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Anisotropic magnetocaloric effect and critical behavior in CrSbSe3

In this work, we report anisotropic magnetocaloric effect and critical behavior in a quasi-one-dimensional ferromagnetic CrSbSe 3 single crystal. The maximum magnetic entropy change - Δ S M max is 2.16 J kg - 1 K - 1 for the easy a axis (2.03 J kg - 1 K - 1 for the hard b axis) and the relative cooling power RCP is 163.1 J kg - 1 for the easy a axis (142.1 J kg - 1 for the hard b axis) near T c with a magnetic field change of 50 kOe. The magnetocrystalline anisotropy constant K u is estimated to be 148.5 kJ m - 3 at 10 K, decreasing to 39.4 kJ m - 3 at 70 K. The rescaled Δ S M ( T , H ) curves along all three axes collapse onto a universal curve, respectively, confirming the second-order ferromagnetic transition. Further critical behavior analysis around T c ~ 70 K gives that the critical exponents β = 0.26 ( 1 ) , γ = 1.32 ( 2 ) , and δ = 6.17 ( 9 ) for H ∥ a , while β = 0.28 ( 2 ) , γ = 1.02 ( 1 ) , and δ = 4.14 ( 16 ) for H ∥ b . The determined critical exponents suggest that the anisotropic magnetic coupling in CrSbSe 3 is strongly dependent on orientations of the applied magnetic field.

2-dimensional systems↗

Spin-Glass-like State and Reversible Room-Temperature Magnetocaloric Effect in Double Distorted Perovskites Nd(Cu 3– x Mn x )Mn 4 O 12

The preparation, complex magnetic properties and room-temperature magnetocaloric effect in Nd(Cu 3–x Mn x )Mn 4 O 12 with cation distribution (Nd 3+ ) A (Cu 3–x 2+x Mn x 3+ ) A' (Mn 1+x 3+ Mn 3–x 4+ ) B O 12 2– (x = 1 and 1.5) have been reported. Both compounds show a sharp paramagnetic-ferromagnetic (FM) transition at T C of 300 and 280 K, respectively. The substitution of Cu by Mn at the A' site induces the emergence of a spin glass state below ≈63 K for x = 1 and ≈72 K for x = 1.5 compound. Another antiferromagnetic-like magnetic transition is also observed in both compounds at 23 and 28 K, respectively, which is discussed as the antiferromagnetic coupling between Nd 3+ at the A' site and (Mn 3+ /Mn 4+ ) at the B site. These two compounds exhibit room-temperature magnetocaloric effect. For a small field of 2 T, the maximum magnetic entropy changes –ΔS M are 1.5 J/kg K at 300 K and 1.4 J/kg K at 280 K, respectively. Furthermore, the –ΔS M (T) curves show an asymmetric distribution, resulting in high refrigerant capacity values for both compounds. We further demonstrate the distinct roles of the A'- and B-site spins on the magnetic properties and the origin of the spin-glass-like state in double distorted perovskites Ln(Cu 3–x Mn x )Mn 4 O 12 family of compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Significant enhancement of magnetocaloric effect in a NiMnCuGa Heusler alloy through textural modification

Magnetocaloric materials are of increasing interest to bring magnetic refrigeration to everyday households and drastically impact the energy demands for temperature control devices. In this work, a polycrystalline Heusler alloy of composition Ni2Mn0.76Cu0.24Ga with coinciding structural and magnetic transformation temperatures was subjected to compressive stress assisted thermal cycling (SATC) to enhance the magnetic properties by inducing a preferred orientation in the martensite. Isofield magnetization measurements showed a sharpening of the transformation between ferromagnetic martensite and paramagnetic austenite due to SATC. In isothermal magnetization measurements, SATC was seen to increase the magnetostructural coupling. With a 2 T applied magnetic field, the magnetocaloric effect (MCE) increased from ∼10 to ∼25 J/kg K and the refrigeration capacity (RC) almost doubled due to SATC. Heat capacity measurements were largely unaffected by SATC. The change in adiabatic temperature was estimated by using Cp and change in magnetic entropy (ΔSM) calculations. SATC was seen to increase ΔTad from ∼1.2 K to 2 K for an applied magnetic field of 2 T. Neutron diffraction measurements revealed highly textured martensite in the as received state that rotated to a more ideal preferred orientation after SATC that enhanced the magnetostructural transformation; and thus, improving the MCE and ΔTad.

McLeod, M. V. (ORCID:0000000329883516)↗

From the Discovery of the Giant Magnetocaloric Effect to the Development of High‐Power‐Density Systems

Caloric cooling and heating promise an efficient and reliable alternative to ubiquitous vapor-compression technology. In 1976, the very first near-room-temperature caloric system is developed, but it took another 20 years for this technology to fully bloom and gain global attention. The discovery of the giant magnetocaloric effect in Gd 5 Si 2 Ge 2 and the advance of the first long-operating magnetic refrigerator, both in 1997, due to the Ames National Laboratory and Astronautics Corporation of America cooperation, are two milestones that sparked ongoing interest in caloric research, which continues to thrive to this day. This review presents a brief history of caloric heat pumping, from the discovery of the magnetocaloric effect to the most recent developments in materials and systems. The contributions of Ames National Laboratory of the U.S. Department of Energy are highlighted, celebrating its 30-year anniversary in caloric research and paying tribute to two outstanding scientists, Vitalij K. Pecharsky and Karl A. Gschneidner, Jr., who inspired the caloric community for decades. The paper concludes with insights into remaining research and development challenges that must be addressed to enable the market transition of caloric technology and its widespread adoption.

caloric materials↗

Hidden first-order phase transitions and large magnetocaloric effects in GdNi 1-x Co x

We report a large magnetocaloric effect tunable between 70 and 115 K in a series of rare earth intermetallic compounds GdNi 1-x Co x with x varying from 0 to 0.15 that manifest rather unconventional second-order phase transitions with concurrent changes in both magnetic and crystallographic sublattices. While the Curie temperature, TC, linearly increases with x(Co), the maximum isothermal entropy change induced by magnetic field varying between 0 and 50 kOe slightly decreases from 14 J/kg K at 71 K when x(Co) = 0 to10 J/kg K at 115 K when x(Co) = 0.15. Additionally, the temperature-averaged entropy change figures of merit calculated at temperature spans of 10 K for all examined compositions are comparable to those of the best known magnetocaloric materials that exhibit second-order phase transitions, including elemental Gd and La(Fe,Co,Si) 13 alloys. Through a detailed analysis of the magnetic field-induced entropy changes along with assessment of critical exponents we explore the role magneto-elastic coupling plays in controlling magnetocaloric properties of GdNi 1-x Co x compounds. We also formulate a model based on the mean field theory approximation to describe both magnetic and magnetocaloric properties of the title materials in qualitative agreement with experimental results.

36 MATERIALS SCIENCE↗

Strong magnetocaloric effect induced by spin reorientation transitions in epitaxial Ho thin films

In this work, magnetocaloric effect (MCE) in an antiferromagnetic holmium (Ho) film is studied near the spin reorientation temperatures. A series of magnetization isotherms from 60 to 150 K around the Néel temperature, $T_N$ ≈ 130 K were recorded for both in-plane and out-of-plane magnetic field orientations. A change in entropy, Δ$S_M$ of –5 J/kgK was found near $T_N$ for an in-plane field orientation. A large change in Δ$S_M$ of –11.8 J/kg K due to a fan-helix spin transition at $\textit{T}$ = 90 K is observed for an in-plane field orientation. Spin transition at both $T_N$ and at the fan-helix transition exhibit larger MCE in the in-plane field orientations in comparison with the perpendicular orientation. The value of the refrigerant capacity extracted from the temperature dependence of Δ$S_M(T)$ is found to be larger for the “in- plane” orientation by a factor of two.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Fathoming the anisotropic magnetoelasticity and magnetocaloric effect in GdNi

Intermetallic GdNi adopts a CrB type of crystal structure (space group Cmcm), and it orders ferromagnetically via a second-order phase transition at 70 K, exhibiting unusually strong spontaneous striction along the three independent crystallographic axes in the ferromagnetically ordered state. Here we introduce a microscopic model to describe anisotropic changes of lattice parameters and elastic contribution to magnetocaloric effect of GdNi. In the model, results of density functional theory (DFT) calculations are used as inputs into a Hamiltonian that includes elastic energy of an anisotropic crystal lattice, exchange interactions, and Zeeman effect. The magnetic and elastic Hamiltonians are coupled through an anisotropic Bean-Rodbell model of magnetoelastic interactions. This coupling gives rise to anisotropic changes in the lattice parameters observed experimentally, and the model reveals good to reasonable agreements between the current theoretical results and earlier experimental data, thus validating the model within the limits of assumptions made. We also show that DFT calculations with 4f electrons of Gd treated as core electrons lead to a more adequate estimate of elastic constants of GdNi in comparison with the LDA + U method where 4f electrons are treated as valence electrons.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Magnetic transitions and magnetocaloric effect of Gd 4 Nd 1 Si 2 Ge 2

In this work, crystal structure and magnetic properties of the quaternary Gd 4 Nd 1 Si 2 Ge 2 compound were investigated using synchrotron X-ray diffraction and magnetic measurements. The compound crystallized into an orthorhombic structure in the temperature range 200-300 K. In zero field cooling, the compound undergoes a spin reorientation following a ferromagnetic-like transition at 276 K. The spin reorientation is hinted at by nonlinear changes of lattice parameters but is suppressed in a high magnetic field of 6 T. Magnetic measurements revealed a magnetocaloric effect with a high relative cooling power. It is suggested that Nd substitution for Gd enlarges magnetic anisotropy and induces a canted spin structure.

36 MATERIALS SCIENCE↗

Site dependence of the magnetocaloric effect in Mn 5–x Fe x Si 3

The nuclear and magnetic structures of Mn 3 Fe 2 Si 3 are investigated in the temperature range from 20 to 300 K. The magnetic properties of Mn 3 Fe 2 Si 3 were measured on a single crystal. The compound undergoes a paramagnetic to antiferromagnetic transition at T N2 ≃ 120 K and an antiferromagnetic to antiferromagnetic transition at T N1 ≃ 69 K. A similar sequence of magnetic phase transitions is found for the parent compound Mn 5 Si 3 upon temperature variation, but the field-driven transition observed in Mn 5 Si 3 is not found in Mn 3 Fe 2 Si 3 , resulting in a strongly reduced magnetocaloric effect. Structurally, the hexagonal symmetry found for both compounds under ambient conditions is preserved in Mn 3 Fe 2 Si 3 through both magnetic transitions, indicating that the crystal structure is only weakly affected by the magnetic phase transition, in contrast to Mn 5 Si 3 where both transitions distort the nuclear structure. Both compounds feature a collinear high-temperature magnetic phase AF2 and transfer into a non-collinear phase AF1 at low temperature. While one of the distinct crystallographic sites remains disordered in the AF2 phase in the parent compound, the magnetic structure in the AF2 phase involves all magnetic atoms in Mn 3 Fe 2 Si 3 . These observations imply that the distinct sites occupied by the magnetic atoms play an important role in the magnetocaloric behaviour of the family.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetocaloric effect in the vicinity of the magnetic phase transition in NdCo 2–x Fe x compounds

In the present paper, the magnetocaloric effect (MCE) of NdCo 2-x Fe x (x = 0, 0.2, 0.4, 0.6) compounds was investigated by magnetization measurements. Here, the temperature-dependent high-resolution synchrotron x-ray diffraction study shows a magnetostructural transition from the paramagnetic cubic phase to the ferromagnetic tetragonal phase below their Curie temperatures. Differential scanning calorimetry analysis shows the absence of thermal hysteresis, indicating the second-order nature of the magnetostructural phase transition in these compounds. The maximum values of magnetic entropy change (ΔS M ) and wide operating temperature (OT) are obtained under a field change of 5 T, which are 7.33 Jkg -1 K -1 , 6.45 Jkg -1 K -1 , 5.71 Jkg -1 K -1 , 4.70 Jkg -1 K -1 and 78 K, 82 K, 85 K, 92 K for x = 0, 0.2, 0.4, and 0.6, respectively. The corresponding values of relative cooling power (RCP) are 529.96 Jkg -1 , 497.25 Jkg -1 , 470.55 Jkg -1 , and 428.31 Jkg -1 . The observed wide OT range and large RCP values are comparable with Gd, Gd 5 Ge 2 Si 2 , and some rare-earth-based giant magnetocaloric materials, making this series of compounds suitable for magnetic refrigeration.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Magnetoelastic transition and magnetocaloric effect in induction melted Fe 100-x Rh x bulk alloys with x = 50, 51

Magnetoelastic transitions (METs) in bulk in nearly equiatomic Fe-Rh alloys produced by arc melting may show poor reproducibility related to insufficient chemical homogeneity and presence of impurity phases in variable concentrations. To better understand the synthesis conditions that reliably yield bulk FeRh materials with reproducible MET characteristics, Fe 100-x Rh x alloys with x = 50, 50.5 and 51 at. % were prepared by induction melting and thermal annealing under identical conditions. The fabricated samples were cut into several slices, followed by characterization of METs in each of the slices using isothermal and isofield magnetization measurements, differential scanning calorimetry, and direct measurements of the magnetocaloric effect. All of the slices exhibit METs between the AFM and FM states, but the transitions are abrupt with nearly the same change of magnetization, ΔM, when x = 50.5 and 51, whereas for the x = 50 alloy the transition spreads over a wide temperature interval and ΔM may fluctuate by as much as 10 % from one specimen to another. A comparison of the magnetocaloric responses of x = 50 and 51 materials is presented. The clearly different effect of the magnetic field on the transition in both directions leads to significant differences in the reversibility and maximum values of the magnetic field-induced entropy and adiabatic temperature changes, as well as average hysteresis losses. In terms of reproducibility, our results suggest that induction melting is a more appropriate technique to prepare these binary alloys.

36 MATERIALS SCIENCE↗

Tablelike magnetocaloric effect and enhanced refrigerant capacity in EuO 1- δ thin films

The effect of electron doping of EuO 1- δ thin films through oxygen vacancies ( δ = 0, 0.025, and 0.09) upon the magnetocaloric response is presented here. The films each showed a paramagnetic to ferromagnetic transition around 65 K, with an additional magnetic ordering transition at higher temperatures in the oxygen deficient samples. All transitions are observed to be of second order. A maximum magnetic entropy change of 6.4 J/kg K over a field change of 2 T with a refrigerant capacity of 223 J/kg was found in the sample with δ = 0, and in all cases the refrigerant capacities of the thin films under study were found to exceed that reported for bulk EuO. Adjusting the oxygen content was shown to produce tablelike magnetocaloric effects, desirable for ideal Ericsson-cycle magnetic refrigeration. These films are thus excellent candidates for small-scale magnetic cooling technology in the liquid nitrogen temperature range.

36 MATERIALS SCIENCE↗

Single-Crystal Growth and Room-Temperature Magnetocaloric Effect of X-Type Hexaferrite Sr 2 Co 2 Fe 28 O 46

X-type hexaferrites have been receiving considerable attention due to their promising applications in many magnetic-electronic fields. However, the growth of single-crystal X-type hexaferrite is still a challenge. Herein we reported, for the first time, the preparation of single crystal X-type hexaferrite Sr 2 Co 2 Fe 28 O 46 (Sr 2 Co 2 X) with high-quality and large size using floating-zone method with laser as the heating source. The crystals show rhombohedral symmetry with space group of R-3m (No. 166, a = 5.8935(1) Å and c = 83.7438(17) Å). Co 2+ and Fe 3+ oxidation states were confirmed by the X-ray absorption near-edge spectroscopy. The prepared Sr 2 Co 2 X exhibits a spin reorientation transition from easy-cone to easy-axis at T 2 of 343 K and a ferrimagnetism–paramagnetism transition at Curie temperature (TC) of ~743 K. The spin reorientation transition was accompanied by magnetocaloric effect (MCE). Both conventional and inverse MCEs were observed near T 2 with a magnetic field applied along the c-axis. The maximum value of the magnetic entropy change along the c-axis was evaluated to be 1.1 J/kg·K for a magnetic field change of 5 T.

36 MATERIALS SCIENCE↗

Magnetic field dependence of the martensitic transition and magnetocaloric effects in Ni 49 BiMn 35 In 15

The structural, magnetic, and magnetocaloric properties of the Bi-doped Heusler alloy Ni 49 BiMn 35 In 15 have been investigated using room temperature X-ray diffraction (XRD) and magnetization measurements in a temperature interval of 5-400 K. The alloy at room temperature was found to be in a mixture of a high temperature austenite phase (AP) and a low temperature martensite phase (MP). A drastic shift in the martensitic transition temperature at the rate of 16 K/T from 197 K to lower temperatures was observed. A kinetic arrest phenomenon of the AP was observed in the magnetization and electrical resistivity measurements during field-cooled (FC) measurements at 5T. A metamagnetic behavior characterized by a jump in magnetization in the isothermal M ( H ) curves near T M was observed. The maximum value of the magnetic entropy change and refrigerant capacity at Curie temperature were found to be 5.5 Jkg -1 K -1 and 312 Jkg -1 for μ o Δ H = 5T, respectively. A large magnetoresistance value of -56% was found near the martensitic transition.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Magnetocaloric effect observations near room temperature in few-layered chromium telluride (Cr 2 Te 3 )

Transition metal telluride compositions are explored extensively for their unique magnetic behavior. Few-layered chromium telluride (Cr 2 T e3 ) exhibits a near-room-temperature phase transition, where the material can be effectively used in applications such as magnetic refrigeration. Compared to existing magnetocaloric materials, Heusler alloys, and rare-earth-based alloys, the large-scale synthesis of mechanically exfoliated Cr 2 Te 3 involves less complexity, resulting in a stable composition. Compared to existing tellurides, Cr 2 Te 3 exhibited a large change in magnetic entropy (|ΔS M |) of 1.88 J k g−1 K −1 at a magnetic field of 4 T. A refrigeration capacity (RC) of ∼82 J kg −1 was determined from the change in magnetic entropy versus temperature curve. The results were comparable with those for existing Cr-based compounds. First-principles density functional theory (DFT) confirmed the magnetic properties of Cr 2 Te 3 , including a near-room-temperature Curie temperature, T C , consistent with experimental results. Here, structural transition was also observed using first-principles DFT, which is responsible for the magnetic behavior.

36 MATERIALS SCIENCE↗

Influence of Ga doping on magnetic properties, magnetocaloric effect, and electronic structure of pseudobinary GdZn 1 - x Ga x ( x = 0 - 0.1 )

Here, we explore the impact of introducing IIIA-group element Ga in place of IIB-group element Zn in binary intermetallic GdZn on its magnetic and magnetocaloric properties, as well as explicate the modified electronic band structure of the compound. The magnetic transition temperature of the compound decreases with the increase of Ga concentration in GdZn 1-x ⁢Ga x ⁢(x = 0–0.1) while the crystal structure (CsCl prototype) and lattice parameters remain unchanged. Our detailed analysis of magnetization and magnetocaloric data conclusively proves that long-ranged magnetic ordering exists in the sample, despite the magnetic interaction considerably weakening with the increase of Ga. The experimental data are rationalized using both a theoretical machine-learning model and first-principle density functional theory. The electronic band structure of GdZn is manifested with some unusual complex features which gradually diminish with Ga doping and the conventional sinusoidal feature of Ruderman-Kittel-Kasuya-Yosida-type interactions also disappears. A mean-field theory model is developed and can successfully describe the overall magnetocaloric behavior of the GdZn 1-x⁢ Ga x series of samples.

36 MATERIALS SCIENCE↗

Enhanced magnetocaloric effects in metastable phases of Mn 1- x Co x NiGe generated through thermal quenching and high-pressure annealing

Metastable phases were formed in Mn 1-x Co x NiGe (x = 0.05 and 0.08) by annealing at 800 °C followed by rapid cooling, i.e., quenching, at ambient pressure (P = 0) and under a pressure of P = 3.5 GPa, and their phase transitions and associated magnetocaloric properties were investigated. The crystal cell volumes of the metastable phases decreased, and their structural transitions significantly shifted to lower temperatures relative to those of the slow-cooled compounds, with a greater reduction observed in the samples where the rapid cooling occurred under high pressures. The magnetic and structural transitions coupled to form a magnetostructural transition in the metastable phases, resulting in large magnetic entropy changes up to -79.6 J kg -1 K -1 (x = 0.08 ) for a 7-T field change. As a result, the experimental results demonstrate thermal quenching and high-pressure annealing as alternative methods to create magnetostructural transitions, without modifying the compositions of the materials.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗