed to discuss the effect of Cu doping into a Ni-Mn-Sn compound on the ground-state structural and magnetic properties. It is shown that with increasing Cu content the martensitic transition temperature decreases and the Curie temperature of austenite slightly increases. In general, the calculated transition temperatures and magnetization values correlated well with the experimental ones. Full article

The metal–radical approach is a well-established synthetic way toward multi-spin systems that relies on the coordination of stable radical ligands with transition metal ions. The advantage offered by the use of paramagnetic ligands is that metal–radical magnetic exchange coupling is direct between the magnetic orbitals of the radical and metal ion. With the aim of further exploring this approach, crystals of four heterspin complexes, [M(hfac)₂L^F]₂ {M = Mn, Co, or Ni and hfac = hexafluoroacetylacetonate} and [Cu(hfac)₂L^F]_n, were obtained using a new fluorinated pyrazolyl-substituted nitronyl nitroxide radical, 4,4,5,5-tetramethyl-2-(5-fluoro-1-methyl-1H-pyrazol-4-yl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (L^F) as a ligand. The newly synthesized complexes were fully characterized, including X-ray crystallography and magnetometry. XRD analysis revealed that complexes [M(hfac)₂L^F]₂ have similar dimer structures in which a metal ion is in a six-coordinated environment with four O atoms from the two hfac ligands, one radical O atom, and one pyrazole N atom from ligand L^F. Nonetheless, the packing patterns of the complexes were found to be considerably different. In [Mn(hfac)₂L^F]₂, there are no magnetically important short contacts between manganese dimers. By contrast, in [Co(hfac)₂L^F]₂ and [Ni(hfac)₂L^F]₂, there are short contacts between non-coordinate O atoms of nitronyl nitroxide moieties. Magnetic behaviors of [M(hfac)₂L^F]₂ showed that the M ions and the directly coordinated radicals are strongly antiferromagnetically coupled (J_Mn-ON = −84.1 ± 1.5 cm⁻¹, J_Co-ON = −134.3 ± 2.6 cm⁻¹, and J_Ni-ON = −276.2 ± 2.1 cm⁻¹; $\widehat{H}=-2J{\widehat{\stackrel{⃑}{S}}}_{\mathrm{M}}{\widehat{\stackrel{⃑}{S}}}_{\mathrm{N}\mathrm{O}}$). Notably, the magnetization of [Mn(hfac)₂L^F]₂ having molecular structure proved to be accompanied by hysteresis. The [Cu(hfac)₂L^F]_n complex has a chain-polymer structure with alternating magnetic fragments: three spin exchange clusters {O_NO–Cu(II)–O_NO} and {Cu(II)} ions. Despite the direct coordination of radicals, its magnetic properties are weakly ferromagnetic (J_Cu-ON = 14.8 ± 0.3 cm⁻¹). Full article

The structural, magnetocaloric, and magnetic characteristics in Heusler Ni₅₀Mn₃₅In₁₀X₅ (X = Ga, Fe, and Al) alloys were examined using X-ray diffraction and field-dependent magnetization measurements. All samples exhibited a mixture structure of cubic L2₁ and tetragonal L1₀ and underwent second-order magnetic transitions at T_C(Al5) = 220 K, T_C(Ga5) = 252 K, and T_C(Fe5) = 298 K. The Ga5 alloy exhibited structural change as indicated by a thermal hysteresis that may be seen in the saturation magnetic field in the M(T) dependences. The transition at the T_C point from a ferromagnetic to a paramagnetic state caused a drop in magnetization, supported by thermal hysteresis, at a low magnetic field (0.01 T). On the other hand, the Fe5 alloy presented a gradual decrease in magnetization with similar hysteresis behavior, also at a low magnetic field (0.01 T), whereas at 0.1 T of field, no features characteristic of this transition were detected. This could be due to a large difference in the metallic radius of Fe compared to that of In. Otherwise, magnetic investigations demonstrated that the replacement of In with Al may cause the structural transformation temperatures and T_C to be shifted to low temperatures. The present results imply that the structural transformation temperatures and the transition itself are highly dependent on chemical composition. Furthermore, under a magnetic field change of 5 T, the maximum magnetic entropy changes of 0.6 J/kg K, 1.4 J/kg K, and 2.71 J/kg K for the Ga5, Fe5, and Al5 alloys, respectively, were determined by their T_C. Refrigeration capacity values were found to be 25 J/kg, 74 J/kg, and 98 J/kg at µ₀∆H = 5 T. These ribbons are viable candidates for multifunctional applications due to their cheaper cost and their physical characteristics disclosed during the magnetostructural transition, which takes place close to the room temperature. Full article

Ni–Mn-based Heusler alloys are known to demonstrate magnetic shape memory and giant magnetocaloric effect (MCE). These effects depend on the phases, crystallographic and magnetic phase transitions, and the crystallographic texture characteristics. These structural characteristics, in turn, are a function of the processing parameters. In the current work, Ni_55.5Mn_18.8Ga₂₄Si_1.7 Heusler alloy was processed by melt-spinning under a helium atmosphere. This process results in a fine microstructure. The ribbon that was produced with a narrower nozzle width, faster wheel speed, and higher cast temperature, indicating a faster cooling rate, had double the magnetic entropy change close to room temperature. However, the other ribbon demonstrated a large entropy change over a broader temperature range, extending its usability. The effect of the melt-spinning process parameters on the developing microstructure, crystallographic structure and texture, transformation temperatures, and the magnetic entropy change were studied to explain the difference in magnetocaloric behavior. Full article

In the present paper, the influence of partial substitution of Mn by Pd on structure, thermomagnetic properties, and phase transitions in the MnCoGe alloys was investigated. The studies of phase constitution revealed an occurrence of the orthorhombic TiNiSi-type and hexagonal Ni₂Ti- type phases. Deep analysis of the XRD pattern supported by the Rietveld analysis allowed us to notice the changes in lattice parameters and quantity of recognized phases depending on the Pd content. An increase of palladium in alloy composition at the expense of manganese induced a rise in the Curie temperature. The values of ΔS_M measured for the variation of external magnetic field ~5 T equaled 8.88, 23.99, 15.63, and 11.09 for Mn_0.97Pd_0.03CoGe, Mn_0.95Pd_0.05CoGe, Mn_0.93Pd_0.07CoGe, and Mn_0.9Pd_0.1CoGe alloy, respectively. The highest magnetic entropy change ΔS_M was observed for samples with Pd content x = 0.05 induced by magnetostructural transformation. The analysis of the n vs. T curves allowed confirmation of the XRD and DSC results of an occurrence of the first-order magnetostructural transition in Mn_0.95Pd_0.05CoGe and Mn_0.93Pd_0.07CoGe alloys samples. Full article

We present detailed first-principles density functional theory-based studies on RbRE₂Fe₄As₄O₂ (RE = Sm, Tb, Dy, Ho) hybrid 12442-type iron-based superconducting compounds with particular emphasis on competing magnetic interactions and their effect on possible magneto-structural coupling and electronic structure. The stripe antiferromagnetic (sAFM) pattern across the xy plane emerges as the most favorable spin configuration for all the four compounds, with close competition among the different magnetic orders along the z-axis. The structural parameters, including arsenic heights, Fe-As-Fe angle, and other relevant factors that influence superconducting T${}_c$ and properties, closely match the experimental values in stripe antiferromagnetic arrangement of Fe spins. Geometry optimization with inclusion of explicit magnetic ordering predicts a spin–lattice coupling for all the four compounds, where a weak magneto–structural transition, a tetragonal-to-orthorhombic structural transition, takes place in the relaxed stripe antiferromagnetic spin configuration. Absence of any experimental evidence of such structural transition is possibly an indication of nematic transition in RE-12442 compounds. As a result of structural distortion, the lattice contracts (expands) along the direction with parallel (anti-parallel) alignment of Fe spins. Introduction of stripe antiferromagnetic order in Fe sub-lattice reconstructs the low-energy band structure, which results in significantly reduced number of bands crossing the Fermi level. Moreover, the dispersion of bands and their orbital characteristics also are severely modified in the stripe antiferromagnetic phase similar to BaFe${}_2$As${}_2$. Calculations of exchange parameters were performed for all the four compounds. Exchange coupling along the anti-parallel alignment of Fe spins J${}_{1a}$ is larger than that for the parallel aligned spins J${}_{1b}$. A crossover between the super-exchange-driven in-plane next-nearest-neighbor exchange coupling J${}_2$ and in-plane exchange coupling J${}_{1a}$ due to lanthanide substitution was found. A large super-exchange-driven next-nearest-neighbor exchange interaction is justified using the construction of 32 maximally localized Wannier functions, where the nearest-neighbor Fe-As hopping amplitudes were found to be larger than the nearest- and the next-nearest-neighbor Fe-Fe hopping amplitudes. We compare the hopping parameters in the stripe antiferromagnetic pattern with non-magnetic configuration, and increased hopping amplitude was found along the anti-parallel spin alignment with more majority-spin electrons in Fe d${}_{xz}$ and d${}_{xy}$ but not in Fe d${}_{yz}$. On the other hand, the hopping amplitudes are increased in stripe antiferromagnetic phase along the parallel spin alignment with more majority-spin electrons in only Fe d${}_{yz}$. This difference in hopping amplitudes in the stripe antiferromagnetic order enables more isotropic hopping. Full article

A simple hybrid thermoelectric-magnetocaloric (TE-MC) system is analytically and numerically simulated using the working parameters of commercial Peltier cells and the properties of a material with a first-order and low-hysteresis magneto-structural phase transition as La(Fe,Mn,Si)${}_{13}$H${}_{1.65}$. The need for a new master equation of the heat diffusion is introduced to deal with these materials. The equation is solved by the Crank–Nicolson finite difference method. The results are compared with those corresponding to a pure TE system and a pure MC system with ideal thermal diodes. The MC material acts as a heat “elevator” to adapt its temperature to the cold or hot source making the TE system very efficient. The efficiency of the realistic hybrid system is improved by at least 30% over the pure Peltier system for the same current supply and is similar to the pure MC with ideal diodes for the same cooling power. Full article

Spin-crossover solids have been studied for many years for their promising applications as optical switches and reversible high-density memories for information storage. This study reports the effect of random metal dilution on the thermal and structural properties of a spin-crossover single crystal. The analysis is performed on a 2D rectangular lattice using an electro-elastic model. The lattice is made of sites that can switch thermally between the low-spin and high-spin states, accompanied by local volume changes. The model is solved by Monte Carlo simulations, running on the spin states and atomic positions of this compressible 2D lattice. A detailed analysis of metal dilution on the magneto-structural properties allows us to address the following issues: (i) at low dilution rates, the transition is of the first order; (ii) increasing the concentration of dopant results in a decrease in cooperativity and leads to gradual transformations above a threshold concentration, while incomplete spin transitions are obtained for big dopant sizes. The effects of the metal dilution on the spatiotemporal aspects of the spin transition along the thermal transition and on the low-temperature relaxation of the photo-induced metastable high-spin states are also studied. Significant changes in the organization of the spin states are observed for the thermal transition, where the single-domain nucleation caused by the long-range elastic interactions is replaced by a multi-droplet nucleation. As to the issue of the relaxation curves: their shape transforms from a sigmoidal shape, characteristic of strong cooperative systems, into stretched exponentials for high dilution rates, which is the signature of a disordered system. Full article

The behavior of magnetostructural transition and the magnetocaloric effect in the MnCoGe_1.02−xGa_x (x = 0, 0.02, 0.04, 0.06) alloys are investigated in this study. The addition of Ga changes the crystal structure of MnCoGe_1.02−xGa_x alloys at room temperature and reduces the phase transition temperatures with increasing Ga content. The coupling of magnetostructural transition and negligible magnetic hysteresis is observed in the Mn-Co-Ge-Ga alloy. At 305 K, under the action of a 5 T magnetic field, the MnCoGeGa_0.02 alloy exhibits 23.47 J/kg∙K magnetic entropy change, and its refrigeration capacity reaches 387 J/kg. The large magnetic entropy change near room temperature and the high refrigeration capacity in the Mn-Co-Ge-Ga alloy make it a promising new type of refrigeration material. Full article

Mn compounds presenting magneto-structural phase transitions are currently intensively studied for their giant magnetocaloric effect; nevertheless, several parameters remain to be further optimized. Here, we explore the Mn(Fe,Ni)(Si,Al) series, which presents two advantages. The Mn content is fixed to unity ensuring a large saturation magnetization, and it is based on non-critical Si and Al elements instead of the more commonly employed Ge. Structural and magnetic properties of MnFe_0.6Ni_0.4Si_1-xAl_x compounds are investigated using powder X-ray diffraction, SEM, EDX, DSC, and magnetic measurements. We demonstrate that a magneto-structural coupling leading to transformation from ferromagnetic with orthorhombic TiNiSi-type structure to a paramagnetic hexagonal Ni₂In-type phase can be realized for 0.06 < x ≤ 0.08. Unfortunately, the first-order transition is relatively broad and incomplete, likely as the result of insufficient sample homogeneity. A comparison between samples synthesized in different conditions (as-cast, quenched from 900 °C, or quenched from 1100 °C) reveals that Mn(Fe,Ni)(Si,Al) samples decompose into a Mn₅Si₃-type phase at intermediate temperatures, preventing the synthesis of high-quality samples by conventional methods such as arc-melting followed by solid-state reaction. By identifying promising MnFe_0.6Ni_0.4Si_1-xAl_x compositions, this study paves the way toward the realization of a giant magnetocaloric effect in these compounds using alternative synthesis techniques. Full article

NiMnSn ferromagnetic shape memory alloys exhibit martensitic transformation at low temperatures, restricting their applications. Therefore, this is a key factor in improving the martensitic transformation temperature, which is effectively carried out by proper element doping. In this research, we investigated the martensitic transformation and magnetic properties of Ni₄₃Mn_46-x Sm_xSn₁₁ (x = 0, 1, 2, 3) alloys on the basis of structural and magnetic measurements. X-ray diffraction showed that the crystal structure transforms from the cubic L2₁ to the orthorhombic martensite and gamma (γ) phases. The reverse martensitic and martensitic transformations were indicated by exothermic and endothermic peaks in differential scanning calorimetry. The martensitic transformation temperature increased considerably with Sm doping and exceeded room temperature for Sm = 3 at. %. The Ni₄₃Mn₄₅SmSn₁₁ alloy exhibited magnetostructural transformation, leading to a large magnetocaloric effect near room temperature. The existence of thermal hysteresis and the metamagnetic behavior of Ni₄₃Mn₄₅SmSn₁₁ confirm the first-order magnetostructural transition. The magnetic entropy change reached 20 J·kg⁻¹·K⁻¹ at 266 K, and the refrigeration capacity reached ~162 J·Kg⁻¹, for Ni₄₃Mn₄₅SmSn₁₁ under a magnetic field variation of 0–5 T. Full article