Magnetism influenced by structural disorder in melt-spun DyMn6 − x Ge6 − x Fe x Al x (x = 2.5, 3)

Different chemical and/or geometrical orders were found in melt-spun DyMn_6???x Ge_6???x Fe _x Al _x with x = 2.5 and 3 having fully amorphous and mixed (crystalline and amorphous) structure, respectively. Thermal variations in magnetization M from liquid helium up to room temperature for both samples are similar. Magnetization value at zero field cooled curve reaches about 0.1 μ_B per formula unit at 2 K and then increases. Two maxima are visible, the first at 50 K (a sharp effect) and the second very broad ranging from 150 to 200 K. ⁵⁷Fe Mössbauer spectrometry investigation revealed a remaining magnetic component in addition to a prevailing quadrupolar feature. Application of a weak external magnetic field causes an increase in the mean hyperfine magnetic field B _hyp and the volume fraction of magnetic component. This observation was confirmed by results of M(T), M(H) and AC magnetic susceptibility measurements. In short-range ordered crystallographic zones characteristic of melt-spun DyMn_6???x Ge_6???x Fe _x Al _x (x = 2.5, 3) alloys, the related magnetic ordering, called the mictomagnetism or the cluster spin glass appears.     

57Fe Mössbauer study of sol–gel synthesized Sn1 − x − y Fe x Sb y O2 − δ powders

Samples of SnO₂ doped with different amount of Fe (10–20%) and Sb (5–25%) were prepared by sol–gel method. Room temperature ferromagnetism was found to increase as a result of co-doping with Sb, as compared to SnO₂ doped only with Fe. ⁵⁷Fe Mössbauer spectra of almost all samples exhibited two paramagnetic doublets and a small subspectrum referring to magnetic relaxation at room temperature. Only the samples Sn_0.65Fe_0.2Sb_0.15O_2???δ and Sn_0.85Fe_0.1Sb_0.05O_2???δ with 4 h long annealing time showed well developed sextets and larger magnetic coercivity compared to that of the other samples. The sextet observed was considered to be due to precipitates like Sn doped α-Fe₂O₃. The results suggest that the origin of the magnetic interactions is enhanced by the presence of magnetic defects, which can interact with the iron ions by free carrier electrons. For the sample with precipitates, the grain boundary defects may play an important role of enhanced ferromagnetism.     

Mössbauer studies of GdFe2 − x Hf x alloys

GdFe_2???x Hf _x alloys, where x?=?0, 0.10, 0.15, 0.20, and 0.30, are produced by arc-melting of pure elements. The samples are investigated by x-ray diffraction and Fe⁵⁷ Mössbauer spectroscopy at 78 K and 300 K. We find that the alloy system GdFe_2???x Hf _x have the single phase cubic Cu₂Mg type structure in the whole concentration range. Mössbauer spectroscopic results show that all the samples studied are magnetically ordered at 78 K, and at room temperature. The room temperature spectra are fitted with two magnetic components where the direction of magnetization is along the [111] while the spectra at 78 K are fitted with four magnetic subspectra indicating a complex direction of magnetization for all samples under investigation. The average magnetic hyperfine field and the average isomer shift are found to decrease almost linearly with increasing the Hf concentration at 78 K and 300 K due to the replacement of Fe by nonmagnetic Hf.     

Characterisation of Ba2In2 − x Sn x O5 + x/2 oxide ion conductors

The Ba₂In_2 − x Sn _x O_5 + x/2 solid solution was confirmed up to x = 1 by solid-state reaction. X-ray diffraction at room and at elevated temperatures, Raman scattering and impedance spectroscopy were used to characterise the samples. The structure refinement of the composition x = 0.1 from neutron diffraction data reveals that tin is preferentially located in the tetrahedral layers of the brownmillerite. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007     

An EIS study of La2 − x Sr x NiO4 + δ SOFC cathodes

La_2 − x Sr _x NiO_{4 +  δ} materials were investigated as cathodes for the electrochemical reduction of oxygen on a Ce_1.9Gd_0.1O_1.95 (CGO10) electrolyte using cone-shaped electrodes together with electrochemical impedance spectroscopy. The area-specific resistance (ASR) of the La_2 − x Sr _x NiO_{4 +  δ} nickelates towards the reduction of oxygen is equal to the ASR of perovskites; however, it is not as low as for the best Fe–Co-based perovskites. The lowest ASR is found for the compound La_1.75Sr_0.25NiO_{4 +  δ} with an ASR of 23.8 Ωcm² measured on a cone-shaped electrode in air at 600 °C. It is suggested that difference in oxide ionic conductivity of the nickelates is the main cause for the different activity of the nickelates towards the electrochemical reduction of oxygen.     

Critical behaviour of Ho 2 Fe 17 − x Mn x —magnetisation and Mössbauer spectroscopy

The magnetic properties of Ho₂Fe_17???xMn_x compounds (x = 0–2) of ferromagnetic ordering temperatures up to T_C ~344 K have been investigated by DC magnetization and Mössbauer effect measurements. The nature of the magnetic phase transitions and the critical behaviour around T_C has been investigated by analysis of the magnetisation data and the critical exponents β, γ and δ determined. The critical exponents are found to be similar to the theoretical values of the mean-field model for which β?=?0.5 and γ?=?1.0, indicating the existence of a long-range ferromagnetic interactions. The isothermal entropy changes ΔS around T_C have been determined as a function of temperature in different magnetic fields.     

Crystalline Al1 − x Ti x phases in the hydrogen cycled NaAlH4 + 0.02TiCl3 system

The hydrogen (H) cycled planetary milled (PM) NaAlH₄?+?0.02TiCl₃ system has been studied by high resolution synchrotron X-ray diffraction and transmission electron microscopy during the first 10?H cycles. After the first H absorption, we observe the formation of four nanoscopic crystalline (c-) Ti-containing phases embedded on the NaAlH₄ surface, i.e. Al₂Ti, Al₃Ti, Al₈₂Ti₁₈ and Al₈₉Ti₁₁, with 100% of the originally added Ti atoms accounted for. Al₂Ti and Al₃Ti are observed morphologically as a mechanical couple on the NaAlH₄ surface, with a moderately strained interface. Electron diffraction shows that the Al₈₂Ti₁₈ phase retains some ordering from the L1₂ structure type, with the observation of forbidden (100) ordering reflections in the fcc Al₈₂Ti₁₈ lattice. After 2?H cycles the NaAlH₄?+?0.02TiCl₃ system displays only two crystalline Ti-containing phases, Al₃Ti and Al₈₉Ti₁₁. After 10?H cycles, the Al₈₉Ti₁₁ is completely converted to Al₈₅Ti_15. Al₈₉Ti₁₁, Al₈₅Ti₁₅ and Al₃Ti do not display any ordering reflections, and they are modeled in the A1 structure type. Quantitative phase analysis indicates that the Al₃Ti proportion continues to increase with further H cycles. The formation of Ti-poor Al_{1??? x} Ti _x (x?<?0.25) phases in later H cycles is detrimental to hydrogenation kinetics, compared to the starting Ti-richer near-surface Al₂Ti/NaAlH₄ interface present during the first absorption of hydrogen.     

Structural characterization and magnetic properties of NiMg3x/2Cr0.9Fe1.1 − x O4

Magnesium-substituted nickel–chrome ferrites have been studied using X-ray diffraction and Mössbauer spectroscopy. A single cubic spinel phase was obtained in the range 0.0?≤?x?≤?0.4. The lattice parameter was found to decrease with the increase of Mg concentration. The Mössbauer spectra measured at 295 and 78 K of all samples showed magnetic patterns interpreted in term of the tetrahedral and octahedral sites occupancies. The magnetic hyperfine field of both sites decrease with the increase of the Mg concentration. The magnetic properties as a function of the Mg concentration have been explained on the basis of the cation distribution among the two crystallographic sites driven from the Mössbauer measurements.     

Mössbauer study on Zn1 − x Fe x O semiconductors prepared by high energy ball milling

We present the preparation of massive Zn_1???x Fe _x O ternary oxides using the mechanical mill. The Fe atom is a particular dopant since it presents two different oxidation states which allow us to vary the starting materials: Fe₂O₃, $\upalpha $ -Fe or FeO. Parameters such as initial concentrations, atmosphere and milling times were varied. X-ray diffraction and ⁵⁷Fe Mössbauer spectrometry (MS) were applied in order to analyze the structure evolution and iron incorporation in the wurtzite crystalline structure with milling time. At final stages, Fe atoms seem to be incorporated in the ZnO structure for those samples milled under Ar atmosphere. In all cases, two paramagnetic components, attributed to Fe atoms in both valence states, were observed by MS.     

Synthesis and characterization of layered perovskite oxides La1 + x Sr2 − x MnCrO7 (x = 0.2, 0.5)

Intergrowth perovskite type complex oxides of composition La_1.2Sr_1.8MnCrO₇ and La_1.5Sr_1.5MnCrO₇ have been synthesized by ceramic method. Rietveld profile analysis shows that the phases crystallize with tetragonal unit cell in the space group I4/mmm. Both the phases behave as insulators in the high temperature region and the linearity of log ρ versus T ^?1/4 plot in the temperature range 150–300 K shows that the electronic conduction occurs by a 3D variable range hopping mechanism. The phases show insulator-metal transition at low temperature which could be due to the mixed valence state of Mn³⁺/Mn⁴⁺ by double exchange mechanism. The ferromagnetic interactions observed for the samples arises from double exchange interaction between Mn ³⁺ and Mn⁴⁺ and Cr³⁺ and Mn³⁺ ions.     

Structural and magnetic study of bulk glassy Fe72 − x Co x B20Si4Nb4 alloys

The influence of the partial replacement of Fe by Co on the structural and magnetic properties of bulk-type glassy Fe_72???x Co _x B₂₀Si₄Nb₄ (x = 0, 5, 10, 15, 20, 25, 30, 35) alloys has been studied using differential scanning calorimetry (DSC), X-ray diffraction (XRD) magnetic measurements and Mössbauer spectroscopy. Results show that the successive Co addition: (1) does not affect the mass density of the studied alloys, (2) affects appreciably the super cooled region, (3) modifies the magnetic properties, exhibiting soft magnetic behavior, (4) modifies the spin texture and disorder within the studied specimens.     

Two new low-temperature phase transitions in the Li(NH4)1 − x Na x SO4 system

Dielectric measurements, X-ray diffraction and Raman scattering techniques have been used to investigate Li(NH₄)_0.99Na_0.01SO₄ (LASS1%) and Li(NH₄)_0.80Na_0.20SO₄ (LASS20%) crystals in the temperature range from 200 to 10?K. These are interesting systems because of the presence of hydrogen bonds and structural defects and because the mother crystal, LiNH₄SO₄, is ferroelectric at room temperature. From the analysis of the results we can conclude that the substitution of Na⁺ ions in the structure of LiNH₄SO₄, even at quantities as low as 1%, is sufficient to induce additional phase transitions to the LiNH₄SO₄ system. The new phase transitions are observed at 181 and 115?K for LASS1% and at 208 and 133?K for LASS20% and both are reversible.     

Electrochemical characteristics of Li4 − x Cu x Ti5O12 used as anode material for lithium-ion batteries

Cu-doped Li₄Ti₅O₁₂ (Li_4???x Cu _x Ti₅O₁₂) materials were synthesized by solid-state method. Cu-doping does not change the crystal structure of Li₄Ti₅O₁₂ material but increases its lattice constant. The particle size of Li_4???x Cu _x Ti₅O₁₂ powders decreases with increasing Cu-doping level. Cu-doping does not change the specific capacity at low current density, but can improve the cycling stability and the rate capability of Li₄Ti₅O₁₂ significantly. This is mainly attributed to the enhanced electronic and ionic conductivity and the decreased charge transfer resistance, caused by the increased specific surface area of active Li_4???x Cu _x Ti₅O₁₂ powders. The Li_3.8Cu_0.2Ti₅O₁₂ anode material exhibits the best cycling stability and rate capability.     

Physicochemical properties of LiAl x Mn2 − x O4 and LiAl0.05Mn1.95O4 − y F y cathode material by the citric acid-assisted sol–gel method

LiAl _x Mn_2 − x O₄ and LiAl_0.05Mn_1.95O_4 − y F _y spinel have been successfully synthesized by citric acid-assisted sol–gel method. The structure and physicochemical properties of this as-prepared powder were investigated by electronic conductivity test, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and galvanostatic charge–discharge test in detail. The electronic conductivity decreases with increasing of the content of doped Al. XRD patterns show that the diffraction of LiAl_0.05Mn_1.95O_4 − y F _y samples is similar, with all the peaks indexable in the Fd3m space group, and a little impurity appears in the LiAl_0.05Mn_1.95O_3.8F_0.2 sample. SEM reveals that all LiAl_0.05Mn_1.95O_4 − y F _y powders have the uniform, nearly cubic structure morphology with narrow size distribution which is less than 500 nm. Galvanostatic charge–discharge test indicates that LiAl_0.05Mn_1.95O₄ has the highest discharge capacity and electrochemical performance among all LiAl _x Mn_2 − x O₄ samples after 50 cycles, and the initial discharge capacity of LiAl_0.05Mn_1.95O_4 − y F _y (y = 0, 0.02, 0.05, 0.1) is 123.9, 124.6, 124.9, and 125.0 mAh g⁻¹, respectively, and their capacity retention ratios are 94.2%, 94.9%, 91.7%, and 89.9% after 50 cycles, respectively. EIS indicates that LiAl_0.05Mn_1.95O_3.98F_0.02 have smaller charge transfer resistance than that of LiAl_0.05Mn_1.95O₄ corresponding to the extraction of Li⁺ ions.     

57Fe Mössbauer study of La0.67Ca0.33Mn1 − x Fe x O3 CMR system

The structural changes of near-equiatomic α-FeCr alloys, ground in a vibratory mill in vacuum and in argon, were followed as a function of milling time. An amorphous phase forms in both cases but at a much faster rate when milling in argon than when milling in vacuum. Amorphisation by ball-milling of α-FeCr alloys is deduced to be an intrinsic phenomenon which is however speeded-up by oxygen. The amorphous phase crystallizes into a bcc Cr-rich phase and a bcc Fe-rich phase when annealed for short times.     

Structure and electrochemical performance of LiV x Mn2 − x O4 (0 ≤ x ≤ 0.20) cathode materials for rechargeable lithium ion batteries

LiMn₂O₄ and vanadium-substituted LiV _x Mn_2???x O₄ (x?=?0.05, 0.10 0.15 and 0.20) cathode materials were synthesized by sol–gel method using aqueous solutions of metal nitrates and tartaric acid as chelating agent at 600 °C for 10 h. The structure and electrochemical properties of the synthesized materials were characterized by using X-ray diffraction, SEM, TEM and charge–discharge studies. X-ray powder diffraction analysis was changed in lattice parameters with increasing vanadium content suggesting the occupation of the substituent within LiMn₂O₄ interlayer spacing. TEM and SEM analyses show that LiV_0.15Mn_1.85O₄ has a smaller particle size and more regular morphological structure with narrow size distribution than LiMn₂O₄. It is concluded that the structural stability and cycle life improvement were due to many factors like better crystallinity, smaller particle size and uniform distribution compared to the LiMn₂O₄ cathode material. The LiV_0.15Mn_1.85O₄ cathode material has improved the structural stability and excellent electrochemical performances of the rechargeable lithium ion batteries.     

Heat treatment effects on spinel phase of Zn x Ni1 − x Fe2O4 and MnFe2O4 nanoferrites

We report the effects of heat treatment on Zn _x Ni_1???x Fe₂O₄ (x?= 0, 0.5 and 1.0) and MnFe₂O₄ ferrite nanoparticles. The as-prepared compounds were sintered from 400°C to 1100°C. Pure ZnFe₂O₄ (x?= 1.0) and MnFe₂O₄ could be obtained under low reaction temperature of 200°C. NiFe₂O₄ (x?= 0) and Zn_0.5Ni_0.5Fe₂O₄ (x?= 0.5) nanoferrites crystallized with single phase cubic spinel structure after annealing at 600°C. The single phase cubic spinel structure of these compounds was destroyed after annealing at temperature above 700°C. The magnetization measurements indicate superparamagnetic behavior of the nanosized compounds produced.     

Effect of Co 2 + content on the magnetic properties of Co x Fe 3 − x O 4 /SiO 2 nanocomposites

Non-stoichiometric Co_xFe_3???xO₄/SiO₂ (x = 0.8, 0.9, 1.0, 1.1) nanocomposites have been prepared by sol-gel method. The structure, morphology and magnetic properties of the obtained samples were characterized by X-ray diffraction, transmission electron microscopy, vibrating sample magnetometer and Mössbauer spectroscopy at room temperature. As the Co^2?+? content increases, the average particle size of the spherical Co_xFe_3???xO₄ in the samples decreases and the lattice constants increases. The hyperfine fields for both A- and B-site decrease, while the fraction of Co^2?+? occupying the A-site increases. Magnetization measurements show the saturation magnetization and coercivity of Co_xFe_3???xO₄/SiO₂ decrease with increasing Co^2?+? content. The decrease in magnetization results from the weakened A-B interactions between Fe^3?+?, and the change in coercivity can be related to the variation of Co^2?+? at B-site and the decreasing particle size.     

Structural and electrochemical properties of LiFe1 − 3x/2Bi x PO4/C synthesized by sol–gel

In this study, LiFe_1???3x/2Bi _x PO₄/C cathode material was synthesized by sol–gel method. From XRD patterns, it was found that the Bi-doped LiFePO₄/C cathode material had the same olivine structure with LiFePO₄/C. SEM studies revealed that Bi doping can effectively decrease the particle sizes. It shortened Li⁺ diffusion distance between LiFePO₄ phase and FePO₄ phase. The LiFe_0.94Bi_0.04PO₄/C powder exhibited a specific initial discharge capacity of about 149.6 mAh g^?1 at 0.1 rate as compared to 123.5 mAh g^?1 of LiFePO₄/C. EIS results indicated that the charge-transfer resistance of LiFePO₄/C decreased greatly after Bi doping.     

Effect of Ni/Mn ratio on the performance of LiNi x Mn2 − x O4 cathode material for lithium-ion battery

Lithium nickel manganate is recognized as a type of promising cathode material for lithium-ion battery, due to its advantages such as high voltage, high power density, and relative lower cost. In this paper, a series of LiNi _x Mn_2???x O₄ cathode materials with various molar ratio of Ni/Mn have been prepared with a co-precipitation method, followed by a solid state reaction, and the effect of the molar ratio of Ni/Mn on the structure and properties of materials are intensively investigated by means of X-ray diffraction (XRD), Fourier transform infrared spectrometer (FTIR), scanning electron microscopy (SEM), and performance measurements, etc. It is revealed that all the samples with x from 0 to 0.5 have well-defined spinel structure and fit well to Fd-3 m space group. With the increase of the molar ratio of Ni/Mn, the diffraction peaks shift to higher angle slightly and the lattice parameter decreases gradually by the XRD results. Furthermore, it is found that the capacity at the 4.0 V plateau decreases while the capacity at 4.7 V plateau increases with the increase of the ratio of Ni/Mn, and the total discharge capacity shows growth trend with the increase of Ni content. It is important that all the samples with various molar ratio of Ni/Mn exhibit good cyclic stability. Based on the experimental results, we suggest that the Ni may incorporate into the lattice of LiMn₂O₄ substituting of Mn. The plateau at 4.7 V is related to the Ni ions and the plateau at 4.0 V is related to the Mn ions in the materials.