An Analytical Approach for Computing the Coefficient of Refrigeration Performance in Giant Inverse Magnetocaloric Materials

An analytical approach for computing the coefficient of refrigeration performance (CRP) was described for materials that exhibited a giant inverse magnetocaloric effect (MCE), and their governing thermodynamics were reviewed. The approach defines the magnetic work input using thermodynamic relationships rather than isothermal magnetization data discretized from the literature. The CRP was computed for only cyclically reversible temperature and entropy changes in materials that exhibited thermal hysteresis by placing a limit on their operating temperature in a thermodynamic cycle. The analytical CRP serves to link meaningful material properties in first-order MCE refrigerants to their potential work and efficiency and can be employed as a metric to compare the behaviors of dissimilar alloy compositions or for materials design. We found that an optimum in the CRP may exist that depends on the applied field level and Clausius–Clapeyron (CC) slope. Moreover, through a large literature review of NiMn-based materials, we note that NiMn(In/Sn) alloys offer the most promising materials properties for applications within the bounds of the developed framework.

Comparative High-Field Magnetization Study of (Sm,Er)2Fe17 and Er2Fe17 Compounds and their Nitrides

Magnetic properties of the R2Fe17 compounds are sensitive to the atomic substitutions and interstitial absorption of nitrogen. In our work, both were combined and their effect on the magnetization behavior of Er2Fe17 compound in magnetic fields up to 58 T was studied. Er2Fe17N2, Sm1.2Er0.8Fe17N2 and Sm1.8Er0.2Fe17N2.1 nitrides were prepared. Magnetization measurements were carried out, mainly on powder samples (excluding Er2Fe17 single crystal). Nanopowders of Sm1.2Er0.8Fe17N2 were obtained by mechanical grinding. The grinding time was varied from 0 to 60 minutes. The strength of the inter-sublattice coupling in samples is estimated by analyzing high-field magnetization data.

3D Metal–Organic Frameworks Based on Co(II) and Bithiophendicarboxylate: Synthesis, Crystal Structures, Gas Adsorption, and Magnetic Properties

Three new 3D metal-organic porous frameworks based on Co(II) and 2,2′-bithiophen-5,5′-dicarboxylate (btdc2−) [Co3(btdc)3(bpy)2]·4DMF, 1; [Co3(btdc)3(pz)(dmf)2]·4DMF·1.5H2O, 2; [Co3(btdc)3(dmf)4]∙2DMF∙2H2O, 3 (bpy = 2,2′-bipyridyl, pz = pyrazine, dmf = N,N-dimethylformamide) were synthesized and structurally characterized. All compounds share the same trinuclear carboxylate building units {Co3(RCOO)6}, connected either by btdc2– ligands (1, 3) or by both btdc2– and pz bridging ligands (2). The permanent porosity of 1 was confirmed by N2, O2, CO, CO2, CH4 adsorption measurements at various temperatures (77 K, 273 K, 298 K), resulted in BET surface area 667 m2⋅g−1 and promising gas separation performance with selectivity factors up to 35.7 for CO2/N2, 45.4 for CO2/O2, 20.8 for CO2/CO, and 4.8 for CO2/CH4. The molar magnetic susceptibilities χp(T) were measured for 1 and 2 in the temperature range 1.77–330 K at magnetic fields up to 10 kOe. The room-temperature values of the effective magnetic moments for compounds 1 and 2 are μeff (300 K) ≈ 4.93 μB. The obtained results confirm the mainly paramagnetic nature of both compounds with some antiferromagnetic interactions at low-temperatures T < 20 K in 2 between the Co(II) cations separated by short pz linkers. Similar conclusions were also derived from the field-depending magnetization data of 1 and 2.

Unconventional Transport Properties of Reduced Tungsten Oxide WO2.9

The temperature and magnetic field dependence of resistivity in WO2.9 was investigated. The variation of resistivity with temperature displayed unusual features, such as a broad maximum around 230 K and a logarithmic increase of resistivity below 16 K. In the temperature range 16–230 K, we observed metallic-like behavior with a positive temperature coefficient. The combined analysis of resistivity and magnetoresistance (MR) data shows that these unusual transport properties of WO2.9 can be understood by considering the (bi)polaronic nature of charge carriers. In contrast to magnetization data, superconducting transition below Tc = 80 K was not detected in resistivity measurements, indicating that the superconductivity is localized in small regions that do not percolate. We found a strong increase in positive MR below 80 K. This effect is similar to that observed in underdoped cuprates, where the substantial increase of MR is attributed to superconducting fluctuations in small clusters. Therefore, the temperature dependence of MR indicates the presence of non-percolating superconducting clusters in WO2.9 below 80 K in agreement with magnetization data.

Nickel(II) complexes based on L-amino-acid-derived ligands: synthesis, characterization and study of the role of the supramolecular structure in carbon dioxide capture

The formation of the symmetrical μ3-carbonate-bridged self-assembled trinuclear NiII complex Na2{[Ni(LO)2(H2O)]3(μ3-CO3)} (LO is the carboxylate anion of a L-tyrosine derivative), involves atmospheric CO2 uptake. The asymmetric unit of the complex comprises an octahedral coordination for the NiII with two L-tyrosine-based ligands, a water molecule and one O atom of the carbonate bridge. The Ni3–μ3-CO3 core in this compound is the first reported of this kind according to the Cambridge Structural Database (CSD). The supramolecular structure is mainly sustained by hydrogen bonds developed by the phenolic functionality of the L-tyrosine moiety of one ligand and the carboxylate group of a neighbouring ligand. The crystal packing is then characterized by three interpenetrated supramolecular helices associated with a diastereoisomer of the type R-sup P, which is essential for the assembly process. Magnetic susceptibility and magnetization data support weak ferromagnetic exchange interactions within the novel Ni3–μ3-CO3 core. The NiII complex obtained under the same synthetic conditions but using the analogous ligand derived from the amino acid L-phenylalanine instead of L-tyrosine gives rise to to a mononuclear octahedral system. The results obtained for the different complexes demonstrate the role of the supramolecular structure regarding the CO2 uptake property for these NiII–amino-acid-based systems.

Chemical Synthesis of Rare Earth (La, Gd) Doped Cobalt Ferrite and a Comparative Analysis of Their Magnetic Properties

Lanthanum (La) and gadolinium (Gd) doped cobalt ferrite nanoparticles are synthesized using a soft chemical approach. The analysis of these ferrites using X-ray diffraction (XRD) and transmission electron microscopy (TEM) shows that lattice spacing decreases in the doped ferrite samples. Magnetization data indicates towards the decrease of saturation magnetisation but increase in coercivity with doping. Mössbauer spectroscopy measurements at room temperature indicate increased occupancy of trivalent cations at tetrahedral site. The addition of rare earth dopants reduces the hard-magnetic character of cobalt ferrite.

Formation of Tetranuclear Nickel(II) Complexes with Schiff-Bases: Crystal Structures and Magnetic Properties

The cubane-type structure is a typical representative of tetranuclear coordination compounds. In this work, two anionic Schiff-base ligands, (L1)2− and (L2)2−, each offering an O^N^O coordination pocket, ligate four NiII ions into a [Ni4O4] cubane core. The ligands are H2L1 = 2−[[(3-ethoxy-2−hydroxyphenyl) methylene]amino]benzenemethanol and H2L2 = 2−[[(5-fluoro-2−hydroxyphenyl)methylene]amino]benzenemethanol. In both compounds, [Ni4(L1)4(EtOH)4] (1) and [Ni4(L2)4(MeOH)4] (2), alkoxy oxygens of the ligands act in a bridging μ3-O binding mode. Magnetic susceptibility and magnetization data for compounds 1 and 2 are presented. The Ni–O–Ni bond angles of the cubane core determined from single crystal X-ray diffraction data play a key role for a magneto-structural correlation. Dominant intracube ferromagnetic behavior is observed, and the coupling parameters were determined for both compounds, leading to nonzero spin ground states in accordance with the broadly accepted bond angle guideline.

Effect of K Substitutions on Structural and Superconducting Properties in Bi1.6Pb0.4Sr2-xKxCa2Cu3O10+ Compounds

Effect of K substitutions on structural and superconducting properties in Bi-Pb-Sr-Ca-Cu-O (BPSCCO) system has been investigated. Bulk Bi1.6Pb0.4Sr2-xKxCa2Cu3O10+d (where x = 0.00; 0.04; 0.08 and 0.1) samples were fabricated by using the solid-state reaction method. Structural properties of the samples were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) measurement. All samples showed co-existence of Bi-2223 and Bi-2212 superconducting phases. Interestingly, a formation of the Bi-2223 was decelerated and that of the Bi-2212 was accelerated with increasing K content (x). Superconducting properties of the samples were characterized by using temperature dependences of resistance and field dependences of magnetization data. Both onset and offset transition temperatures were found to decrease, those were correlated to the decreases in residual resistance ratio (RRR). The 65 K magnetization curves of K- substituted samples were enlarged in comparison with that of the pure one. Enlargements of the magnetization curves were possibly attributed to the appearance of additional point-like defects generated by substitutions of K into Sr site. Keywords: BPSCCO, substitutions, flux pinning, defects.

Magnetocaloric effect and piezoresponse of engineered ferroelectric- ferromagnetic heterostructures

Present study reports the magnetocaloric effect (MCE) and piezoresponse of integrated ferroelectric-ferromagnetic heterostructures of PbZr0.52Ti0.48O3 (PZT) (5 nm)/ Bi-Sr-Ca-Cu2-OX (BSCCO) (5 nm)/ La0.67Sr0.33MnO3 (LSMO) (40 nm)/ MgO. Magnetic and pizoresponse behavior of the heterostructures are found to be governed by magneto-electric coupling and induced lattice strains. In addition, the MCE is studied using Maxwell equations from both Field Cooled (FC) and Zero Field Cooled (ZFC) magnetization data. Maximum MCE entropy change (|∆S|) of 42.6 mJkg-1K-1 (at 258 K) and 41.7 mJkg-1K-1 (at 269 K) are found corresponding to FC and ZFC data, respectively. The variation in maximum entropy change and corresponding temperatures for FC and ZFC data revealed that the application of a magnetic field can significantly contribute towards tuning of the MCE. Interestingly, these multilayered structures are found to sustain MCE over a broad temperature range, which makes them attractive for improved solid-state energy conversion devices.