Search Results (128)

This paper presents a comprehensive investigation into the synthesis, morphological characteristics, electrical conductivity, dielectric behavior, and electrocatalytic activity of perovskite-structured iron manganite (FeMnO₃), with a specific focus on its performance in the hydrogen evolution reaction (HER). FeMnO₃(FMO) nanoparticles (NPs) were synthesized using a sol–gel-type Pechini method and characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and field-emission scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (FESEM-EDS). XRD analysis confirmed the formation of a crystalline structure with cubic symmetry assigned to the Ia-3 space group, with an average crystallite size of 52.47 nm. FESEM images revealed a relatively uniform morphology with an average particle diameter of 55.84 nm. The redox and oxidation states of Fe and Mn can be studied by temperature-programmed oxidation (TPO-O₂) in order to understand oxygen uptake and metal oxidation processes occurring within the FMO lattice. The dielectric constant, dielectric loss, electric modulus and electrical conductivity were calculated as a function of frequency and temperature using a Novocontrol Alpha-A broadband dielectric spectrometer (Novocontrol system) coupled with the LCR-800 precision meter. The dielectric data reveal that the FMO has semiconducting behavior with dominant charge- or ionic-relaxation processes. The electrocatalytic activity toward the HER was evaluated using linear sweep voltammetry (LSV), with the working electrode modified by an FMO catalyst ink. The material exhibited significant catalytic activity within the HER potential range, and an increase in the number of cycles led to stabilized current and enhanced hydrogen evolution. These results highlight the stability of FeMnO₃ for hydrogen generation. Full article

Experimental and numerical investigations of the alternating current (AC) susceptibility, $\mathsf{\chi }\left(H\right) ~ \mathrm{d}M/\mathrm{d}H,$ examined multigrain La_0.66Sr_0.34MnO₃ (LSMO) thin films (thickness d = 250 nm) grown by radio-frequency (RF) magnetron sputtering on lattice-mismatched yttria-stabilized zirconia YSZ(001) substrates. The films exhibit a columnar structure comprising two types of grains, with (001)- and (011)-oriented planes of a pseudocubic lattice aligned parallel to the film surface. Field- and angle-dependent AC susceptibility measurements at 78 K reveal characteristic peak- and tip-like anomalies, attributed to contributions from grains with three distinct directions of easy magnetization axes within the film plane. Numerical modeling based on the transverse susceptibility theory for single-domain ferromagnetic grains, incorporating first- and second-order anisotropy constants, corroborates the experimental findings and elucidates the role of different grain types in magnetization switching and AC susceptibility response. This study provides a quantitative determination of the three in-plane easy magnetization axes in LSMO/YSZ(001) films and clarifies their influence on the magnetization dynamics of multigrain thin films. The demonstrated control over multigrain LSMO/YSZ(001) thin films with distinct in-plane easy magnetization axes and well-characterized AC susceptibility suggests potential applications in magnetic memory, spintronic devices, and precision magnetic sensing. Full article

Egg white was chosen as a renewable, non-toxic agent for the synthesis of FeMn₂O₄ spinel pre-catalysts to avoid the use of critical transition metals such as Ni and Co. However, synthesizing phase-pure FeMn₂O₄ remains challenging due to (i) the requirement of low oxygen partial pressures to counter rapid reoxidation of Mn₃O₄ in the presence of iron oxides, which can be achieved by the preferred oxidation of the egg white during the calcination, and (ii) the probable formation of Fe₃O₄ and Mn₃O₄ during intermediate steps in the reaction, leading to multiphase spinel formation caused by a miscibility gap between the spinels. In contrast, spinels with Ni, Co, Zn, or Al are phase-pure. Egg white has significant environmental impacts in the synthesis of all spinel manganites, as assessed from a life-cycle perspective, which can exceed those of petroleum-based agents such as ethylenediaminetetraacetic acid (EDTA) in most impact categories. Therefore, our results show that the investigated synthesis route is not more sustainable, and we demonstrate that implementing quantitative evaluation of environmental impacts already at an early stage is essential to determine whether a synthesis is truly sustainable. Full article

Hexagonal rare-earth manganites, as prototypical improper ferroelectrics in which structural distortions give rise to ferroelectricity, exhibit unique physical phenomena that are absent in conventional proper ferroelectrics. Owing to their Z₂ × Z₃ topologically protected ferroelectric domain structure, characterized by the convergence of six domains at vortex core, hexagonal manganites can host charged domain walls exhibiting multiple distinct conductive states and unconventional physical effects such as the half-wave rectification effect within a single bulk single crystal, opening up promising avenues for the practical applications. Moreover, as an excellent experimental platform for verifying the Kibble–Zurek mechanism, hexagonal manganites not only possess a broad application potential but also embody rich and fundamental physical insights. Given a series of recent advances in this field, it is essential to systematically summarize and discuss the key findings, current progress, and future research perspectives concerning the hexagonal manganite system. In this review, the origin of ferroelectricity in hexagonal manganites are first clarified, followed by a discussion of the formation and transformation mechanisms of unique ferroelectric domain structures, as well as the intrinsic mechanical properties. Subsequently, the manipulation of topological defects are compared, including electric fields, thermal treatment, oxygen vacancies, and stress–strain fields. Building upon these discussions, the distinct physical effects observed in hexagonal manganites are comprehensively summarized, such as domain wall conductance, dielectric and ferroelectric properties, and thermal conductivity. Finally, based on a detailed summary of the major achievements, the unresolved issues that warrant further investigation are highlighted, thereby offering guidance for future research directions and providing valuable insights for the broader study of ferroelectric materials. Full article

A-site-ordered quadruple perovskite manganites, AMn₇O₁₂, show many interesting physical phenomena, including orbital and spin modulations, spin-induced multiferroic properties, and competitions between different magnetic ground states. Doping with Cu²⁺ can result in colossal magnetoresistance properties, ferrimagnetism, and additional structural modulations producing electric–dipole helicoidal textures. Many previous works have focused on large-concentration doping, reaching ACu₃Mn₄O₁₂ compositions. Small-concentration doping has been investigated in a limited number of systems, e.g., in BiCu_xMn_7−xO₁₂. In this work, we investigated solid solutions of NdCu_xMn_7−xO₁₂ with x = 0.1, 0.2, and 0.3, prepared at 6 GPa and 1500 K. Specific heat measurements detected three magnetic transitions at x = 0 (at T_N3 = 9 K, T_N2 = 12 K, and T_N1 = 84 K) and two transitions at x = 0.1 (at T_N2 = 10 K and T_N1 = 78 K), while only one transition was found at x = 0.2 (T_N1 = 72 K) and x = 0.3 (T_N1 = 65 K). Differential scanning calorimetry (DSC) measurements showed sharp and strong peaks near T_OO = 664 K at x = 0, corresponding to an orbital-order (OO) structural transition from I2/m to Im-3 symmetry. DSC anomalies were significantly broadened and their intensities were significantly reduced at x = 0.1–0.3, and structural transitions were observed near T_OO = 630 K at x = 0.1, T_OO = 600 K at x = 0.2, and T_OO = 570 K at x = 0.3. The x = 0.1 sample clearly showed double-peak features on the DSC curves near T_OO because of the presence of two close phases. High-resolution synchrotron powder X-ray diffraction studies gave strong evidence that phase separation phenomena took place in the x = 0.1–0.3 samples, where two I2/m phases with an approximate ratio of 1:1 were present (e.g., a = 7.47143 Å, b = 7.36828 Å, c = 7.46210 Å, and β = 90.9929° for one phase and a = 7.46596 Å, b = 7.37257 Å, c = 7.45756 Å, and β = 90.9328° for the second phase at x = 0.3). The Curie–Weiss temperature changed from negative (for x = 0, 0.1, and 0.2) to positive (for x = 0.3). T_OO, T_N1, the Curie–Weiss temperature, and magnetization (at 5 K and 70 kOe) changed almost linearly with x. Full article

This study presents a dual-phase lanthanum manganite ceramic composite based on a mixture of equal weight ratios of La_0.7Ca_0.2Sr_0.1MnO₃ and La_0.7Ca_0.25Sr_0.05MnO₃ designed to enhance the magnetocaloric effect (MCE) of individual compounds, under a low magnetic field (≤18 kOe). X-ray diffraction (XRD) analysis revealed the coexistence of two orthorhombic manganite phases corresponding to the individual compounds, with no secondary phases detected. Temperature-dependent magnetization measurements in the composite evidenced two Curie temperatures at 286.8 K and 307.6 K, reflecting the effect of Ca²⁺ and Sr²⁺ concentrations. Arrott plots and β parameters confirmed that the phase transition is of second order. Although the maximum magnetic entropy change (ΔS_M) of the composite is slightly lower than that of the individual manganite phases, its relative cooling power (RCP) reaches 188.82 J·kg⁻¹, with an extended operational temperature window (OTW) of approximately 85 K, spanning from around 243 K to 328 K. This broad OTW enables efficient operation over a wider temperature range compared to similar materials, such as the individual La_0.7Ca_0.2Sr_0.1MnO₃ and La_0.7Ca_0.25Sr_0.05MnO₃ compounds, which exhibit an RCP of 55.24 and 65.12 J·kg⁻¹, respectively, under a comparable magnetic field (~18 kOe). The improved magnetocaloric performance is attributed to interfacial exchange coupling and strain-mediated effects that broaden the ΔS_M response and generate a non-additive RCP. These results demonstrate that interphase coupling and microstructural tuning effectively broaden the operating temperature range for magnetic refrigeration under moderate fields, making this composite a strong candidate for practical cooling applications. Full article

The appearance of spin-induced ferroelectric polarization in the so-called type-II multiferroic materials has received a lot of attention. The nature and mechanisms of such polarization were intensively studied using perovskite rare-earth manganites, RMnO₃, as model systems. Later, multiferroic properties were discovered in some RFeO₃ perovskites and possibly in some RCrO₃ perovskites. However, R₂NiMnO₆ double perovskites have ferromagnetic structures that do not break the inversion symmetry. It was found recently that more complex magnetic structures are realized in A-site-ordered quadruple perovskites, RMn₃Ni₂Mn₂O₁₂. Therefore, they have the potential to be multiferroics. In this work, dielectric properties in magnetic fields up to 9 T were investigated for such perovskites as RMn₃Ni₂Mn₂O₁₂ with R = Ce to Ho and for BiMn₃Ni₂Mn₂O₁₂. The samples with R = Bi, Ce, and Nd showed no dielectric anomalies at all magnetic fields, and the dielectric constant decreases with decreasing temperature. The samples with R = Sm to Ho showed qualitatively different behavior when the dielectric constant started increasing with decreasing temperature below certain temperatures close to the magnetic ordering temperatures, T_N. This difference could suggest different magnetic ground states. The samples with R = Eu, Dy, and Ho still showed no anomalies on the dielectric constant. On the other hand, peaks emerged at T_N on the dielectric constant in the R = Sm sample from about 2 T up to the maximum available field of 9 T. The Gd sample showed peaks on dielectric constant at T_N between about 1 T and 7 T. Transition temperatures increase with increasing magnetic fields for R = Sm and decrease for R = Gd. These findings suggest the presence of magnetic-field-induced multiferroic states in the R = Sm and Gd samples with intermediate ionic radii. Dielectric properties at different magnetic fields are also reported for Lu₂NiMnO₆ for comparison. Full article

Spinel-structured hausmannite (Mn(II)Mn(III)₂O₄) is a vital intermediate in Mn mineralogy and a key player in redox chemistry in the environment. Its transformation into other Mn oxides is a critical factor in controlling its environmental occurrence and reactivity. Yet structural impurities and solution pH, as well as the fate of impurities during transformation, which influence hausmannite transformation processes and products, remain largely unknown. In the present work, we address this knowledge gap by investigating pristine and metal-substituted hausmannite, specifically nickel (Ni) or cobalt (Co), equilibrated at two time periods (8 h and 30 days) and three different pH levels (4, 5, and 7). Solution chemistry data revealed that both the equilibration period and pH had a significant impact on hausmannite dissolution rates and the concomitant repartitioning of Ni or Co. Hausmannite with Ni or Co substitution exhibited lower dissolution rates than pristine mineral under acidic conditions. Mineralogy and crystal chemistry data indicated that hausmannite was the major host phase after 30-day equilibration, followed by minor transformed products, including birnessite and manganite. Although minor, birnessite became more abundant than manganite at low pHs. Analytical high-resolution transmission electron microscopy (HRTEM) analyses revealed a poorly crystalline, nano-scaled MnO₂ formed from hausmannite and the majority of metal impurities remaining in the host hausmannite. Yet Co was associated with both hausmannite and the newly formed birnessite, whereas Ni was only found with hausmannite, indicating the strong sequestration of Co by Mn(II/III) and Mn(IV) mineral phases. This study highlights the significant impacts of metal impurities and pH on the stability of hausmannite and its transformation into birnessite, as well as the control of Mn-oxide minerals on the solubility and sequestration of transition metals in the environment. Full article

For the first time, neodymium nickel manganites NdNa₂NiMnO₅ and NdK₂NiMnO₅ were synthesized via the solid-state interaction method, and they crystallize in a cubic system. Using experimental dynamic calorimetry in the temperature range of 298.15–673 K, the temperature dependences of the heat capacity of NdNa₂NiMnO₅ and NdK₂NiMnO₅ were studied. At 423 K, both compounds exhibited anomalous heat capacity jumps on the C⁰_p~f(T) dependency, likely corresponding to second-order phase transitions. Considering the phase transition temperatures, equations for the temperature dependence of heat capacity were derived, accurately describing the experimental data. Based on the experimental C⁰_p(T) data and calculated S⁰ (298.15) values, temperature dependences of C⁰_p(T) and the thermodynamic functions S⁰(T), H°(T)–H⁰(298.15), and Φ^xx(T) were determined for the studied compounds within the 298.15–673 K range. The analysis of electrophysical data confirmed the semiconducting and metallic nature of the conductivity, as well as identified the band gap and activation energy of conductivity. These results are valuable for the application of these materials in electronics and for controlling conductivity. Full article

Manganese oxides (manganites) are among the most studied materials in condensed matter physics due to the famous colossal magnetoresistance and very rich phase diagrams characterized by strong competition between ferromagnetic (FM) metallic and antiferromagnetic (AFM) insulating phases. One of the key questions that remains open even after more than thirty years of intensive research is the exact conductivity mechanism in insulating as well as in metallic phases and its relation to the corresponding magnetic structure. In order to shed more light on this problem, here, we report magnetotransport measurements on sintered nanocrystalline samples of the very poorly explored manganites ${\mathrm{Ca}}_{1-x}{\mathrm{Gd}}_x{\mathrm{MnO}}_3$ with $x=0.05$ and $x=0.10$, in the temperature range 2–300 K, and in magnetic fields up to 16 T. Our results indicate that both compounds at low temperatures exhibit metallic behavior with a peculiar resistivity upturn and a large negative magnetoresistance. We argue that such behavior is consistent with a Kondo-like scattering on Gd impurities coupled with the percolation of FM metallic regions within insulating AFM matrix. Full article

The Curie temperature (Tc) of LaMnO₃-based perovskites is one of the most important properties associated with their magnetic and spintronic applications. The search for new perovskites with even higher Tc is a challenging problem in material design. Through the systematic optimization of support vector regression (SVR) architecture, we establish a predictive framework for determining the Curie temperature (Tc) of doped LaMnO₃ perovskites, leveraging fundamental atomic descriptors. The correlation coefficient (R) between the predicted and experimental Curie temperatures demonstrated high values of 0.9111 when evaluated through the leave-one-out cross-validation (LOOCV) approach, while maintaining a robust correlation of 0.8385 on the independent test set. The subsequent high-throughput screening of perovskite compounds exhibiting higher Curie temperatures was implemented via our online computation platform for materials data mining (OCPMDM), enabling the rapid identification of candidate materials through systematic screening protocols. The findings demonstrate that machine learning exhibits significant efficacy and cost-effectiveness in identifying lanthanum manganite perovskites with elevated Tc, as validated through comparative computational and empirical analyses. Furthermore, a web-based computational infrastructure is implemented for the global dissemination of the predictive framework, enabling the open-access deployment of the validated machine learning model. Full article

Polypyrrole (PPy)-doped bismuth calcium manganite (BCM) nanocomposites were synthesized by chemical polymerization. The amorphous nature of the polypyrrole and the monoclinic crystal structure of the BCM particles (35–65 nm) were confirmed by various microstructural, X-ray powder, and spectroscopy techniques. The DC conductivity analysis via the correlated barrier-hopping (CBH) model and Mott’s variable-range hopping (MVRH) model showed that the nanocomposites exhibited ionic conduction. Activation energies, evaluated from the Arrhenius plots, showed that PPy/BCM-30 (30 wt.% of BCM) had the minimum value of 0.09 eV, indicating maximum conductivity and normal NTCR behavior, with resistance decreasing with temperature. The CBH model described the conduction process, and the AC conductivity measurements indicated that the conductivity was frequency-independent at lower frequencies but became dispersive and frequency-dependent at higher frequencies, conforming to Jonscher’s power law. The study revealed that the transport of electrical charge in the material followed the correlated barrier-hopping (CBH) model. These results demonstrate how promising PPy/BCM nanocomposites are for energy storage, sensors, and electronic materials. Full article

The use of perovskite manganite nanoparticles in magnetic hyperthermia has attracted significant attention due to their tunable magnetic properties and high specific absorption rate (SAR). In this work, we present a combined experimental and theoretical investigation of the frequency- and amplitude-dependent magnetic heating behavior of La_0.51Sr_0.49MnO₃ (LSMO) and Dy-doped La_0.51Dy_0.045Sr_0.445MnO₃ (DLSMO) nanoparticles. The nanoparticles were synthesized via the sol–gel method and characterized by XRD and SEM, while SAR values were experimentally evaluated under varying magnetic field strengths (60–120 Oe) and frequencies (150–300 kHz). In parallel, theoretical modeling based on Néel and Brownian relaxation mechanisms was employed to predict SAR behavior as a function of particle size, magnetic anisotropy, and fluid viscosity. The results reveal that Dy doping enhances magnetic anisotropy, which modifies the relaxation dynamics and leads to a reduction in SAR. The model identifies the optimal nanoparticle size (~18–20 nm) and ferrofluid viscosity to maximize heating efficiency. This combined approach provides a comprehensive framework for designing and optimizing perovskite-based nanoparticles for magnetic hyperthermia applications. Full article

By leveraging machine learning insights from prior perovskite studies and employing the sol–gel method, we successfully synthesized two novel perovskite nanoceramics—M_0.5 Ca_0.25Mg_0.25MnO₃ (M = La, Pr)—as multifunctional nanomaterials. X-ray diffraction (XRD) confirmed their orthorhombic Pnma crystal structure. The Williamson–Hall method estimated average particle sizes of 59.5 nm for PCMMO and 21.8 nm for LCMMO, while the Scherrer method provided corresponding values of 32.59 nm and 20.43 nm. SEM, UV-Vis, and FTIR analyses validated the chemical composition, homogeneity, and optical properties of the synthesized compounds, revealing band gaps of 3.25 eV (LCMMO) and 3.71 eV (PCMMO) with Urbach energies of 0.29 eV and 0.26 eV, respectively. These findings provide valuable insights into the structural and optical properties of LCMMO and PCMMO, highlighting their potential as multifunctional materials for advanced device applications. Full article

This study presents a system for precisely measuring pulsed magnetic fields with high amplitude and microsecond duration with minimal interference. The system comprises a probe with an advanced magnetic field sensor and a measurement unit for signal conversion, analysis, and digitization. The sensor uses a thin nanostructured manganite La-Sr-Mn-O film exhibiting colossal magnetoresistance, which enables precise magnetic field measurement independent of its orientation. Films with different compositions were optimized and tested in pulsed magnetic fields. The measurement unit includes a pulsed voltage generator, an ADC, a microcontroller, and an amplifier unit. Two versions of the measurement unit were developed: one with a separate amplifier unit configured for the sensor positioned more than 1 m away from the measurement unit, and the other with an integrated amplifier for the sensor positioned at a distance of less than 0.5 m. A bipolar pulsed voltage supplying the sensor minimized the parasitic effects of the electromotive force induced in the probe circuit. The data were transmitted via a fiber optic cable to a PC equipped with a special software for processing and recording. Tests with 20–30 μs pulses up to 15 T confirmed the effectiveness of the system for measuring high pulsed magnetic fields. Full article