Large Entropy Change Research Articles

Magnetostructural transformation and magnetocaloric response in Mn(Fe)NiSi(Al) alloys

An efficient magnetocaloric refrigerant must have certain characteristics such as a sharp transition near the desired working temperature, a large cyclic magnetocaloric response, and the use of raw materials with reduced costs and low environmental consequences. In this sense, this work focuses on a series of rare-earth- and Co-free Mn0.5Fe0.5NiSi1-xAlx alloys (x = 0.0525, 0.060, 0.0685) with promising magnetocaloric properties. The alloys were synthesized using combined arc melting and induction melting techniques, as this synthesis route provides improved control on the sample composition and homogeneity. We investigated how the heat treatment temperature and Al content affect the magnetostructural and magnetocaloric properties of the alloys. On the one hand, it is found that annealing at 1173 K for 7 days leads to a sharp magnetostructural transformation with no traces of impurities for the alloy with x = 0.0525. Under these conditions, a large isothermal entropy change of –11.5 J kg−1 K−1 for 1 T is obtained near room temperature, significantly improving the value of the as-cast sample. On the other hand, following this optimal heat treatment, the influence of Al content is studied: upon increasing the Al concentration the magnetostructural transformation shifts to lower temperatures, ranging from 320 K for x = 0.0525 to 220 K for x = 0.0685 (measured upon heating).

Temperature-dependent lattice dynamics study on phase stability, martensitic transformation mechanism, and vibrational entropy properties of B2-type Ni–Mn–Ti Heusler alloy

The all-d-metal Ni–Mn–Ti Heusler alloy with its good mechanical properties and colossal caloric effects has attracted significant attention for mechanocaloric refrigeration. However, the phase stability of the B2-type disordered structure at finite temperatures and the physical origin of large phase transformation entropy change in theoretical calculation remain unclear. In view of thermal and strongly anharmonic effects, we combined the first-principles and temperature dependent effective potential calculations to systematically study the phase stability, martensitic transformation mechanism, and vibrational entropy properties of B2 partial disordered structures for Ni8Mn5Ti3 and Ni8Mn6Ti2. Our results showed the austenitic structures of Ni8Mn5Ti3 and Ni8Mn6Ti2 both exhibit antiferromagnetic interaction behaviors at targeted temperatures, resolving the contradiction between previous calculations and experiments. By the analysis of phonon dispersion relations and Helmholtz free energies at low and high temperatures, we provided a deeper explanation for the underlying mechanism of martensitic transformation. Meanwhile, the phase transformation temperatures and vibrational entropy changes were accurately predicted compared with the experiment results. Specifically, we demonstrated that the large vibrational entropy change of Ni–Mn–Ti material originates from the contributions of both the tetragonal distortion ratio and volume change, which provides important theoretical guidance and has great practical significance for designing the solid-state material with large vibrational entropy change in the application of solid-state refrigeration.

Colossal Barocaloric Effect near Ambient Temperature in 1-Dodecanol under a Low Pressure.

Solid-state refrigeration based on the barocaloric effect is an effective alternative to traditional vapor compression refrigeration. Here 1-dodecanol has been studied due to its large latent heat at a solid-liquid phase transition point around room temperature. The transition temperature will vary with the applied hydrostatic pressure, exhibiting with a sensitivity of 0.14 K MPa-1, which indicates its potential for refrigeration. A pressure of 40 MPa can result in a large isothermal entropy change of 520 J kg-1 K-1 (equivalent to that obtained in vapor compression refrigeration) at 297 K. A large adiabatic temperature change of >20 K in 1-dodecanol was acquired by direct measurement. A wide temperature window of ∼50 K (288-337 K) can be obtained in 1-dodecanol, which demonstrates broad application prospects. These discoveries offer promising prospects for barocaloric cooling and high-efficiency refrigeration technologies relying on solid-liquid phase transitions.

Structural Order in the Hydration Shell of Nonpolar Groups versus that in Bulk Water.

The poor solubility of nonpolar compounds in water around room temperature is governed by a large and negative entropy change, whose molecular cause is still debated. Since the Frank and Evans original proposal in 1945, the large and negative entropy change is usually attributed to the formation of ordered structures in the hydration shell of nonpolar groups. However, the existence of such ordered structures has never been proven. The present study is aimed at providing available structural results and thermodynamic arguments disproving the existence of ordered structures in the hydration shell of nonpolar groups.

Landau theory of barocaloric plastic crystals

We present a minimal Landau theory of plastic-to-crystal phase transitions in which the key components are a multipole-moment order parameter that describes the orientational ordering of the constituent molecules, coupling between such order parameter and elastic strains, and thermal expansion. We illustrate the theory with the simplest non-trivial model in which the orientational ordering is described by a quadrupole moment, and use such model to calculate barocaloric effects in plastic crystals that are driven by hydrostatic pressure. The model captures characteristic features of plastic-to-crystal phase transitions, namely large changes in volume and entropy at the transition, as well as the linear dependence of the transition temperature with pressure. We identify temperature regions in the barocaloric response associated with the individual plastic and crystal phases, and those involving the phase transition. Our model is in overall agreement with previous experiments in powdered samples of fullerite C60, and predicts peak isothermal entropy changes of ∼90JK−1kg−1 and peak adiabatic temperature changes of ∼35K under 0.60 GPa at 265 K in fullerite single crystals.

Colossal Reversible Barocaloric Effects in a Plastic Crystal Mediated by Lattice Vibrations and Ion Diffusion.

Solid-state methods for cooling and heating promise a sustainable alternative to current compression cycles of greenhouse gases and inefficient fuel-burning heaters. Barocaloric effects (BCE) driven by hydrostatic pressure (p) are especially encouraging in terms of large adiabatic temperature changes (|ΔT| ≈ 10K) and isothermal entropy changes (|ΔS| ≈ 100JK-1kg-1). However, BCE typically require large pressure shifts due to irreversibility issues, and sizeable |ΔT| and |ΔS| seldom are realized in a same material. Here, the existence of colossal and reversible BCE in LiCB11H12 is demonstrated near its order-disorder phase transition at ≈380K. Specifically, for Δp ≈ 0.23(0.10)GPa, |ΔSrev| = 280(200)JK-1kg-1 and |ΔTrev| = 32(10)K are measured, which individually rival with state-of-the-art BCE figures. Furthermore, pressure shifts of the order of 0.1GPa yield huge reversible barocaloric strengths of ≈2JK-1kg-1MPa-1. Molecular dynamics simulations are performed to quantify the role of lattice vibrations, molecular reorientations, and ion diffusion on the disclosed BCE. Interestingly, lattice vibrations are found to contribute the most to |ΔS| while the diffusion of lithium ions, despite adding up only slightly to the entropy change, is crucial in enabling the molecular order-disorder phase transition.

Reversible Colossal Barocaloric Effect of a New FeII Molecular Complex with Low Hysteretic Spin Crossover Behavior

AbstractBarocaloric cooling, that is, lowering the temperature of a material under pressure action, is an attractive solid‐state effect that can potentially compete with volatile gas‐based cooling. To observe the barocaloric effect (BCE), it is necessary for materials to have high‐entropy, low‐hysteretic phase transitions with a large volume change between phases. Here details on a new FeII complex [Fe(L)(NCS)2], L = N1,N3‐bis((1‐propyl‐1H‐1,2,3‐triazol‐4‐yl)methylene)‐2,2‐dimethylpropane‐1,3‐diamine) possessing spin crossover (SCO) behavior near room temperature with large entropy and volume change are reported, which provides high sensitivity to external pressure. The observed BCE effect, characterized using variable pressure calorimetry, powder X‐ray diffraction, UV–vis, IR, and Raman spectroscopy, shows a colossal isothermal entropy change of >100 J kg−1 K−1 and a reversible adiabatic temperature change of ≈16 K at a pressure of 1 kbar, demonstrating a high refrigerant efficiency compared to other solid‐state materials. These results stimulate further investigations of SCO materials as barocaloric refrigerants, which depend on the proper design of their constituent organic ligands.

Colossal barocaloric effect of plastic crystals imbedded in silicon frame near room temperature: Molecular dynamics simulation

Solid-state refrigeration technology has been attracting tremendous attention in recent decades. Plastic crystal pentaerythritol (PE) is a crucial barocaloric material in the solid-state refrigeration field due to its high entropy. However, its refrigeration temperature range and extremely low thermal conductivity are far from meeting the requirements of practical application. Here, we systematically investigate the barocaloric effect (BCE) of composite PE and silicon frame [consisting of silicon nanotube and silicene architectures (SNT-Sil)] and analyze the effects of different silicon models on the BCE performance based on molecular dynamics simulations and statistical analysis. A colossal BCE of PE/silicon frame composite is observed, and refrigeration temperature can be altered to the room temperature range by alloying neopentane (PA) into the PE matrix. It is found that the composite PE0.8PA0.2/SNT-Sil and PE0.9PA0.1/SNT-Sil demonstrate excellent comprehensive refrigeration performance near room temperature (300–320 K), with large isothermal entropy change ΔS (654–842 J kg−1 K−1), adiabatic temperature ΔT (34–47 K), and thermal conductivity κ (4.0–4.2 W m−1 K−1). The microscopic mechanism is discussed through pressure induced changes in bonding, structural, and vibrational properties. Importantly, the plastic crystal/silicon framework is easy to deform and requires smaller input work in the barocaloric refrigeration process compared to other nanomaterials such as carbon framework. This work provides important guidance on improving plastic crystals with colossal comprehensive refrigeration performance for practical applications.

Low pressure reversibly driving colossal barocaloric effect in two-dimensional vdW alkylammonium halides

Plastic crystals as barocaloric materials exhibit the large entropy change rivalling freon, however, the limited pressure-sensitivity and large hysteresis of phase transition hinder the colossal barocaloric effect accomplished reversibly at low pressure. Here we report reversible colossal barocaloric effect at low pressure in two-dimensional van-der-Waals alkylammonium halides. Via introducing long carbon chains in ammonium halide plastic crystals, two-dimensional structure forms in (CH3–(CH2)n-1)2NH2X (X: halogen element) with weak interlayer van-der-Waals force, which dictates interlayer expansion as large as 13% and consequently volume change as much as 12% during phase transition. Such anisotropic expansion provides sufficient space for carbon chains to undergo dramatic conformation disordering, which induces colossal entropy change with large pressure-sensitivity and small hysteresis. The record reversible colossal barocaloric effect with entropy change ΔSr ~ 400 J kg−1 K−1 at 0.08 GPa and adiabatic temperature change ΔTr ~ 11 K at 0.1 GPa highlights the design of novel barocaloric materials by engineering the dimensionality of plastic crystals.

Operando Investigation of the Molecular Origins of Dipole Switching in P(VDF‐TrFE‐CFE) Terpolymer for Large Adiabatic Temperature Change

AbstractRelaxor ferroelectric polymers exhibiting a giant electrocaloric effect (ECE) can potentially be used to create next‐generation solid‐state coolers. Under an electric field, poly(vinylidene fluoride‐trifluoroethylene‐chlorofluoroethylene) terpolymer goes through a large dipolar entropy change producing a high adiabatic temperature change (ΔTECE). This work resolves the molecular origins of the large entropy change behind the electric field‐induced dipole switching. A Fourier transform infrared spectroscopy equipped with a high voltage source is used to operandoly observe the characteristic molecular vibrational modes. A short‐range trans (T) conformation of the CF2‐CH2 dyads interrupted by a gauche (G) conformation, e.g., TTTG in the terpolymer chain, undergoes a dynamic transformation that leads to a corresponding ΔTECE whenever an electric field is applied. The molecular dynamics simulation also proves that the energy barrier that the transformation from TTTGs into a long T sequence overcomes is smaller than that for all other conformations. A mixed solvent system is used to obtain T3G‐enriched terpolymer films exhibiting a 4.02 K ΔTECE at 60 MV m−1 and these films are employed to manufacture a 2‐layer‐cascaded cooling device that achieves a 6.7 K temperature lift, the highest reported value for a 2‐layer cascaded device made of fluoropolymers.

Colossal Barocaloric Effect of Binary Fatty Acid Methyl Esters under Low Pressures near Room Temperature.

Refrigeration technology based on the caloric effect is one of the more environmentally friendly alternatives to gas compression refrigeration. The barocaloric effect utilizes pressure to induce phase transition and results in a large entropy change. In this work, a colossal barocaloric effect in the liquid-solid transition (L-S-T) of binary fatty acid methyl esters (BFAMEs) was discovered. At 295 K, an isothermal entropy change as high as 591 J kg-1 K-1 and a reversible entropy change of 356 J kg-1 K-1 at a hydrostatic pressure of 80 MPa were obtained by mixing methyl palmitate and methyl stearate with a specific ratio to synthesize a BFAME. The value of the isothermal entropy change of the BFAME is comparable to that of a commercial gas compression refrigerant, R134a. This work will provide a new L-S-T candidate material to replace commercial refrigerants for the potential application of caloric effect refrigeration technology.

Low-k nano-dielectrics facilitate electric-field induced phase transition in high-k ferroelectric polymers for sustainable electrocaloric refrigeration

Ferroelectric polymer-based electrocaloric effect may lead to sustainable heat pumps and refrigeration owing to the large electrocaloric-induced entropy changes, flexible, lightweight and zero-global warming potential. Herein, low-k nanodiamonds are served as extrinsic dielectric fillers to fabricate polymeric nanocomposites for electrocaloric refrigeration. As low-k nanofillers are naturally polar-inactive, hence they have been widely applied for consolidate electrical stability in dielectrics. Interestingly, we observe that the nanodiamonds markedly enhances the electrocaloric effect in relaxor ferroelectrics. Compared with their high-k counterparts that have been extensively studied in the field of electrocaloric nanocomposites, the nanodiamonds introduces the highest volumetric electrocaloric enhancement (~23%/vol%). The resulting polymeric nanocomposite exhibits concurrently improved electrocaloric effect (160%), thermal conductivity (175%) and electrical stability (125%), which allow a fluid-solid coupling-based electrocaloric refrigerator to exhibit an improved coefficient of performance from 0.8 to 5.3 (660%) while maintaining high cooling power (over 240 W) at a temperature span of 10 K.

Revisiting the driving force inducing phase separation in PEG-phosphate aqueous biphasic systems.

Liquid phase separation using aqueous biphasic systems (ABS) is widely used in industrial processes for the extraction, separation and purification of macromolecules. Using water as the single solvent, a wide variety of solutes have been used to induce phase separation including polymers, ionic liquids or salts. For each system, polymer-polymer, polymer-ionic liquid, polymer-salt or salt-salt, different driving forces were proposed to induce phase separation. Specifically, for polymer-salt systems, a difference in solvation structure between the polymer-rich and the salt-rich was proposed, while other reports suggested that a large change in enthalpy and entropy accompanied the phase separation. Here, we reinvestigated the PEG/K2HPO4/H2O systems using a combination of liquid-phase nuclear magnetic resonance (NMR) and high-resolution Raman spectroscopies, coupled with injection microcalorimetry. Both NMR and Raman reveal a decreased water concentration in the PEG-rich phase, with nonetheless no significant differences observed for both 1H chemical shift or OH stretching vibrations. Hence, both PEG- and salt-rich phases exhibit similar water solvation properties, which is thus not the driving force for phase separation. Furthermore, NMR reveals that PEG interacts with salt ions in the PEG-rich solution, inducing a downfield shift with increasing salt concentration. Injection microcalorimetry measurements were carried out to investigate any effect due to enthalpy change during mixing. Nevertheless, these measurements indicate very small enthalpy changes when mixing PEG- and salt-rich solutions in comparison with that previously recorded for salt-salt systems or associated with mixing of two solvents. Hence, our study discards any large change of enthalpy as the origin for phase separation of PEG/K2HPO4 systems, in addition to large difference in solvation properties.

Exploring the local solvation structure of redox molecules in a mixed solvent for increasing the Seebeck coefficient of thermocells.

A thermocell is an emerging alternative to thermoelectric devices and exhibits a high Seebeck coefficient (Se) due to the large change of solvation entropy associated with redox reactions. Here, the Se of p-chloranil radicals/dianions (CA˙-/2-) in acetonitrile was drastically increased from -1.3 to -2.6 mV K-1 by the addition of ethanol, and the increment surpassed the estimation of the classical Born model with continuum solvent media. UV-vis spectroscopy and electrochemical measurements at various mixing ratios of acetonitrile to ethanol revealed that the strong hydrogen bonding between ethanol and oxygen atoms of CA2- forms a 4 : 1 solvent-ion pair, while the ethanol molecules binding to CA2- dissociate upon its oxidation to CA˙-. The local solvation structures of CA2- are in good agreement with density functional theory. This order-disorder transition of the local solvation structure around the CA˙-/2- ions produces a large entropy change and results in a large Se value. The tailored solvation structure of redox ions by hydrogen bonding is a versatile method applicable to a variety of redox pairs and solvents, contributing to the development of electrolyte engineering for thermocells.

Optimized Electrocaloric Refrigeration in Lead-Free NaNbO3-Based Ceramics via AFE ↔ FE Phase Transition Modulation.

An outstanding challenge for eco-friendly ferroelectric (FE) refrigeration is to achieve a large adiabatic temperature change within a broad temperature range originating from the electrocaloric (EC) effect, which is expected to be realized in antiferroelectric (AFE) materials owing to the large entropy change during electric field and thermally induced phase transition. In this work, a large EC response over a wide response temperature range can be achieved slightly above room temperature via designing the phase transition of NaNbO3. An irreversible to reversible AFE-FE phase transition on heating induced by the introduction of CaZrO3 into NaNbO3 plays a key role in the optimized electrocaloric refrigeration. Accordingly, accompanying the local structure transformation corresponding to the B-site ions, the transition temperature between the square polarization-electric field (P-E) hysteresis loop (the irreversible AFE-FE phase transition induced by the electric field) and the repeatable double P-E hysteresis loop (the electric field induced reversible AFE-FE phase transition) was tailored to around room temperature, in favor of extending large entropy change to the wide temperature range. This work provides an efficient approach to designing lead-free EC materials with excellent EC performance, promoting the advancement of environmentally friendly solid-state cooling technology.

Crystallography of stress-induced martensitic transformation and giant elastocaloric effect in a A textured Ni27Cu21Mn46Sn6 shape memory alloy

Shape memory alloys exploit the latent heat yielded by stress-induced martensitic transformation to achieve elastocaloric effect, being suited for solid-state cooling technology as an alternative to conventional vapor-compression refrigeration. In this work, the crystallography of stress-induced martensitic transformation and elastocaloric effect in a polycrystalline Ni27Cu21Mn46Sn6 shape memory alloy with <001>A preferential orientation produced by means of directional solidification were studied. By performing ex-situ electron backscatter diffraction (EBSD) measurements, the transition from austenite to a single variant of 6 M martensite induced by compressive loading was evidenced, following a specific transformation orientation relationship of {1 0 1}A//{1 –2 –6}M and <1 0 − 1>A//<–6 –6 1>M between two phases. Moreover, owing to the synergistic effect of large transformation entropy change tailored through manipulating the lattice volume change across the phase transformation and microstructure texturing promoted by temperature gradient effect during solidification process, the present alloy can demonstrate very remarkable elastocaloric effect, with an extremely high value of adiabatic temperature variation up to –31.8 K upon releasing a moderate compressive loading of 460 MPa. This work is expected to give insight into stress-induced martensitic transformation crystallography and offer some inspirations for designing high-performance elastocaloric materials.

Significantly enhanced reversibility and mechanical stability in grain-oriented MnNiGe-based smart materials

Materials that undergo a magnetostructural transition (MST) usually exhibit fascinating magnetoresponsive properties, making them an important class of smart materials. However, practical application of this class of smart materials has been hindered by structural degradation as well as large irreversibility of the MST during consecutive thermal and field cycles. Here we report a significant improvement of the reversibility and mechanical stability in grain-oriented MnNiGe-based alloys that were fabricated using a directional solidification method. The preferred grain orientation enables synergistic deformations between neighboring grains during the MST, leading to a substantial reduction in the transition-induced stress concentration. As a result, in situ and ex situ microscopic observations demonstrate a good mechanical stability of the textured alloys across the MST, in strong contrast to conventional MM'X (M, M’ = Mn, Fe, Co, Ni; X = Si, Ge) materials with randomly-oriented grains. The detailed transition stages of the MST have also been observed at the microscopic scale, and are reported for the first time in the MM'X family. Besides, a low thermal hysteresis (ΔThys) of ∼ 4 K was obtained in the textured alloys, which is the lowest ΔThys in the MM'X material family. Textured MnNiGe-based alloys show a large reversible isothermal entropy change (≥ 35.9 Jkg−1K−1) in a 5 T field change, which is the highest among typical magnetocaloric materials. Consequently, this work provides a promising strategy for enhancing the cyclic stability of materials with a MST, which may boost their practical applications in solid-state refrigerators, energy harvesters and high-precision actuators.

Modified (Ba,Sr)(Sn,Ti)O3 via hydrothermal synthesis for electrocaloric application

Electrocaloric cooling systems require components with large entropy change at the desired working temperature, high electric breakdown strength and low dielectric losses. We here report on hydrothermal synthesis (HTS) route for preparation of lead-free electrocaloric (EC) material Ba0.82Sr0.18Sn0.065Ti0.935O3 (BSSnT-18-6.5) with a median particle size of d50 = 150 nm. Influence of molar ratio (Ba,Sr):(Sn,Ti) on the purity and particle size of hydrothermally synthesized powders is investigated. The sintering behavior and the resulting microstructure of bulk ceramic samples prepared with HTS powders as well as their dielectric, ferroelectric, and electrocaloric properties are analyzed and discussed in detail. By using HTS powders we could significantly reduce sintering temperature from 1400 °C to 1275 °C. Samples prepared with a molar ratio (Ba,Sr):(Sn,Ti) of 1.6 show a maximum EC temperature change |ΔTEC| of 0.59 K around 30 °C with a broad peak of |ΔTEC| > 0.3 K in the temperature range from 5 °C to 65 °C under an applied electric field change of 5 V μm−1. Our results show that hydrothermal synthesis is well suited to produce starting powders of lead-free electrocaloric materials for future fabrication of multilayer ceramic (MLC) components.

Variation of CI-2 Conformers upon Addition of Methanol to Water: An IMS-MS-Based Thermodynamic Analysis.

Chymotrypsin inhibitor 2 (CI-2) is a well-studied, textbook example of a cooperative, two-state, native ↔ denatured folding transition. A recent hybrid ion mobility spectrometry (IMS)/mass spectrometry (MS) thermal denaturation study of CI-2 (the well-studied truncated 64-residue model) in water reported evidence that this two-state transition involves numerous (∼41) unique native and non-native (denatured) solution conformations. The characterization of so many, often low-abundance, states is possible because of the very high dynamic range of IMS-MS measurements of ionic species that are produced upon electrospraying CI-2 solutions from a variable temperature electrospray ionization source. A thermodynamic analysis of these states revealed large changes in enthalpy (ΔH) and entropy (ΔS) at different temperatures, and it was suggested that such variation might arise because of temperature-dependent conformational changes of the protein in response to changes in the conformational entropy and the dielectric permeability of water, which drops from a value of ε ∼ 79 at 24 °C to ∼ 60 at 82 °C. Herein, we examine how adding methanol to water influences the distributions of CI-2 conformers and their ensuing stabilities. The dielectric constant of a 60:40 water:methanol (MeOH) drops from ε ∼ 60 at 24 °C to ∼ 51 at 64 °C. Although the same set of conformers observed in water appears to be present in 60:40 water:MeOH, the abundance of each is substantially altered by the presence of methanol. Relative free energy values (ΔG) and thermodynamic values [ΔH and ΔS and heat capacities (ΔCp)] are derived from a Gibbs-Helmholtz analysis. A comparison of these data from water and water:MeOH systems allows rare insight into how variations in solvation and temperature affect many-state protein equilibria. While these studies confirm that variations in solvent dielectric constant with temperature affect the distributions of conformers that are observed, our findings suggest that other solvent differences may also affect abundances.

Effect of Melt-Spinning Parameters on the Structure and Properties of Ni55.5Mn18.8Ga24Si1.7 Heusler Alloy Ribbons.

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, Ni55.5Mn18.8Ga24Si1.7 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.