Influence of zeolite water on paramagnetic and ferromagnetic resonances in the Co2[Nb(CN)8] · 8H2O molecular magnet

The contributions of Co²⁺ and Nb⁴⁺ ions to the high-frequency dynamic magnetic susceptibility of the Co₂[Nb(CN)₈] · 8H₂O molecular magnet in the paramagnetic state at T > 12 K are separated. It is found that the ferromagnetic ordering, which leads to the reconstruction of the electron paramagnetic resonance spectrum into the ferromagnetic resonance spectrum, occurs at T < 12 K. The influence of zeolite water on the spectra of the paramagnetic and ferromagnetic resonances is found. Dehydration leads to a decrease in the time of the spin relaxation of the ferromagnetic system from 50 ps to 17 ps at T = 4 K and to the variation in the temperature dependences of the widths of the lines and g factors in the electron spin resonance spectra.     

Magnetism and the magnetocaloric effect in PrMn1.6Fe0.4Ge2

The magnetic and magnetocaloric properties of PrMn_1.6Fe_0.4Ge₂around the ferromagnetic transitions T _C ^inter ~ 230 K and T _C ^Pr ~ 30 K have been investigated by magnetisation, ⁵⁷Fe Mössbauer spectroscopy and electron paramagnetic resonance (EPR) measurements over the temperature range 5–300 K. The broad peaks in magnetic entropy around T_C ^inter (intralayer antiferromagnetism of the Mn sublattice to canted ferromagnetism) and T_C ^Pr (onset of ferromagnetic order of Pr sublattice in addition to ferromagnetically ordered Mn sublattice) are typical of second order transitions with maximum entropy values of -ΔS _M ~ 2.0 J/kg K and -ΔS _M ~ 2.2 J/kg K respectively for ΔB = 0–6 T. The EPR signal around T = 48 K of g value g ~ 0.8 is consistent with paramagnetic free ion Pr^3?+?. Below T_C ^Pr ~ 30 K the g value increases steadily to g ~ 2.5 at 8 K as saturation of the Pr^3?+? ion is approached. The EPR measurements indicate additional effects in this system below T ~ 20 K with the appearance of EPR signals of low g value g ~ 0.6.     

Antiferromagnetic Ordering of Magnetic Clusters Units in Nb6F15

We have studied the magnetic cluster compound Nb₆F₁₅ which has an odd number of 15 valence electrons per (Nb₆F₁₂)³⁺ cluster core, as a function of temperature using nuclear magnetic resonance, magnetic susceptibility, electron magnetic resonance and neutron powder diffraction. Nuclear magnetic resonance of the ¹⁹F nuclei shows two lines corresponding to the apical F^a?a nucleus, and to the inner Fⁱ nuclei. The temperature dependence of the signal from the Fⁱ nuclei reveals an antiferromagnetic ordering at T < 5 K, with a hyperfine field of ~2 mT. Magnetic susceptibility exhibits a Curie–Weiss behavior with T _N ~5 K, and μ _eff ~1.57 μ_B close to the expected theoretical value for one unpaired electron (1.73 μ_B). Electron magnetic resonance linewidth shows a transition at 5 K. Upon cooling from 10 to 1.4 K, the neutron diffraction shows a decrease in the intensity of the low-angle diffuse scattering below Q ~0.27 Å^?1. This decrease is consistent with emergence of magnetic order of large magnetic objects (clusters). This study shows that Nb₆F₁₅ is paramagnetic at RT and undergoes a transition to antiferromagnetic order at 5 K. This unique antiferromagnetic ordering results from the interaction between magnetic spins delocalized over each entire (Nb₆F ₁₂ ⁱ )³⁺ cluster core, rather than the common magnetic ordering.     

Magnetic properties and charge ordering in Pr0.75Na0.25MnO3 manganite

The structural and magnetic properties of Pr_0.75Na_0.25MnO₃ have been investigated experimentally. At room temperature, the compound shows paramagnetic characteristic. Along with decreasing temperature, a peak appears in the magnetization versus temperature curve around 220 K. To clarify whether this peak is associated with the ordering arrangement of Mn³⁺ and Mn⁴⁺ ions, electron diffraction experiments were carried out below and above 220 K respectively. Only basic Brag diffraction spots can be observed at high temperatures, however, superlattice diffraction appears below 220 K. This provides direct evidence for the existence of charge ordering in Pr_0.75Na_0.25MnO₃. We find the Mn³⁺ and Mn⁴⁺ cations form zigzag chains in a-c plane by analyzing the diffraction patterns. Combining with the magnetization measurements and the results of electron spin resonance, we confirm the antiferromagnetic phase and ferromagnetic component coexist in Pr_0.75Na_0.25MnO₃ below 120 K.     

Spin-glass-like behaviour and magnetic order in Mn[Cr0.5Ga1.5]S4 spinels

Magnetization and susceptibility were investigated as a function of temperature and magnetic field in polycrystalline Mn[Cr_0.5Ga_1.5]S₄ spinel. The dc susceptibility measurements at 919 Oe showed a disordered ferrimagnetic behaviour with a Curie-Weiss temperature θ_CW=−55 K and an effective magnetic moment of 5.96 μ_B close to the spin-only value of 6.52 μ_B for Cr³⁺ and Mn²⁺ ions in the 3d³ and 3d⁵ configurations, respectively. The magnetization measured at 100 Oe revealed the multiple magnetic transitions with a sharp maximum at the Néel temperature T_N=3.9 K, a minimum at the Yafet-Kittel temperature T_YK=5 K, a broad maximum at the freezing temperature T_f=7.9 K, and an inflection point at the Curie temperature T_C=48 K indicating a transition to paramagnetic phase. A large splitting between the zero-field-cooled (ZFC) and field-cooled (FC) magnetizations at a temperature smaller than T_C suggests the presence of spin-glass-like behaviour. This behaviour is considered in a framework of competing interactions between the antiferromagnetic ordering of the A(Mn) sublattice and the ferromagnetic ordering of the B(Cr) sublattice.     

Inhomogeneous magnetic states in the Nd(Mn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cr<Subscript>x</Subscript>)O<Subscript>3</Subscript> system

The crystal structure and magnetic properties of the Nd(Mn_?xCr_x)O₃ system (x≤0.85) have been studied. Substitution of chromium for manganese was shown to induce a transition from the antiferromagnetic to ferromagnetic state (x≈0.2) and a decrease in the critical temperature followed, conversely, by an increase in the Néel temperature and decay of spontaneous magnetization. At low temperatures, the magnetization was found to behave anomalously as a result of magnetic interaction between the ferromagnetic and antiferromagnetic phases. The formation of the ferromagnetic phase is attributed to destruction of cooperative static orbital ordering, while the coexistence of different magnetic phases is most probably due to internal chemical inhomogeneity of the solid solutions.     

Evolution of structural,magnetic and magnetocaloric properties in Sn-doped manganites La0.57Nd0.1Sr0.33Mn1−x Sn x O3 (x = 0.05–0.3)

Structural and magnetic properties of manganites series La_0.57Nd_0.1Sr_0.33Mn_1?x Sn _x O₃ with (0.05 ≤ x ≤ 0.30) have been investigated, and the critical exponents and magnetocaloric effect are studied around the room temperature, to shed light on Sn substitution influence. A solid-state reaction method was used in the preparation. A structural study using Rietveld refinement of XRD patterns indicates rhombohedral structure with R \( \overline{3} \) c space group for (0.05 ≤ x ≤ 0.20) and shows the existence of a secondary phase attributed to the neodymium tin oxide (Nd₂Sn₂O₇) pyrochlore for x = 0.3. The variation of the magnetization (M) vs. temperature (T), under an applied magnetic field of 0.05 T, reveals a ferromagnetic–paramagnetic transition at the Curie temperature T _C. In addition, it was discovered that increasing the tin content leads to a reduction in magnetization and a lowering of T _C from 282 K (x = 0.05) to 158 K (x = 0.20) with increasing Sn substitution. The samples exhibit the characteristics of spin/cluster-glass state which is evident from (zero-field-cooled and field-cooled) magnetization vs. temperature curves. Indeed, the thermal evolution of magnetization in the ferromagnetic phase at low temperature varies as T ^3/2, in accordance with Bloch’s law. The spin-stiffness constant D obtained from the Bloch constant was determined. A large magnetocaloric effect has been observed in both samples (x = 0.05 and x = 0.10): the maximum entropy change, \( \left| {\varDelta S_{\text{M} }^{\text{peak}} } \right| \) , reaches the highest value of 3.22 J/kg K under a magnetic field change of 5 T with a RCP value of 56 J/kg for x = 0.10 composition. This opens an interesting opportunity to this compound to compete with materials which work as magnetic refrigerants near room temperature. Besides, we show that the samples follow the conventional behavior of a second-order ferromagnetic transition. This was possible by investigating the critical behavior at the transition region by adopting the modified Arrott plot method. The values of the critical exponents (β, γ, δ and n) are determined and they are between those predicted by the three-dimensional Heisenberg model.     

Magnetic properties of stuffed copper chromium tellurides Cu1+xCr2+yTe4 (x=0-1, y<0.3)

We present a detail study of the effect of excess metal atoms on the magnetic properties of Cu_1+xCr_2+yTe₄ at 2-400 K. With the increase in x=0-1 and y<0.3, these compounds retain metallic behavior, while ferromagnetic ordering temperature reduces from 325 to 160 K. Our low field susceptibility χ_ac measurements reveal a second transition on cooling below the ferromagnetic ordering; the transition at around 160-180 K intensifies with the excess amount of copper and chromium atoms. The value of spontaneous magnetization at 2 K remains between 2.6 and 2.9μ_B across all the compositions and it reduces with temperature as M(T)∼A₀T^3/2+A₁T^5/2, as expected for the excitation of Bloch's spin waves in a model of the Heisenberg ferromagnet. Our terminal composition Cu_1.9Cr_2.25Te₄ showed only second transition at 160 K with short range magnetic order much above the transition temperature and in the absence of the specific heat jump at this temperature. The magnetic properties are explained as a result of random magnetic anisotropy in the excess-metal compositions induced by the interstitial atomic defects in their parent spinel structure. The large stuffing of cations has been made possible in the telluride compounds because of the large size of tellurium and also by the covalent bonding that stabilizes the defect structure.     

Magnetization and Mössbauer studies of 57Fe doped SrCoO3

⁵⁷Fe (1%) doped SrCoO₃ obtained by high-pressure method, has been investigated by magnetization and Mössbauer spectroscopy studies (MS) in the temperature range 4.2 K to 300 K. The ferromagnetic ordering temperature T _C obtained is 272(2) K. Isothermal magnetization curves have been measured at various temperatures, from which the saturation moments (M _sat) have been deduced. The ⁵⁷Fe MS spectra display standard six-line patterns with an isomer shift typical of Fe^3?+? and a very small quadrupole splitting (QS = 0.14(1) mm/s above T _C). The magnetic hyperfine field at 4.2 K is 276(1) kOe. The temperature dependencies of the iron hyperfine field and M _sat (1.83 µ _B at 5 K) are almost identical. This shows that the Fe^3?+? is replacing Co^4?+?, both of the same electronic configuration. They also interact similarly, namely the Fe–Co exchange is almost identical to the Co–Co exchange.     

Microwave absorption properties of Al- and Cr-substituted M-type barium hexaferrite

Aluminum- and chromium-substituted barium ferrite particles with single magnetic domain were prepared using self-propagating combustion method. The crystalline structure, size, coercivity and microwave absorption property of the particles were investigated by means of X-ray diffraction, transmission electron microscopy, vibrating sample magnetometry and vector network analyzer. The results show that the crystalline structure of BaFe_12−xAl_xO₁₉ is still hexagonal. But when the chromium substitution amount y exceeds 0.6, the extra chromium ions cannot enter the lattice of BaFe_12−yCr_yO₁₉. After Fe³⁺ is partly substituted with Al³⁺ and Cr³⁺, the microwave absorption properties of barium ferrite are improved. The maximum absorption reaches 34.76 dB. The ferromagnetic resonance is an important channel of barium ferrite to absorb microwaves with high frequency. Aluminum and chromium substitutions change the ferromagnetic resonant frequency of barium ferrite. The multipeak phenomenon of the ferromagnetic resonance increases the microwave absorption capability of barium ferrite.     

Physical properties and phase diagram of the magnetic compound Cr<Subscript>0.26</Subscript>NbS<Subscript>1.74</Subscript> at high pressures

We report the results of a study of magnetic, electrical, and thermodynamic properties of a single crystal of the magnetic compound Cr_0.26NbS_1.74 at ambient and high pressures. Results of the measurements of magnetization as a function of temperature reveal the existence of a ferromagnetic phase transition in Cr_0.26NbS_1.74. The effective number of Bohr magnetons per Cr atom in the paramagnetic phase of Cr_0.26NbS_1.74 is µ_eff ≈ 4.6µB, which matches the literature data for Cr1/3NbS2. Similarly, the effective number of Bohr magnetons per Cr atom in the saturation fields is rather close in both substances and corresponds to the number of magnetons in the Cr⁺³ ion. In contrast to the stoichiometric compound, Cr_0.26NbS_1.74 does not show a metamagnetic transition, that indicates the lack of a magnetic soliton. A high-pressure phase diagram of the compound reveals the quantum phase transition at T = 0 and P ≈ 4.2 GPa and the triple point situated at T ≈ 20 K and P ≈ 4.2 GPa.     

Ferromagnetic phase transitions in the magnetically heterogeneous solid solution system EuxLa1−xS

The ferromagnetic phase transitions of the solid solution system Eu_xLa_1-xS with Eu-concentrations x=0.85, 0.65 and 0.50 are analyzed by measurements of the initial permeability, the specific heat and the magnetization. For the sample with x=0.85 the spontaneous magnetization develops continuously between two temperatures T_c1 and T_c2. For the sample with x=0.65 a well defined magnetic ordering temperature exists. One observes strongly curved magnetization isotherms when plotting the magnetization data in form of modified Arrott plots. The M(H, T) data above the curved region show usual ferromagnetic scaling with the critical exponents β=0.5 and δ=4.7. These exponents fulfill the scaling relations with the exponents γ=2.1 and α≈-1 derived for the initial susceptibility and the magnetic specific heat. The sample with the concentration x=0.50 turns out to be not truely ferromagnetic. It is a spin glass with strong ferromagnetic short range order.     

Effect of a structural disorder on the magnetic properties of the sodium–cobalt tellurate Na<Subscript>3.70</Subscript>Co<Subscript>1.15</Subscript>TeO<Subscript>6</Subscript>

A new layered oxide, sodium–cobalt tellurate Na_3.70Co_1.15TeO₆, is synthesized and structurally characterized, and its static and dynamic magnetic properties are studied. This compound has a new monoclinic structure type with quasi-one-dimensional cation ordering in magnetically active layers. This compound is antiferromagnetically ordered at a Néel temperature T _N ~ 3.3 K, and the temperature and field dependences of magnetization suggest competing antiferromagnetic and ferromagnetic interactions. EPR spectroscopy reveals complex spin dynamics when temperature changes and the presence of two different paramagnetic centers, which is attributed to the existence of two structurally nonequivalent (regular and antisite) positions for magnetic Co²⁺ ions.     

Dopant Spin States and Magnetic Interactions in Transition Metal (Fe3+)-Doped Semiconductor Nanoparticles: An EMR and Magnetometric Study

In this work, electron magnetic resonance (EMR) spectroscopy and magnetometry studies were employed to investigate the origin of the observed room-temperature ferromagnetism in chemically synthesized Sn_1?x Fe _x O₂ powders. EMR data clearly established the presence of two different types of signals due to the incorporated Fe ions: paramagnetic spectra due to isolated Fe³⁺ ions and broad ferromagnetic resonance (FMR) spectra due to magnetically coupled Fe³⁺ dopant ions. EMR data analysis and simulation suggested the presence of high-spin (S = 5/2) Fe³⁺ ions incorporated into the SnO₂ host lattice both at substitutional and at interstitial sites. The FMR signal intensity and the saturation magnetization M _s of the ferromagnetic component increased with increasing Fe concentration. For Sn_0.953Fe_0.047O₂ samples, well-defined EMR spectra revealing FMRs were observed only for samples prepared in the 350–600°C range, whereas for samples prepared at higher annealing temperatures up to 900°C, the FMRs and saturation magnetization were vanished due to diffusion and eventual expulsion of the Fe ions from the nanoparticles, in agreement with data obtained from Raman and X-ray photoelectron spectroscopy.     

Electron spin resonance study of bulk and nanosized La0.875Sr0.125MnO3

The structural, transport and electron spin resonance properties of bulk and nanosized La_0.875Sr_0.125MnO₃ prepared by a sol-gel method have been investigated. The bulk sample has an orthorhombic structure and a ferromagnetic insulating ground state. The ESR spectra indicate the coexistence of the ferromagnetic insulating and ferromagnetic metallic phases below T_C. In addition to a sharp peak in the vicinity of T_C, another sharp peak close to is clearly observed in the intensity of the spectra, which may be correlated with the structural transition and orbital ordering at this temperature. For the nanosized sample, a drastically different behavior is found. With a rhombohedral structure down to 70 K, the nanosized sample shows a ferromagnetic metallic ground state. The ESR studies reveal the coexistence of the paramagnetic and ferromagnetic resonance signals. The resonance intensity shows a broad peak around 200 K, which may be due to the wide ferromagnetic transition in the nanoparticle.     

Critical nuclear relaxation in cobalt metal

Nuclear magnetic resonance of cobalt metal was investigated in the paramagnetic and ferromagnetic states and in the critical region below T_c. The Knight shift and spin lattice relaxation times were measured in the paramagnetic phase in the solid and liquid states from 1578 K to 1825 K. The resonant frequency, spin-lattice and spin-spin relaxation times were measured in the ferromagnetic phase from room temperature to 1385 K. The main part of (T₁T)^-1 results from fluctuating orbital moments in both phases except near T_c where this process forms the background for critical spin relaxation. The critical exponents for T^-1₁ and for the magnetization in the ferromagnetic state were found to be n' = 0.96 ± 0.07 and β = 0.308 ± 0.012, respectively.     

Investigation of magnetocaloric effect in La0.45Pr0.25Ca0.3MnO3 by magnetic,differential scanning calorimetry and thermal analysis

We investigated magnetocaloric effect in La_0.45Pr_0.25Ca_0.3MnO₃ by direct methods (changes in temperature and latent heat) and indirect method (magnetization isotherms). This compound undergoes a first-order paramagnetic to ferromagnetic transition with T_C=200 K upon cooling. The paramagnetic phase becomes unstable and it transforms into a ferromagnetic phase under the application of magnetic field, which results in a field-induced metamagnetic transition (FIMMT). The FIMMT is accompanied by release of latent heat and temperature of the sample as evidenced from differential scanning calorimetry and thermal analysis experiments. A large magnetic entropy change of ΔS_m=−7.2 J kg⁻¹ K⁻¹ at T=212.5 K and refrigeration capacity of 228 J kg⁻¹ are found for a field change of ΔH=5 T. It is suggested that destruction of magnetic polarons and growth of ferromagnetic phase accompanied by a lattice volume change with increasing magnetic field is responsible for the large magnetocaloric effect in this compound.     

Charge order melting and magnetic transition in Nd0.5(1+x)Ca0.5(1−x)Mn(1−x)CrxO3 system

The magnetic property of double doped manganite Nd_0.5(1+x)Ca_0.5(1−x)Mn_(1−x)Cr_xO₃ with a fixed ratio of Mn³⁺:Mn⁴⁺=1:1 has been investigated. For the undoped sample, it undergoes one transition from charge disordering to charge ordering (CO) associated with paramagnetic (PM)-antiferromagnetic (AFM) phase transition at T<250 K. The long range AFM ordering seems to form at 35 K, rather than previously reported 150 K. At low temperature, an asymmetrical M-H hysteresis loop occurs due to weak AFM coupling. For the doped samples, the substitution of Cr³⁺ for Mn³⁺ ions causes the increase of magnetization and the rise of T_c. As the Cr³⁺ concentration increases, the CO domain gradually becomes smaller and the CO melting process emerges. At low temperature, the FM superexchange interaction between Mn³⁺ and Cr³⁺ ions causes a magnetic upturn, namely, the second FM phase transition.     

Electronic transport properties of stuffed compositions of ferromagnetic copper chromium telluride: Cu1+xCr2Te4 (x=0-1)

We present here a detailed study of electronic transport properties of the metallic-ferromagnetic compounds Cu_1+xCr₂Te₄, having excess Cu atoms with x=0-1, from 2 to 400 K. The stuffing of the copper atoms in the parent structure reduces the ferromagnetic ordering temperature T_C from 325 to 156 K, while for the entire range the dependence of the electrical resistance and the thermopower with temperature and the anomalies in them on the magnetic ordering remain similar. All the compounds show a magnon-drag contribution in thermopower as a positive maximum around T_C/3, and a T² - dependence of resistivity at low temperatures. The increasing effects of the short range magnetic ordering in the paramagnetic resistivity are seen with the increase in the stuffing of atoms in these compounds. The transport properties are explained by the current carriers —the holes in a wide energy band dominated by the p-state of Te-atoms, which are scattered by the spindisorder in the paramagnetic phase and from the magnons in the ferromagnetic phase.     

Al-doping effect on the structural and physical properties of delafossite-type oxide CuCrO2

The structure, Raman spectroscopy, magnetization, and dielectric properties of delafossite-type oxide CuCr_1−xAl_xO₂ have been characterized. It was found that Al substitution generates an anisotropic effect on the structure, besides magnetic dilution. The temperature dependence of all samples exhibits paramagnetic behavior at high temperature. Above x=0.2 the ferromagnetic transition at 120 K disappears. It is argued that Al substitution destabilizes the antiferromagnetic order of Cr³⁺ ions and modulates the spin configuration, leading to a weak ferromagnetism. The coupling between the magnetic order and ferroelectric order is also characterized.