Search

The binary GdNi adopting the orthorhombic CrB-type (oS8, Cmcm) dissolves up to 21 at% Co (GdCo0.42Ni0.58), but when the Co content reaches 23.7 at% the crystal structure of the GdCoxNi1−x phase changes from the orthorhombic CrB-type to the tetragonal MoB-type (tI16, I41/amd). The latter remains stable between 23.7 and 36.0 at% Co (0.47 ≤ xCo ≤ 0.72), and there is a two-phase region compositional gap of ≈ 2.5 at% Co between the two structures. One of the two 8e sites available in the MoB-type structure is filled by Gd atoms, while Co and Ni atoms are randomly occupying the other 8e site. The lattice parameter a increases from 3.9485(1) Å to 3.9591(1) Å, while c decreases from 21.3286(1) Å to 21.2404(1) Å as xCo increases, both following a quadratic trend. As a result, the unit cell volume increases from 332.53(2) Å3 to 332.93(2) Å3 for, respectively, the Co-poor (GdCo0.47Ni0.53) and the Co-rich (GdCo0.72Ni0.28) sides of the solid solution, also following a quadratic trend with a negative deviation of the Zen's law. The title compound becomes ferromagnetic with TC increasing linearly from 150 K for GdCo0.50Ni0.50 to 171 K for GdCo0.70Ni0.30; linear interpolation leads to TC = 127 K and 174 K for the two ends of the solid solution with xCo = 0.47 and 0.72, respectively. The magnetic susceptibility follows the Curie-Weiss law, indicating a trivalent state of Gd ions, with an effective magnetic moment slightly increasing with the Co content. The magnetocaloric effect, calculated in terms of the isothermal magnetic entropy change, decreases slightly as xCo increases, remaining large in the range 127–174 K.

The realization of spin-glass (S-G) state in Heusler alloys is very rare despite the presence of inherent structural and elemental disorder in those compounds. Although a few half and full Heusler alloys are known to exhibit S-G state, there is hardly any manifestation of the same in cases of quaternary Heusler compounds. Here we report the observation of S-G state in a highly disordered equiatomic quaternary Heusler compound: FeRuMnGa, where the S-G state is in between of canonical S-G and cluster glass. Different intricate features of S-G state including non-equilibrium magnetic dynamics at low temperature in the compound are unveiled through our comprehensive magnetic, heat capacity and neutron diffraction studies. The structural disorder in the sample is neither conventional \textit{A2}- nor \textit{B2}-type while those two types are commonly observed for Heusler compounds. The presence of disorder also plays a significant role in electron transport properties of the alloy, which is reflected in its exhibition of semi-metallic behavior and anomalous Hall effect at low temperature., Comment: 11 pages, 13 figures

We report two new rare-earth (R) ternary intermetallic compounds—Ho2Ni0.8T1.2 with T = Si and Ge—that correspond to the R5Ni2T3 phase earlier reported to form in Dy–Ni–T and Ho–Ni–T ternary systems. The compounds crystallize in a filled version of the orthorhombic Zr2Ni1–xP-type structure with x = 0.52; their stoichiometry, determined from both single-crystal and powder X-ray diffraction data, is centered on Ho2Ni0.8T1.2 with a narrow solid solubility range for the silicide, while the germanide appears to be a line phase. In addition to R = Dy and Ho, R2Ni0.8T1.2 compounds also form for R = Y and Tb, representing the first examples of rare-earth-based compounds adopting the Zr2Ni1–xP structural prototype. Bulk magnetization data reveal the main transitions of the ferrimagnetic or ferromagnetic type at TC = 38 K for Ho2Ni0.8Si1.2 and TC = 37 K for Ho2Ni0.8Ge1.2, which are followed by subsequent magnetic reordering at lower temperatures. Neutron diffraction shows complex magnetic structures below TC with both ferromagnetic and antiferromagnetic components and magnetic propagation vector κ1 = [0, 0, 0]. Below TN ≅ 24 K (22 K) for the silicide (germanide), an additional antiferromagnetic coupling following an incommensurate magnetic propagation vector κ2 = [κx, 0, 0] appears to coexist with the first magnetic structure., The crystal structure of Ho2Ni0.8Si1.2 (and Ho2Ni0.8Ge1.2) [Zr2Ni0.48P-type (oP32-Pnma)] viewed along the b axis is given. The Ho, Ni1, Ni2/Si, Si1 and Si2 atoms are represented as red, turquoise, blue, light-gray, and dark-gray spheres, respectively. The distinctive structural fragment is built up of five differently oriented trigonal prisms. The magnetic structure of Ho2Ni0.8Ge1.2 with the antiferromagnetic component in the c direction and the ferromagnetic component along the a axis.

Magnetocaloric heat pumping near room temperature, a.k.a. magnetic cooling, relies on the active regenerator cycle to achieve functional temperature spans and realize economic and societal benefits promised by this emerging solid-state cooling technology. The cycle itself depends upon synchronizing oscillating flow of a heat transfer fluid through a solid porous active material matrix, or the refrigerant, with periods when the refrigerant is in the highest available (field-on) and in nearly zero (field-off) magnetic fields to accomplish heat transfer. With this in mind, we analyze varying flow and magnetic field wave forms and the timing between when the fluid is pumped and when the magnetic field is turned on and off. We demonstrate that the volume and the cost of permanent magnet generating the field changes can be cut nearly in half with little to no effect on the device temperature span and cooling power normalized by the refrigerant mass.

Tuning the chemistry of materials often leads to discoveries of interesting phenomena that expand basic science and support practical applications. Here we show how different spin–orbit coupling in light and heavy lanthanides can be exploited to create complex magnetic ground states and thereby unusual spontaneous exchange bias (SEB), conventional exchange bias (CEB), and magnetic memory effects in almost ideally magnetically compensated Pr0.75Gd0.25ScGe, which is a representative of the PrScGe–GdScGe solid solution. We report the synthesis and detailed characterization of Pr0.75Gd0.25ScGe by X-ray powder diffraction, scanning electron microscopy, and magnetization measurements in magnetic fields up to 140 kOe. Partial substitution of a light lanthanide, Pr, with a heavy lanthanide, Gd, results in a complex magnetic ground state, which includes large spontaneous and conventional exchange biases reaching magnitudes of ∼1.7 kOe and ∼3.5 kOe, respectively, at T = 2 K, as well as shape dependent magnetic compensation and bias phenomena occurring in small external fields.

A new family of heterostructured transition-metal dichalcogenides (TMDCs) with incommensurate (“misfit”) spatial arrangements of well-defined layers was prepared from structurally dissimilar single-phase 2H-MoS2 and 1T-HfS2 materials. The experimentally observed heterostructuring is energetically favorable over the formation of homogeneous multi-principle element dichalcogenides observed in related dichalcogenide systems of Mo, W, and Ta. The resulting three-dimensional (3D) heterostructures show semiconducting behavior with an indirect band gap around 1 eV, agreeing with values predicted from density functional theory. Results of this joint experimental and theoretical study open new avenues for generating unexplored metal-dichalcogenide heteroassemblies with incommensurate structures and tunable physical properties.

Three-dimensional heterostructures are usually created either by assembling two-dimensional building blocks into hierarchical architectures or using stepwise chemical processes that sequentially deposit individual monolayers. Both approaches suffer from a number of issues, including lack of suitable precursors, limited reproducibility, and poor scalability of the preparation protocols. Therefore, development of alternative methods that enable preparation of heterostructured materials is desired. We create heterostructures with incommensurate arrangements of well-defined building blocks using a synthetic approach that comprises mechanical disassembly and simultaneous reordering of layered transition-metal dichalcogenides, MX2, and non-layered monochalcogenides, REX, where M = Ta, Nb, RE = Sm, La, and X = S, Se. We show that the discovered solid-state processes are rooted in stochastic mechanochemical transformations directed by electronic interaction between chemically and structurally dissimilar solids toward atomic-scale ordering, and offer an alternative to conventional heterostructuring. Details of composition–structure–properties relationships in the studied materials are also highlighted., 3D heterostructures offer properties that are inaccessible in bulk single-phase solids, but synthetic approaches are limited. The authors use mechanochemical reshuffling of binary precursors and subsequent annealing to design structurally aligned misfit heterostructures with well-defined atomic arrangements.

Mechanochemical reactions of benzene-1,4-dicarboxylate (BDC2−) and lanthanide carbonates, Ln2(CO3)3·xH2O (Ln = Sm, Eu, Gd, Tb) yield phase pure lanthanide coordination polymers, (Ln0.5Gd0.5)2(1,4-BDC)3(H2O)4 with Ln = Sm, Eu, Tb, which are isostructural with Tb2(1,4-BDC)3(H2O)4 as confirmed by powder X-ray diffraction and vibrational spectroscopy. Upon excitation with UV light all three compounds display strong emissions, characteristic for the respective optically active lanthanide ion, namely, red for Eu3+, green for Tb3+ and orange-red for Sm3+. In case of the Tb3+-containing compound, the energy difference between the triplet energy level of benzene-1,4-dicarboxylate ligand (BDC2−) allows for the most efficient BDC2−–Tb3+ energy transfer. As a consequence, an intense green luminescence with rather long lifetime (0.81 ms) and high quantum yield (22%) is observed after allowed excitation of the BDC2− ligand. The compounds are paramagnetic with no onset of long range magnetic ordering down to liquid He temperatures.

Chemical substitution is one of the most efficient tools to tune and optimize magnetic and magnetocaloric properties of the giant magnetocaloric materials. In particular, Indium substitutions could be useful both for tuning properties of these interesting intermetallic materials and to unveil their local-scale behavior across the magnetostructural transition via hyperfine techniques. Hence, in order to investigate the effect of Indium additions on the crystal structure, micro-structure, magnetic and magnetocaloric properties, a series of In-containing samples derived from the base Gd5Si1.2Ge2.8 stoichiometry were prepared. The major findings are that while In is insoluble in the 5: 4 phase, it will instead promote the emergence of the impurity 5: 3 phase and segregates into this phase. Hence, In leads to major crystallographic changes, which enhance atomic disorder and disrupt the Si to Ge ratio in the 5: 4 phase. Subsequently, a higher 5: 4 unit cell volume and a lower magnetic ordering temperature are found in the In-substituted samples. Finally, the magnetocaloric properties of the In-substituted samples reveal a detrimental effect on the maximum magnetic entropy change., Work is partially supported by the projects POCI/CTM/61284/2004, PTDC/CTM-NAN/115125/2009, FEDER/POCTI n0155/94 from Fundacão para a Ciência ex Tecnologia (FCT), Portugal. A.M.P. thanks FCT for the Grant No. SFRH/BPD/63150/2009. J H Belo thanks FCT for the Grant SFRH/BD/88440/2012, the project PTDC/FISMAC/ 31302/2017 and his contract DL57/2016 reference SFRH-BPD-87430/2012. Work at IFIMUP is supported by the following funding projects: POCI-01-0145-FEDER-032527, POCI-01–0145-FEDER-029454 and CERN-FIS-PAR-0005-2017. Work at the INMA is supported by the Spanish Ministerio de Ciencia, Innovacion y Universidades through project MAT2017-82970-C2, PID2020-112914RB-I00 and Spanish DGA (grant no. E28−20R). The research at Ames Laboratory is supported by the Materials Sciences and Engineering Division, Office of Basic Energy Sciences of the U.S. Department of Energy (DOE). Ames Laboratory is operated for the U.S DOE by Iowa State University under Contract No. DE-AC02-07CH11358.

The coupling between structural and magnetic degrees of freedom is crucial for realization of interesting physical phenomena associated with magneto-structural transformations resembling austenite-to-martensite transitions. Despite substantial efforts in design and discovery of materials with strong magnetocaloric effects, a majority of viable candidates are composed of non-earth-abundant and toxic elements, while others involve challenging syntheses and post processing. Guided by advanced density functional theory calculations, we report a new family of compounds, i.e., Mn0.5Fe0.5NiSi1-xAlx [x = 0.045–0.07] exhibiting a giant magnetocaloric effect (MCE) that is tunable near room temperature. Their MCE functionality arises from a distinct magneto-structural transformation between a paramagnetic hexagonal Ni2In-type phase and ferromagnetic orthorhombic TiNiSi-type phase that can be actuated by magnetic field and/or pressure. As the transition is sensitive to external hydrostatic pressure, the same materials should also exhibit a strong barocaloric response in addition to the giant MCE.

Materials exhibiting a large magnetocaloric effect (MCE) at or near room temperature are critical for solid-state refrigeration applications. The MCE is described by a change in entropy (ΔSM) and/or temperature (ΔTad) of a material in response to a change in applied magnetic field. Ball milled materials generally exhibit smaller ΔSM values compared to bulk; however, milling broadens the effect, potentially increasing the relative cooling power (RCP). The as-cast Gd5Si4 is an attractive option due to its magnetic transition at 340 K and associated MCE. Investigation of effect of particles size and transition temperature in the binary material, Gd5Si4, can lead to development of functionally graded bulk material with higher MCE and RCP than the traditional bulk materials. A two-step ball-milling process, in which coarse powder of Gd5Si4 was first milled with poly(ethylene glycol) followed by milling in heptane was used to produce fine particles of Gd5Si4 that showed a broad distribution in particle size. Magnetic measurement on the milled sample obtained after washing with water show a decrease in Curie temperature and significant broadening of the magnetic transition. Compared to bulk Gd5Si4, the maximum MCE of the milled samples is also reduced and shifted down by close to 30 K, but the MCE remains substantial over a broader temperature range. The RCP of both milled samples increased 75% from the bulk material.

Magnetocaloric refrigeration is a solid-state cooling approach that promises high energy efficiency and low environmental impact. It remains uncompetitive with conventional vapor-compression technologies due to lack of high-performing materials that exhibit large magnetocaloric effects in low magnetic fields. Here we report a game-changing enhancement of the magnetocaloric response in a transition-metal-based Ni–Co–Mn–Ti. Mechanically and chemically stable rapidly solidified ribbons exhibit magnetic entropy changes as high as ∼ 27 J⋅kg−1K−1 for a moderate field change of 2 T, comparable to or larger than the best known materials for near-room temperature applications. The ribbons can be easily manufactured in large quantities and the transition temperature can be adjusted by varying Co concentration.

A study on the formation and stability of new quaternary compounds with the general chemical formula Gd3TAl3Ge2(T = Mn, Cu) has been undertaken by experimental investigations (SEM-EDX, DTA and XRD) and density functional theory (DFT) calculations. These compounds crystallize in the hexagonal Y3NiAl3Ge2-type structure (hP9, P–62m, Z = 1) (an ordered, quaternary derivative of the ternary ZrNiAl or of the binary Fe2P prototypes), with lattice parameters values a = 7.0239(2) Å and c = 4.2580(1) Å for Gd3MnAl3Ge2and a = 7.0434(1) Å and c = 4.2089(1) Å for Gd3CuAl3Ge2. DTA suggests a peritectic reaction for the formation of these compounds (at 1245°C for Gd3CuAl3Ge2). The existence and stability of these phases has been explained on the basis of DFT calculations, and a comparison of ground state properties of the studied compounds with the earlier known Gd3CoAl3Ge2phase is outlined. The negative formation energies in all three cases govern the stability of compounds from theory as well, predicting Gd3MnAl3Ge2as the most stable phase with highest formation energy (–13.01 eV/f.u.). The total DOS are generic in nature and suggest the robust magnetism, with the Gd-f moments of ≈7 μB. An antiparallel coupling among Gd-f and T-d states is observed for all compounds, as usually seen in rare earth (R) - transition metal (T) compounds. Preliminary magnetization measurements on Gd3MnAl3Ge2show two ferromagnetic/ferrimagnetic (FM/FIM) like transitions at TC1= 142 K and TC2= 97 K, with another anomaly seen at ≈15 K. Isothermal magnetization data show no hysteresis even at 5 K, and the magnetization does not saturate up to 50 kOe, further suggesting a possible FIM behavior.

The kinetic arrest observed in the parent Gd5Ge4 gradually vanishes when a small fraction (x = 0.025, 0.05 and 0.10) of Gd is replaced by Sc in (Gd1−xScx)5Ge4, and the magnetic ground state changes from antiferromagnetic (AFM) to ferromagnetic (FM). A first order phase transition coupled with the FM-AFM transition occurs at TC = 41 K for x = 0.05 and at TC = 53 K for x = 0.10 during heating in applied magnetic field of 1 kOe, and the thermal hysteresis is near 10 K. The first-order magnetic transition is coupled with the structural Sm5Ge4-type to Gd5Si4-type transformation. The magnetization measured as a function of applied magnetic field shows sharp metamagnetic-like behavior. At the same time, the AFM to paramagnetic transition in (Gd1−xScx)5Ge4 with x = 0.10, is uncharacteristically broad indicating development of strong short-range AFM correlations above the Neel temperature. Comparison of the magnetization data of bulk, powdered, and metal-varnish composite samples of (Gd0.95Sc0.05)5Ge4 shows that mechanical grinding and fabrication of a composite have little effect on the temperature of the first-order transformation, but short-range ordering and AFM/FM ratio below TC are surprisingly strongly affected.

The hydrogen storage properties, and phase compositions of mechanochemically prepared mixtures of xMBH4-SiS2 (x = 2–8), where M = Li or Na, were investigated using gas sorption analysis, powder X-ray diffraction, and infrared and solid-state NMR spectroscopic methods. The 2LiBH4:1SiS2 system forms an amorphous product that releases ca. 4.3 wt % of H2 below 385 °C with a Tonset of 88 °C without detectable diborane emission. The dehydrogenated sample reversibly absorbs 1.5 wt % of H2 at 385 °C under 160 bar pressure. The H2 release from materials with varying LiBH4:SiS2 ratios peaks at 8.2 wt % for the 6LiBH4:1SiS2 composition, with a reversible hydrogen storage capacity of 2.4 wt %. The H2 desorption capacities of the Li-containing systems surpass those of Na-containing systems. Solid-state NMR studies indicate that products of mechanochemical reactions in the LiBH4 SiS2 system consist of one-dimensional chains of edge-sharing SiS4/2 tetrahedra in which the non-bridging S-ends are terminated with Li+, which are further coordinated to the [BH4]− anions. A variety of possible polymorphs in the Li Si S-(BH4) composition space have been identified using first principles and thermodynamic modeling that supports the likelihood of formation of such novel complexes.

The magnetic and magnetocaloric properties of DyCo2Cx (x = 0, 0.05, 0.1, and 0.15) alloys were investigated. The results show that the Curie temperature (TC) of the DyCo2Cx alloys increases with increasing C content, from 136 K (x = 0) to 152 K (x = 0.15), but the lattice parameter a of DyCo2Cx exhibits a maximum at x = 0.05. The suppression of the ac susceptibility of DyCo2Cx at low temperature indicates the enhancement of the domain wall pinning effect by carbon doping. The positive slops of the Arrott plots of the doped compounds indicate that the phase transition is second order for the carbon-doped alloys, and the maximum value of the isothermal magnetic entropy change (ΔSM) for the magnetic field change of 50 kOe decreases from −13.9 J/kg· K (x = 0) to −7.8 J/kg·K (x = 0.15). The relative cooling power (RCP) of DyCo2Cx is nearly the same in all studied alloys, while the temperature-averaged entropy change over 10 K temperature span, TEC(10), indicates decreasing magnetocaloric performance of carbon doped materials.

A facile method to produce few-layer graphene (FLG) nanosheets is developed using protein-assisted mechanical exfoliation. The predominant shear forces that are generated in a planetary ball mill facilitate the exfoliation of graphene layers from graphite flakes. The process employs a commonly known protein, bovine serum albumin (BSA), which not only acts as an effective exfoliation agent but also provides stability by preventing restacking of the graphene layers. The latter is demonstrated by the excellent long-term dispersibility of exfoliated graphene in an aqueous BSA solution, which exemplifies a common biological medium. The development of such potentially scalable and toxin-free methods is critical for producing cost-effective biocompatible graphene, enabling numerous possible biomedical and biological applications. A methodical study was performed to identify the effect of time and varying concentrations of BSA towards graphene exfoliation. The fabricated product has been characterized using Raman spectroscopy, powder X-ray diffraction, transmission electron microscopy and scanning electron microscopy. The BSA-FLG dispersion was then placed in media containing Astrocyte cells to check for cytotoxicity. It was found that lower concentrations of BSA-FLG dispersion had only minute cytotoxic effects on the Astrocyte cells.

A new mixed alkali metal–aluminum borohydride LiAl(BH4)2Cl2 has been prepared via mechanochemical synthesis from the 2LiBH4–AlCl3 mixture. Structural characterization, performed using a combination of X-ray powder diffraction and solid-state NMR methods, indicates that the LiAl(BH4)2Cl2 phase adopts a unique 3D framework and crystallizes in an orthorhombic structure with the space group C2221, a = 11.6709(6) Å, b = 8.4718(4) Å, c = 7.5114(3) Å. The material shows excellent dehydrogenation characteristics, where hydrogen evolution starts at Tons = 70 °C, releasing approximately 2 wt.% of nearly pure (99.8 vol.%) hydrogen and a very small amount (~0.2 vol.%) of diborane. When compared to halide-free mixed alkali metal–aluminum borohydrides, the presence of Al‒Cl bonding in the LiAl(BH4)2Cl2 structure likely prevents the formation of Al(BH4)3 upon decomposition, thus suppressing the formation of diborane.

A new family of heterostructured transition-metal dichalcogenides (TMDCs) with incommensurate ("misfit") spatial arrangements of well-defined layers was prepared from structurally dissimilar single-phase 2H-MoS

Binary intermetallic ${\mathrm{Eu}}_{2}\mathrm{In}$ was recently reported to exhibit a giant anhysteretic magnetocaloric effect due to a first-order magnetic phase transition between paramagnetic and ferromagnetic states. Experimentally, the transition occurs with a small phase volume change, $\mathrm{\ensuremath{\Delta}}V/V$, of approximately 0.1% around ${T}_{C}$ of $ca.$ 55 K. We represent magnetic and compute magnetocaloric properties of a ${\mathrm{Eu}}_{2}\mathrm{In}$ compound using a microscopic description based on a model Hamiltonian that takes into account magnetic exchange and magnetoelastic interactions. In the model the thermodynamic nature of the transition is conveniently represented by a single magnetoelastic interaction parameter. A good agreement between the theoretical results and earlier published experimental data confirms the effectiveness of our approach.

While binary $R{E}_{2}\mathrm{In}$, where $RE=\mathrm{rare}\phantom{\rule{0.16em}{0ex}}\mathrm{earth}$, have been reported a few decades ago, recent investigations revealed intriguing new physical insights. For instance, the discovery of a nearly ideal first-order ferromagnetic transition in ${\mathrm{Eu}}_{2}\mathrm{In}$ calls for further exploration of structures and properties of $R{E}_{2}\mathrm{In}$, in particular for the least-documented $RE=\mathrm{Eu}$ and Yb cases. Here, we investigate ${\mathrm{Eu}}_{2\text{\ensuremath{-}}x}{\mathrm{Yb}}_{x}\mathrm{In}$ pseudobinaries with nominal values of $x=0.25$, 0.5, 0.75, 1, 1.5, 2 by powder x-ray diffraction (including as function of temperature from 100 to 375 K for ${\mathrm{Yb}}_{2}\mathrm{In}$), magnetization (5--300 K), as well as electrical resistivity (5--300 K) and calorimetric (2--150 K) measurements for ${\mathrm{Yb}}_{2}\mathrm{In}$. Compared to other RE, Yb or Eu always raise challenging questions linked to their valence states. From average atomic volume, Yb is anticipated to be divalent in ${\mathrm{Yb}}_{2}\mathrm{In}$, at least between 100 and 375 K, which is in line with the absence of $4f$ magnetism. In agreement with x-ray diffraction and magnetization data, the resistivity of ${\mathrm{Yb}}_{2}\mathrm{In}$ is rather featureless and typical of a metal. Establishing ${\mathrm{Yb}}_{2}\mathrm{In}$ as a nonmagnetic isostructural reference for ${\mathrm{Eu}}_{2}\mathrm{In}$ allows one to use its heat capacity to revisit that of the latter, and get experimental insights into the exceptional magnetocaloric effect of the compound with Eu. In particular, we show that a third of the total magnetic entropy (${S}_{\mathrm{m}}\ensuremath{\approx}35.6\phantom{\rule{0.16em}{0ex}}\mathrm{J}\phantom{\rule{0.16em}{0ex}}\mathrm{mo}{\mathrm{l}}^{\ensuremath{-}1}\phantom{\rule{0.16em}{0ex}}{\mathrm{K}}^{\ensuremath{-}1}$ at $T=100\phantom{\rule{0.16em}{0ex}}\mathrm{K}$) is concentrated in a 3 K temperature window around the ${T}_{\mathrm{C}}$ of ${\mathrm{Eu}}_{2}\mathrm{In}$. Starting from the ferromagnetic compound ${\mathrm{Eu}}_{2}\mathrm{In}$ $[{T}_{\mathrm{C}}=55.2(5)\phantom{\rule{0.16em}{0ex}}\mathrm{K}]$, we show that Yb substitutions in ${\mathrm{Eu}}_{2\text{\ensuremath{-}}x}{\mathrm{Yb}}_{x}\mathrm{In}$ lead to a decrease in both the Curie temperature [${T}_{\mathrm{C}}=41(2)$ and 32(2) K for $x=0.25$ and 0.5] and magnetic saturation, while weakening the first-order character of the transition as $x$ increases. A significant isothermal entropy change of $5.1(4)\phantom{\rule{0.16em}{0ex}}\mathrm{J}\phantom{\rule{0.16em}{0ex}}\mathrm{mo}{\mathrm{l}}^{\ensuremath{-}1}\phantom{\rule{0.16em}{0ex}}{\mathrm{K}}^{\ensuremath{-}1}$ for $\mathrm{\ensuremath{\Delta}}B=2\phantom{\rule{0.16em}{0ex}}\mathrm{T}$ is found at 44 K in ${\mathrm{Eu}}_{1.75}{\mathrm{Yb}}_{0.25}\mathrm{In}$, demonstrating that the giant magnetocaloric effect of ${\mathrm{Eu}}_{2}\mathrm{In}$ can be tuned to lower temperatures by Yb substitutions.

Using first-principles calculations, based on disordered local moment (DLM) theory combined with the self-interaction corrected local spin density approximation (SIC-LSDA), we study magnetic correlations in the paramagnetic state of $\mathrm{Gd}X\phantom{\rule{4pt}{0ex}}(X$=Cu, Zn, Ga, Ag, Cd, In, Au, Hg, and Tl) intermetallics and their alloys. The predicted magnetic orders and ordering temperatures that these correlations lead to are in overall good agreement with available experiments. The interactions between the Gd $f$-electron local moments are mediated by the valence electrons of the intermetallics which comprise both Gd and $X\phantom{\rule{4pt}{0ex}}d$ bands as well as $sp$ bands. There are RKKY-like features such as dependence on the number of $sp$-valence electrons but other variations manifest themselves in the phase diagrams as regions of incommensurate magnetic ordering, the origin and range of which are related to the binding energies of the alloying anion $d$ states, and their propensity to hybridize with the Gd states at the Fermi level.

Magnetic and magnetocaloric properties of H o 1 - x D y x A l 2 compounds with x = 0 , 0.05 , 0.10 , 0.15 , 0.25 and 0.50 , modelled using a Hamiltonian that includes the exchange interactions between Ho-Dy, Ho-Ho and Dy-Dy ions in addition to the crystalline electric field and the Zeeman effects, have been compared with those determined experimentally. In order to reproduce experimentally observed global ferromagnetic ordering temperatures and spin reorientation transition temperatures as xDy varies, the exchange interactions between Ho-Dy and Ho-Ho were set as free parameters and adjusted to match the experimental results. We demonstrate that heat capacity of polycrystalline materials in non-zero magnetic fields can be satisfactory reproduced by using the average of multiple magnetic field directions with respect to the crystallographic coordinate system, while reasonably good agreement between experimentally determined and theoretically predicted magnetocaloric effects can be achieved considering an average of only three field directions.

Conventional magnetometry is irreplaceable in evaluating bulk magnetization of materials over broad temperature and field ranges. The technique is also effective in quantifying hysteresis that may be associated with magnetic and structural phase transitions that occur during the magnetizing/demagnetizing cycling, and the derived magnetic field-induced isothermal entropy change – one of the most important properties in the field of magnetocalorics. Both systematic and random errors present during the measurements of magnetization, however, may lead to erroneous conclusions. Using two well-known materials – elemental Gd and intermetallic Gd5Si2Ge2 as examples, we consider best practices in performing reliable and rapid magnetization measurements for proper characterization of magnetocaloric properties.

The fundamentals and applications of ferroic materials—ferromagnetic, ferroelectric, and ferroelastic—are common subjects discussed in just about every graduate course related to functional materials. Looking beyond today’s traditional uses, such as in permanent magnets, capacitors, and shape-memory alloys, there are worthwhile and interesting questions common to the caloric properties of these ferroic materials. Can ferroic materials be used in a cooling cycle? Why are these materials susceptible to external fields? Which combination of properties is required to make some of them suitable for efficient cooling and heat pumping? We address these questions in this introduction to ferroic cooling, which comprises magnetocaloric, electrocaloric, elastocaloric and barocaloric approaches and combinations thereof (i.e., multicalorics). These are addressed in greater detail in the articles in this issue.

Future advancements in magnetocaloric refrigeration/heat pumping technologies depend on the discovery of new materials that demonstrate large, tunable magnetocaloric effects (MCEs) in the vicinity of coupled magnetic and structural phase transitions that occur reversibly with minimum hysteresis. With this in mind, we investigate phase transitions, microstructure, magnetic, thermal, magnetocaloric, and transport properties of (Gd5-xScx)Si1.8Ge2.2 compounds. Replacement of magnetic Gd with non-magnetic Sc in Gd5-xScxSi1.8Ge2.2 increases the ferromagnetic to paramagnetic first order phase transition temperature, TC, with only a minor reduction in MCE when x ≤ 0.2. We also demonstrate that hydrostatic pressure further increases TC and reduces the hysteresis of the first order phase transition in Gd4.8Sc0.2Si1.8Ge2.2 from 7 to 4 K. Temperature-dependent x-ray powder diffraction study of Gd4.8Sc0.2Si1.8Ge2.2 confirms the monoclinic ↔ orthorhombic structural transformation at TC, in agreement with magnetic, calorimetric, and electrical transport measurements. In addition to the substantial magnetocaloric effect, a large magnetoresistance of ∼20% is also observed in Gd4.8Sc0.2Si1.8Ge2.2 for ΔH = 50 kOe in the vicinity of the magnetostructural transition. In a drastic reversal of the initial doping behavior further additions of Sc (x > 0.2) suppress formation of the monoclinic phase, change the nature of the transition from first-to second-order, and reduce both the transition temperature and magnetocaloric effect.

Using first-principles calculations, based on disordered local moment theory, combined with the self-interaction corrected local spin density approximation, we study magnetic interactions in GdX intermetallics for X = Cu, Zn, Ga, Cd, and Mg. Our predicted magnetic orders and ordering temperatures both at zero and other pressures agree well with experiments including the large increase in the Curie temperature of GdCd under pressure that is shown by our own experimental measurements. From our results it emerges that the Ruderman-Kittel-Kasuya-Yosida interaction on its own can not explain the observed behaviour under pressure, and that the magnetic ordering mechanism is strongly influenced by the occupations of both Gd and anion d -bands.

The double-cation metal borohydride, Li4Al3(BH4)13, mechanochemically produced from a 13:3 mixture of lithium borohydride (LiBH4) and aluminum chloride (AlCl3), has a low hydrogen desorption temperature; however, the material’s decomposition is accompanied by a large emission of toxic diborane (B2H6). We found that a decrease of the LiBH4:AlCl3 ratio in the starting mixture yields increased amounts of partially chlorinated products that also dehydrogenate at low temperature, but release negligibly small amounts of diborane. Extensive characterization by solid-state NMR spectroscopy (SSNMR) and powder X-ray diffraction (XRD) found that the 11:3 ratio product maintains the Li4Al3(BH4)13-like structure, with additional Cl– anions substituting for [BH4]– compared to the 13:3 mixture. Further decrease of relative LiBH4 concentration in the starting mixture to 9:3 results in a different product composed of tetrahedral [Al(BH4)4]− and [Al(BH4)2Cl2]− complexes, in which two hydrogen atoms of each borohydride grou...

Three series of intermetallic compounds Eu(T1,T2)5In (T = Cu, Ag, Au) have been investigated over their full compositional ranges. Single crystals of all compounds have been obtained by self-flux and were analyzed by single crystal X-ray diffraction revealing that the representatives fall into two structure types: CeCu6 (oP28, Pnma, a = 8.832(3)–9.121(2) A, b = 5.306(2)–5.645(1) A, c = 11.059(4)–11.437(3) A, V = 518.3(3)–588.9(2) A3) and YbMo2Al4 (tI14, I4/mmm, a = 7.139(2)–7.199(2) A, c = 5.417(3)–5.508(1) A, V = 276.1(2)–285.8(1) A3). The structural preference was found to depend on the cation/anion size ratio, while the positional preference within the CeCu6 type structure shows an apparent correlation with the anion size. Chemical compression, hence, a change in cell volume, which occurs upon anion substitution, appears to be the main driving force for the change of magnetic ordering. While EuAg5In shows antiferromagnetic behavior at low temperatures, mixing Cu and Au within the same type of structure results in considerable changes in the magnetism. The Eu(Cu,Au)5In alloys with CeCu6 structure show complex magnetic behaviors and a strong magnetic field-induced spin-reorientation transition with the critical field of the transition being dependent on Cu/Au ratio. The alloys adopting the YbMo2Al4 type structure are ferromagnets exhibiting unusually high magnetic moments. The heat capacity of EuAu2.66Cu2.34In reveals a double-peak structure evolving with the magnetic field. However, low-temperature X-ray powder diffraction does not show a structural transition.