Study on the Magnetocaloric Effect of Room Temperature Magnetic Refrigerant Material La0.5Pr0.5(Fe1−xCox)11.4Si1.6 and the Effect Arising from Co Doping on Its Curie Temperature

The arc-melting method was adopted to prepare the compound La_0.5Pr_0.5(Fe_1−xCo_x)_11.4Si_1.6 (x = 0, 0.02, 0.04, 0.06, 0.08), and the magnetocaloric effect of the compound was investigated. As indicated by the powder X-ray diffraction (XRD) results, after receiving 7-day high temperature annealing at 1373 K, all the compounds formed a single-phase cubic NaZn₁₃ crystal structure. As indicated by the magnetic measurement, the most significant magnetic entropy change |∆S_M(T)| of the sample decreased from 28.92 J/kg·K to 4.22 J/kg·K with the increase of the Co content under the 0–1.5 T magnetic field, while the Curie temperature T_C increased from 185 K to the room temperature 296 K, which indicated that this series of alloys are the room temperature magnetic refrigerant material with practical value. By using the ferromagnetic Curie temperature theory and analyzing the effect of Co doping on the exchange integral of these alloys, the mechanism that the Curie temperature of La_0.5Pr_0.5(Fe_1−xCo_x)_11.4Si_1.6 and La_0.8Ce_0.2(Fe_1−xCo_x)_11.4Si_1.6 increased with the increase in the Co content was reasonably explained. Accordingly, this paper can provide a theoretical reference for subsequent studies.     

Magnetic and Magnetocaloric Properties of Nano- and Polycrystalline Manganites La(0.7−x)EuxBa0.3MnO3

Here, we report synthesis and investigations of bulk and nano-sized La_(0.7−x)Eu_xBa_0.3MnO₃ (x ≤ 0.4) compounds. The study presents a comparison between the structural and magnetic properties of the nano- and polycrystalline manganites La_(0.7−x)Eu_xBa_0.3MnO₃, which are potential magnetocaloric materials to be used in domestic magnetic refrigeration close to room temperature. The parent compound, La_0.7Ba_0.3MnO₃, has Curie temperature T_C = 340 K. The magnetocaloric effect is at its maximum around T_C. To reduce this temperature below 300 K, we partially replaced the La ions with Eu ions. A solid-state reaction was used to prepare bulk polycrystalline materials, and a sol-gel method was used for the nanoparticles. X-ray diffraction was used for the structural characterization of the compounds. Transmission electron spectroscopy (TEM) evidenced nanoparticle sizes in the range of 40–80 nm. Iodometry and inductively coupled plasma optical emission spectrometry (ICP-OES) was used to investigate the oxygen content of the studied compounds. Critical exponents were calculated for all samples, with bulk samples being governed by tricritical mean field model and nanocrystalline samples governed by the 3D Heisenberg model. The bulk sample with x = 0.05 shows room temperature phase transition T_C = 297 K, which decreases with increasing x for the other samples. All nano-sized compounds show lower T_C values compared to the same bulk samples. The magnetocaloric effect in bulk samples revealed a greater magnetic entropy change in a relatively narrow temperature range, while nanoparticles show lower values, but in a temperature range several times larger. The relative cooling power for bulk and nano-sized samples exhibit approximately equal values for the same substitution level, and this fact can substantially contribute to applications in magnetic refrigeration near room temperature. By combining the magnetic properties of the nano- and polycrystalline manganites, better magnetocaloric materials can be obtained.     

Tuning of the Structure and Magnetocaloric Effect of Mn1−xZrxCoGe Alloys (Where x = 0.03, 0.05, 0.07, and 0.1)

The aim of the present work is to study the influence of a partial substitution of Mn by Zr in MnCoGe alloys. The X-ray diffraction (XRD) studies revealed a coexistence of the orthorhombic TiNiSi-type and hexagonal Ni₂In- type phases. The Rietveld analysis showed that the changes in lattice constants and content of recognized phases depended on the Zr addition. The occurrence of structural transformation was detected. This transformation was confirmed by analysis of the temperature dependence of exponent n given in the relation ΔS_M = C·(B_MAX)ⁿ. A decrease of the Curie temperature with an increase of the Zr content in the alloy composition was detected. The magnetic entropy changes were 6.93, 13.42, 3.96, and 2.94 J/(kg K) for Mn_0.97Zr_0.03CoGe, Mn_0.95Zr_0.05CoGe, Mn_0.93Zr_0.07CoGe, and Mn_0.9Zr_0.1CoGe, respectively. A significant rise in the magnetic entropy change for samples doped by Zr (x = 0.05) was caused by structural transformation.     

Magnetic and Magneto-Caloric Properties of the Amorphous Fe92−xZr8Bx Ribbons

Magnetic and magnetocaloric properties of the amorphous Fe_92−xZr₈B_x ribbons were studied in this work. Fully amorphous Fe₈₉Zr₈B₃, Fe₈₈Zr₈B₄, and Fe₈₇Zr₈B₅ ribbons were fabricated. The Curie temperature (T_c), saturation magnetization (M_s), and the maximum entropy change with the variation of a magnetic field (−ΔS_m^peak) of the glassy ribbons were significantly improved by the boron addition. The mechanism for the enhanced T_c and −ΔS_m^peak by boron addition was studied.     

Microstructure and Magnetocaloric Effect by Doping C in La-Fe-Si Ribbons

The melt-spun ribbons of LaFe_11.5Si_1.5C_x (x = 0, 0.1, 0.2, 0.3) compounds are prepared by the melt fast-quenching method. The doping of C is beneficial to the nucleation and precipitation of the La (Fe, Si)₁₃ phase, which is indicated by the microstructure observation and the elemental analysis. Subsequently, the ribbons of LaFe_11.5Si_1.5C_0.2 are annealed at different times, and the phase composition, the microstructures, and the magnetic properties are investigated. The LaFe_11.5Si_1.5C_0.2 ribbons annealed at 1273 K for 2 h achieved the best magnetic properties, and the maximum isothermal magnetic entropy change with a value of 9.45 J/(kg·K) upon an applied field of 1.5 T at an increased Curie temperature 255 K.     

Structure,Magnetocaloric Effect and Critical Behavior of the Fe60Co12Gd4Mo3B21 Amorphous Ribbons

The aim of the paper was to study the structure, magnetic properties and critical behavior of the Fe₆₀Co₁₂Gd₄Mo₃B₂₁ alloy. The X-ray diffractometry and the Mössbauer spectroscopy studies confirmed amorphous structure. The analysis of temperature evolution of the exponent n (ΔS_M = C·(B_max)ⁿ) and the Arrott plots showed the second order phase transition in investigated material. The analysis of critical behavior was carried out in order to reveal the critical exponents and precise T_C value. The ascertained critical exponents were used to determine the theoretical value of the exponent n, which corresponded well with experimental results.     

Regulation of Magnetocaloric Effect in Ni40Co10Mn40Sn10 Alloys by Using a Homemade Uniaxial Strain Pressure Cell

In this study, a homemade uniaxial strain pressure cell was designed to be directly used in the standard magnetometers whereby the magnetic properties of samples subjected to a uniaxial strain and magnetic field were characterized. Its feasibility has been demonstrated by the uniaxial strain control of the phase transition and magnetocaloric effect in Ni₄₀Co₁₀Mn₄₀Sn₁₀ (NCMS) alloys. With the assistance of a uniaxial strain of ~0.5%, the cooling temperature span of NCMS alloys is broadened by 2 K, and the refrigeration capacity under a 3 T magnetic field change increases from 246 to 277 J/kg. This research provides not only direct experimental assistance for the tuning of phase transition by the uniaxial strain but also possibilities for studying the coupled caloric effect in first-order phase transition materials under a combined uniaxial strain and magnetic field by the thermodynamic analysis.     

Antiferromagnet–Ferromagnet Transition in Fe1−xCuxNbO4

Iron niobates, pure and substituted with copper (Fe_1−xCu_xNbO₄ with x = 0–0.15), were prepared by the solid-state method and characterized by X-ray diffraction, Raman spectroscopy, and magnetic measurements. The results of the structural characterizations revealed the high solubility of Cu ions in the structure and better structural stability compared to the pure sample. The analysis of the magnetic properties showed that the antiferromagnetic–ferromagnetic transition was caused by the insertion of Cu²⁺ ions into the FeNbO₄ structure. The pure FeNbO₄ structure presented an antiferromagnetic ordering state, with a Néel temperature of approximately 36.81K. The increase in substitution promoted a change in the magnetic ordering, with the state passing to a weak ferromagnetic order with a transition temperature (T_c) higher than the ambient temperature. The origin of the ferromagnetic ordering could be attributed to the increase in super-exchange interactions between Fe/Cu ions in the Cu²⁺-O-Fe³⁺ chains and the formation of bound magnetic polarons in the oxygen vacancies.     

The Low-Field Microwave Absorption in EMR Spectra for Ni50−xCoxMn35.5In14.5 Ribbons

This paper contains a detailed study of low-field microwave absorption, which is observed in EMR spectra registered for a series of Ni50−xCoxMn35.5In14.5 (x=0,3,5) Heusler alloys polycrystalline in situ and annealed at 1173 K ribbons. The LFMA spectra for all ribbons were performed at X-band (∼9.5 GHz), at temperatures below Curie temperature. Additionally, for annealed Ni45Co5Mn35.5In14.5 ribbons, the LFMA signal dependencies of the external magnetic field modulation amplitude, modulation frequency, microwave power and microwave magnetic field phase were registered. These results confirm the resonant character of LFMA. To determine the basic EMR parameters, such as linewidth and resonance field, the experimental data were fitted by the Dyson function. The LFMA signal is satisfactorily matched by the two lines, and the variability of the component lines with temperature is remarkable.     

Atomic Interactions and Order–Disorder Transition in FCC-Type FeCoNiAl1−xTix High-Entropy Alloys

Single-phase high-entropy alloys with compositionally disordered elemental arrangements have excellent strength, but show a serious embrittlement effect with increasing strength. Precipitation-hardened high-entropy alloys, such as those strengthened by L1₂-type ordered intermetallics, possess a superior synergy of strength and ductility. In this work, we employ first-principles calculations and thermodynamic simulations to explore the atomic interactions and order–disorder transitions in FeCoNiAl_1−xTi_x high-entropy alloys. Our calculated results indicate that the atomic interactions depend on the atomic size of the alloy components. The thermodynamic stability behaviors of L1₂ binary intermetallics are quite diverse, while their atomic arrangements are short-range in FeCoNiAl_1−xTi_x high-entropy alloys. Moreover, the order–disorder transition temperatures decrease with increasing Ti content in FeCoNiAl_1−xTi_x high-entropy alloys, the characteristics of order–disorder transition from first-principles calculations are in line with experimental observations and CALPHAD simulations. The results of this work provide a technique strategy for proper control of the order–disorder transitions that can be used for further optimizing the microstructure characteristics as well as the mechanical properties of FeCoNiAl_1−xTi_xhigh-entropy alloys.     

Low-Pb High-Piezoelectric Ceramic System (1−x)Ba(Zr0.18Ti0.82)O3–x(Ba0.78Pb0.22)TiO3

Piezoelectric materials, especially Pb-based piezoelectric materials, are widely used in the key components of sensors, actuators, and transducers. Due to the rising concern of the toxicity of Pb, global legislation has been adopted to restrict the use of Pb. Given that the available Pb-free piezoelectric materials cannot replace the Pb-based ones for various reasons, we designed and fabricated a low-Pb piezoelectric solid-solution ceramic system, (1–x)Ba(Zr_0.18Ti_0.82)O₃–x(Ba_0.78Pb_0.22)TiO₃ (denoted as BZ_0.18T–xBP_0.22T herein). The crystal structure, ferroelectric, dielectric, and piezoelectric properties of the BZ_0.18T–xBP_0.22T system were systematically studied. With the increase in BP_0.22T content, the structure of the samples changed from a rhombohedral phase to a tetragonal phase; the intermediate composition x = 0.5 was located at the morphotropic phase boundary of the system and corresponded to the state with the coexistence of the rhombohedral and tetragonal phases. Moreover, x = 0.5 exhibited the optimum comprehensive properties among all the samples, with a piezoelectric coefficient d₃₃ of 240 pC/N, a maximum dielectric temperature Tm of 121.1°C, and a maximum polarization Pm of 15 μC/cm². Our work verifies the validity of the route to design low-Pb high-piezoelectric materials and may stimulate the interests for exploring new low-Pb high-performance ferroelectric and piezoelectric materials.     

Magnetic and Magnetostrictive Behaviors of Laves-Phase Rare-Earth—Transition-Metal Compounds Tb1−xDyxCo1.95

The magnetic morphotropic phase boundary (MPB) was first discovered in Laves-phase magnetoelastic system Tb–Dy–Co alloys (PRL 104, 197201 (2010)). However, the composition-dependent and temperature-dependent magnetostrictive behavior for this system, which is crucial to both practical application and the understanding of transitions across the MPB, is still lacking. In this work, the composition-dependence and temperature-dependence of magnetostriction for Tb_1−xDy_xCo_1.95 (x = 0.3~0.8) are presented. In a ferrimagnetic state (as selected 100 K in the present work), the near-MPB compositions x = 0.6 and 0.7, exhibit the largest saturation magnetization M_S and the lowest coercive field H_C; by contrast, the off-MPB composition x = 0.5, exhibits the largest magnetostriction, the lowest M_S, and the largest H_C. Besides, a sign change of magnetostriction is observed, which occurs with the magnetic transition across the MPB. Our results suggest the combining effect from the lattice strain induced from structure phase transition, and the influence of the MPB on magnetocrystalline anisotropy. This work may stimulate the research interests on the transition behavior around the MPB and its relationship with physical properties, and also provide guidance in designing high-performance magnetostrictive materials for practical applications.     

Phase Composition,Microstructure, Multiple Shape Memory Effect of TiNi50−xVx (x = 1; 2; 4 at.%) System Alloys

The phase composition, microstructure, and multiple shape memory effect of TiNi_50−xV_x alloys were studied in this work. The phase composition of the TiNi_50−xV_x system is the TiNi matrix, spherical particles of TiNiV, the secondary phase Ti₂Ni(V). Doping of TiNi alloys with vanadium atoms leads to an increase in the stability of high-temperature B2 and rhombohedral R-phases. An increase in the atomic volume with an increase in the concentration of the alloying element V from 1 to 4 at.% was established. Vanadium doping of the Ti–Ni–V system alloys leads to an increase in the temperature interval for the manifestation of the multiple shape memory effect. It has been established that the value of the reversible deformation of the multiple shape memory effect both during heating and during cooling increases linearly from 2 to 4% with an increase in the vanadium concentration.     

Effect of Co Substitution and Thermo-Magnetic Treatment on the Structure and Induced Magnetic Anisotropy of Fe84.5−xCoxNb5B8.5P2 Nanocrystalline Alloys

In the present work, we investigated in detail the thermal/crystallization behavior and magnetic properties of materials with Fe_84.5-xCo_xNb₅B_8.5P₂ (x = 0, 5, 10, 15 and 20 at.%) composition. The amorphous ribbons were manufactured on a semi-industrial scale by the melt-spinning technique. The subsequent nanocrystallization processes were carried out under different conditions (with/without magnetic field). The comprehensive studies have been carried out using differential scanning calorimetry, X-ray diffractometry, transmission electron microscopy, hysteresis loop analyses, vibrating sample magnetometry and Mössbauer spectroscopy. Moreover, the frequency (up to 300 kHz) dependence of power losses and permeability at a magnetic induction up to 0.9 T was investigated. On the basis of some of the results obtained, we calculated the values of the activation energies and the induced magnetic anisotropies. The X-ray diffraction results confirm the surface crystallization effect previously observed for phosphorous-containing alloys. The in situ microscopic observations of crystallization describe this process in detail in accordance with the calorimetry results. Furthermore, the effect of Co content on the phase composition and the influence of annealing in an external magnetic field on magnetic properties, including the orientation of the magnetic spins, have been studied using various magnetic techniques. Finally, nanocrystalline Fe_64.5Co₂₀Nb₅B_8.5P₂ cores were prepared after transverse thermo-magnetic heat treatment and installed in industrially available portable heating equipment.     

Athermal ω Phase and Lattice Modulation in Binary Zr-Nb Alloys

To further explore the potential of Zr-based alloys as a biomaterial that will not interfere with magnetic resonance imaging (MRI), the microstructural characteristics of Zr-xat.% Nb alloys (10 ≤ x ≤ 18), particularly the athermal ω phase and lattice modulation, were investigated by conducting electrical resistivity and magnetic susceptibility measurements and transmission electron microscopy observations. The 10 Nb alloy and 12 Nb alloys had a positive temperature coefficient of electrical resistivity. The athermal ω phase existed in 10 Nb and 12 Nb alloys at room temperature. Alternatively, the 14 Nb and 18 Nb alloys had an anomalous negative temperature coefficient of the resistivity. The selected area diffraction pattern of the 14 Nb alloy revealed the co-occurrence of ω phase diffraction and diffuse satellites. These diffuse satellites were represented by g_β + q when the zone axis was [001] or [113], but not [110]. These results imply that these diffuse satellites appeared because the transverse waves consistent with the propagation and displacement vectors were q = <ζ ζ¯ 0>* for the ζ~1/2 and <110> directions. It is possible that the resistivity anomaly was caused by the formation of the athermal ω phase and transverse wave. Moreover, control of the athermal ω-phase transformation and occurrence of lattice modulation led to reduced magnetic susceptibility, superior deformation properties, and a low Young’s modulus in the Zr-Nb alloys. Thus, Zr-Nb alloys are promising MRI-compatible metallic biomaterials.     

The Characteristic of Fe as a β-Ti Stabilizer in Ti Alloys

It is well known that adding elements, especially β-Ti stabilizers, are holding a significant effect on titanium alloy strength due to the solution and precipitate strengthening mechanisms. In order to reveal the Fe strengthening mechanism in titanium, this study investigate the effect of Fe on the stability of β-Ti and the phase transition between α, β and ω phase with first-principle calculations. According to our study, Fe is a strong β-Ti phase stabilizer could owe to the 3d orbital into e_g and t_2g states which results in strong hybridization between Fe-d orbital and Ti-d orbital. The phase transition from ω to β or from α to β becomes easier for Fe-doped Ti compared to pure titanium. Based on our results, it is found that one added Fe atom can lead the phase transition (ω → β) of at least nine titanium atoms, which further proves that Fe has a strong stabilizing effect on β-Ti phase. This result provides a solid guide for the future design of high-strength titanium with the addition of Fe.     

EPR Spectra of Sintered Cd1−xCrxTe Powdered Crystals with Various Cr Content

In this paper, we show a simple method of producing ferromagnetic materials with a Curie temperature above room temperature. The electron paramagnetic resonance (EPR) spectra of Cd_1−xCr_xTe (0.002 < x < 0.08) were measured with a dependence on temperature (82 K < T < 381 K). Obtained EPR lines were fitted to a Lorentz-shaped curve. The temperature dependencies of the parameters of the EPR lines, such as the peak-to-peak linewidth (H_pp), the intensity (A), as well as the resonance field (H_r), were studied. Ferromagnetism was noticed in samples at high temperatures (near room temperature). For a sample with a nominal concentration of chrome of x = 0.05, a very strong intrinsic magnetic field is observed. The value of the effective gyromagnetic factor for this sample is g_e = 30 at T = 240 K. An increase of chrome concentration above x = 0.05 reduces the ferromagnetic properties considerably. Analysis of the temperature dependencies of the integral intensity of EPR spectra was carried out using the Curie–Weiss law and the paramagnetic Curie temperature was obtained.     

Hf1−xSixO2 Nanocomposite Coatings Prepared by Ion-Assisted Co-Evaporation Process for Low-Loss and High-LIDT Optics

Hf_1−xSi_xO₂ nanocomposites with different SiO₂ doping ratios were synthesized using an ion-assisted co-evaporation process to achieve dense amorphous Hf_1−xSi_xO₂ coatings with low loss and a high laser-induced damage threshold (LIDT). The results showed that the Hf_1−xSi_xO₂ nanocomposites (x ≥ 0.20) exhibited excellent comprehensive performance with a wide band gap and a dense amorphous microstructure. High-temperature annealing was carried out to ensure better stoichiometry and lower absorption. Precipitation and regrowth of HfO₂ grains were observed from 400 °C to 600 °C during annealing of the Hf_0.80Si_0.20O₂ nanocomposites, resulting in excessive surface roughness. A phenomenological model was proposed to explain the phenomenon. The Hf_1−xSi_xO₂ nanocomposites (x = 0.3 and 0.4) maintained a dense amorphous structure with low absorption after annealing. Finally, a 1064-nm Hf_0.70Si_0.30O₂/SiO₂ high-performance reflector was prepared and achieved low optical loss (15.1 ppm) and a high LIDT (67 J/cm²).     

Sequence and Characteristics of Atomic Ordering in Ni2Mn1−xCuxGa Ferromagnetic Shape Memory Alloys

Post-quench atomic reordering processes undergone by Ni₂Mn_1−xCu_xGa alloys have been characterized in detail. The obtained results corroborate the hypothesis that proposes an atomic ordering process additional to the B2↔L2₁ one, consisting of the relocation in the Mn sublattice of Cu atoms misplaced by quench in the Ni sublattice. In addition, the results suggest that the ordering of the Cu atoms and the L2₁ ordering can occur in different sequences depending on the starting state of order. The analysis of the saturation magnetization validates the occurrence of two types of atomic movements; the values corresponding to different post-quench stages have been compared with those calculated for different atomic configurations, supporting the relocation mechanism of Cu atoms as the most plausible mechanism. The effect of the quenching temperature on the reordering processes has been also studied, and an assessment of the degree of quenched disorder is provided, suggesting the existence of an order–disorder transition associated with Cu atoms ordering. Finally, the effect of the Cu amount has been analyzed, confirming that a greater amount of Cu intensifies the process associated to ordering of Cu atoms, which takes place even in martensite.     

Structural,Magnetic, Dielectric and Piezoelectric Properties of Multiferroic PbTi1−xFexO3−δ Ceramics

PbTi_1−xFe_xO_3−δ (x = 0, 0.3, 0.5, and 0.7) ceramics were prepared using the classical solid-state reaction method. The investigated system presented properties that were derived from composition, microstructure, and oxygen deficiency. The phase investigations indicated that all of the samples were well crystallized, and the formation of a cubic structure with small traces of impurities was promoted, in addition to a tetragonal structure, as Fe³⁺ concentration increased. The scanning electron microscopy (SEM) images for PbTi_1−xFe_xO_3−δ ceramics revealed microstructures that were inhomogeneous with an intergranular porosity. The dielectric permittivity increased systematically with Fe³⁺ concentration, increasing up to x = 0.7. A complex impedance analysis revealed the presence of multiple semicircles in the spectra, demonstrating a local electrical inhomogeneity due the different microstructures and amounts of oxygen vacancies distributed within the sample. The increase of the substitution with Fe³⁺ ions onto Ti⁴⁺ sites led to the improvement of the magnetic properties due to the gradual increase in the interactions between Fe³⁺ ions, which were mediated by the presence of oxygen vacancies. The PbTi_1−xFe_xO_3−δ became a multifunctional system with reasonable dielectric, piezoelectric, and magnetic characteristics, making it suitable for application in magnetoelectric devices.