Magnetism and phase transformation of Cu-Fe composite oxides prepared by the sol-gel route

The Cu-Fe composite oxides were prepared by an epoxide assisted sol-gel route. The structural and magnetic properties of Cu-Fe composite oxides calcinated at different temperatures were determined by X-ray diffraction (XRD), Mössbauer spectroscopy measurements, and magnetic measurements. These results indicated that CuFe₂O₄ was only formed as calcination temperature increased to 500 °C, and a crystalline phase transformation from c-CuFe₂O₄ to t-CuFe₂O₄ occurred in elevating calcination temperature above it. All Cu-Fe oxides had ferromagnetic nature, and the significant superparamagnetic behavior was observed in the results of magnetic and Mössbauer spectroscopy measurements.     

Amorphization of ice near the melting point

In addition to reflections of the hexagonal phase of ice I _h, the intense diffuse scattering of X-rays mainly due to the amorphization of ice is revealed on the X-ray diffraction patterns of water ice samples prepared at liquid nitrogen (studied by the authors earlier) and samples prepared at T = ?10°C (this work). The measurements are performed in the temperature range from ?25 to 0°C. The existence of reflections of the crystalline phase and intense diffuse scattering on the X-ray diffraction patterns makes it possible make a conclusion about the coexistence of crystalline and amorphous structures of ice. Splitting of the first maximum on the electron-density radial distribution function is detected on the basis of an X-ray diffraction pattern recorded at T = ?3°C. This splitting is explained by an increase in the interatomic distances between the nearest-neighbor atoms located at different levels. Similar splitting was also detected on a radial distribution function constructed using an X-ray diffraction pattern recorded at ?10°C.     

Low-temperature synthesis of nanocrystalline β-dicalcium silicate with high specific surface area

β-Dicalcium silicate (β-Ca₂SiO₄) was synthesized for the first time by a simple solution combustion method using citric acid as fuel. The influence of calcination temperature on the average crystallite size, specific surface area and morphology of the powders were investigated by X-ray diffraction technique (XRD), scanning electron microscopy (SEM) and N₂ adsorption measurements (BET). The results showed that the increase of calcination temperature from 650°C to 1100°C resulted in larger crystallite size and lower specific surface area of β-Ca₂SiO₄. The highest specific surface area could reach as high as 26.7 m²/g when the as-burnt powders were calcined at 650°C.     

Effect of phase transformation on optical and dielectric properties of zirconium oxide nanoparticles

Zirconium oxide nanoparticle (ZrO₂) is synthesized by the hydrothermal method at different calcination temperatures. The structural analysis is carried out by X-ray diffraction and Raman spectra. The sample prepared at 400 °C and 1100 °C showed the cubic and monoclinic phase, respectively, and the sample calcined at 600 °C and 800 °C showed the mixed phase with co-existence of cubic and monoclinic phases. Furthermore, the morphology and particle size of these samples were investigated by scanning electron microscope (SEM) and transmission electron microscope (TEM) analysis. The band gap estimated from UV–Vis spectra of ZrO₂ (zirconia) nanocrystalline materials calcined at different temperatures from 400 °C to 1100 °C was in the range of 2.6–4.2 eV. The frequency dependence of dielectric constant and dielectric loss was investigated at room temperature. The low frequency region of dielectric constant is attributed to space charge effects.     

Local atomic and magnetic structures of nanocrystalline Fe75Cr10B15 alloy

The crystal, local atomic and magnetic structures of Fe₇₅Cr₁₀B₁₅ alloys annealed at 440?C473°C for 5 min have been studied using X-ray diffraction and ⁵⁷Fe M?ssbauer spectroscopy. At the annealing temperature T _a = 440°C, nanocrystals of the ??-Fe phase (??1%) precipitate in the amorphous matrix of the alloy. The complete crystallization of the amorphous alloy occurs at T _a = 473°C with the formation of ??-Fe nanocrystals 26 ± 2 nm in size and nanocrystals of tetragonal boride t-Fe₃B 47 ± 2 nm in size. It has been found that chromium atoms are located in nanocrystals of the ??-Fe and y-Fe₃B types. The distribution functions of hyperfine fields in the nanocrystalline Fe₇₅Cr₁₀B₁₅ alloy reconstructed from the M?ssbauer spectra (at T _a = 473°C) show that there are three allowed states of iron atoms in the ??-Fe phase and three equally probable crystallographic nonequivalent states of iron in the t-(Fe,Cr)₃B phase. The chromium concentration x in the ??-Fe(Cr) phase is found to be ??10 at %. The substitution of chromium atoms for iron atoms in t-Fe₃B substantially decreases local magnetic moments of the iron atoms.     

Characteristics of molecular beam epitaxy-grown GaFeAs

Diluted magnetic semiconductors GaFeAs were grown by molecular beam epitaxy and characterized. Ga_1−xFe_xAs ternary alloys were obtained at the growth temperature T_s=200 °C ranging from x=0.005 to 0.03. The effects of thermal treatment on behaviors of defects, affecting to the magnetic properties of GaFeAs layer were particularly elucidated. As-grown samples were annealed at temperatures varying from 400 to 600 °C. From the measurement of double crystal X-ray diffraction, we observed Fe-related peak which shifted to a higher diffraction angle as the Fe content increased, indicating that the lattice constant decreases with increasing Fe content. In contrast, above the annealing temperature 500 °C, the lattice constant becomes smaller than that of GaAs. Using the deep level transient spectroscopy, various defects in GaFeAs layer were observed and identified in conjunction with magnetic properties.     

Correlation between magnetotransport properties and the microstructure of the Co20Cu80 granular alloy

We report on the structural, transport and magnetic properties of Co₂₀Cu₈₀ metallic granular films. The granular films are prepared by ion-beam sputtering at room temperature on glass substrates. The structural properties have been investigated using X-ray diffraction and transmission electron microscopy. Structural characterisation confirmed that the samples consist of fine magnetic particles embedded in the non-magnetic Cu matrix. Giant magnetoresistance (GMR) of 3% is observed at room temperature after annealing at 250°C for 30 min. Detailed structural analysis is performed to understand the origin of the small GMR signal. It is confirmed that this result is directly correlated to the small size, density, and non-uniform distribution of Co particles.     

Firing-Induced Microstructural Properties of Quasi-Diamagnetic Carbonate-Based Porous Ceramics: a <Superscript>1</Superscript>H NMR Relaxation Correlation Study

This study deals with the application of two-dimensional proton nuclear magnetic resonance relaxometry (2D ¹H NMR-R) to the characterization of porous ceramics nearly free of magnetic compounds. Different microstructural properties were obtained by firing a diamagnetic mixture of kaolin, calcium, and magnesium carbonate over a wide range of maximum temperatures (600–1100 °C) and firing times at the maximum temperature (soaking times) (0–10 h). The 2D ¹H NMR-R method relies on the correlated measurement of ¹H longitudinal (T ₁) and transverse (T ₂) relaxation times of pore-filling water by which the properties of the interconnected pore space may be investigated. In the absence of significant magnetic susceptibility effect due to para- and ferro-magnetic compounds, the 2D ¹H NMR-R maps allow studying the conjoint effects on pore size distribution and inter-pore coupling due to the variations in both time and temperature of firing. The NMR experiments were performed with a low-field ¹H NMR sensor, which allows non-destructive and in situ analysis. For ceramic specimens fired at 600 and 700 °C, the fraction of smallest pores increases with firing time at the expenses of those with intermediate size. The pore shrinkage occurring at this stage, and likely associated with the transformation of kaolinite in metakaolinite, is affected in a similar way by soaking time and firing temperature, in line with the concept of equivalent firing temperature. At temperatures from 800 to 1100 °C, the structural modifications involving interconnectivity and average pore size are driven primarily by firing temperature and, secondarily, by soaking time. The 2D ¹H NMR-R results are confirmed by more traditional, but destructive, mineralogical, and structural analyses like X-ray powder diffraction, helium pycnometry, mercury intrusion porosimetry, and nitrogen adsorption/desorption method.     

Structural transformation study of TiO2 nanoparticles annealing at different temperatures and the photodegradation process of eosin-Y

Hydrothermal method was used to prepare TiO₂ nanoparticles with annealing temperature at 500 °C–700 °C. The mixture of anatase-rutile phase was investigated by powerful tool of X-ray diffraction (XRD). The structural parameters of anatase and rutile mixture phaseTiO₂ nanoparticles were calculated from the Rietveld refinement. The transformation rate of rutile was increased linearly with an annealing temperature of 500 °C–700 °C. The spherical morphology of the anatase and rutile mixed phase were obtained by scanning electron microscope and transmission electron microscope. The spherical particle of the anatase and rutile TiO₂ shows with great aggregation with different size and within the range of few tens nm. The EDAX study revealed the presence of titanium and oxygen. The best photocatalytic activity was identified as the 87.04% of anatase and 12.96% of rutile mixer phase of TiO₂. Various factors could be involved for a better photocatalytic activity.     

Specific features of electrical properties of porous biocarbons prepared from beech wood and wood artificial fiberboards

This paper reports on comparative investigations of the structural and electrical properties of biomorphic carbons prepared from natural beech wood, as well as medium-density and high-density fiberboards, by means of carbonization at different temperatures T _carb in the range 650–1000°C. It has been demonstrated using X-ray diffraction analysis that biocarbons prepared from medium-density and high-density fiberboards at all temperatures T _carb contain a nanocrystalline graphite component, namely, three-dimensional crystallites 11–14 Å in size. An increase in the carbonization temperature T _carb to 1000°C leads to the appearance of a noticeable fraction of two-dimensional graphene particles with the same sizes. The temperature dependences of the electrical resistivity ρ of the biomorphic carbons have been measured and analyzed in the temperature range 1.8–300 K. For all types of carbons under investigation, an increase in the carbonization temperature T _carb from 600 to 900°C leads to a change in the electrical resistivity at T = 300 K by five or six orders of magnitude. The dependences ρ(T) for these materials are adequately described by the Mott law for the variable-range hopping conduction. It has been revealed that the temperature dependence of the electrical resistivity exhibits a hysteresis, which has been attributed to thermomechanical stresses in an inhomogeneous structure of the biocarbon prepared at a low carbonization temperature T _carb. The crossover to the conductivity characteristic of disordered metal systems is observed at T _carb ? 1000°C.     

Unusual structural phase transition in nanocrystalline zirconia

The present work is the first example demonstrating that a hydrous zirconia formed by precipitation can yield a nearly pure nanocrystalline monoclinic zirconia at a temperature as low as 320 °C. The X-ray diffraction pattern of the hydrous zirconia heated to 310 °C shows that diffraction peaks begin to emerge and reveals a just crystallized mixture of predominantly monoclinic zirconia (70%) with some tetragonal zirconia(30%). In other words, the hydrous zirconia formed in the present work yields the predominantly monoclinic structure coexisting with the tetragonal one as soon as crystallization starts at low temperature (310 °C). This is an important exception to the general principle that amorphous zirconia precursors first convert to the tetragonal structure of zirconia with increasing calcination temperature and then transform to the monoclinic one at a higher temperature (∼600 °C). At the crystallization temperature (310 °C), the monoclinic crystallite size is about 17 nm and the tetragonal one 28 nm. The monoclinic crystallite is much smaller than the tetragonal one with which it co-exists. This result is also not consistent with the traditional view that a critical particle size effect is responsible for the stability of the tetragonal and monoclinic structures. When the temperature (310 °C) is slightly raised to 320 °C, the XRD pattern shows a nearly pure monoclinic zirconia. The crystallite size of the monoclinic zirconia is around 15 nm, and it does not change appreciably as calcination temperature is increased from 320 to or above 400 °C. The unusual structural phase transition has been investigated by several complementary experimental tools: X-raydiffraction and surface analyses, and infrared and Raman spectroscopies. PACS 81.07.-b; 64.70.Nd; 82.80.-d; 78.67.-n; 81.05.Je     

Self-organization of the structure in the Cu60Fe40 composite during deformation-thermal treatment

The deformation-thermal stability of a clusterized amorphous-crystalline structure prepared from a Cu₆₀Fe₄₀ powder mixture at a logarithmic strain e = 4.6 and subjected to isochronous (40 min) annealings at T _a = 200–800°C has been investigated. Periodic changes (ΔT = 300°C) in the order and disorder with a maximum ordering at T _a = 300 and 600°C and a maximum disordering at T _a = 400 and 700°C have been observed. The periodicity of the dominant crystallographic order with a period ΔT = 400°C in the annealing temperature has been revealed for face-centered cubic copper phase planes separated by a singular point at T = 500°C characterized by the dominant body-centered cubic iron phase ordering. It has been shown that the sawtooth shape of the size distribution of strain clusters formed within the crystal structure of deformed samples slowly changes with increasing annealing temperature from exponential (T _a = 200–700°C) to linear (T _a = 800°C). This indicates a high density of internal local distortions in structural units.     

Influence of synthesis method on structural and magnetic properties of cobalt ferrite nanoparticles

The Co–ferrite nanoparticles having a relatively uniform size distribution around 8 nm were synthesized by three different methods. A simple co-precipitation from aqueous solutions and a co-precipitation in an environment of microemulsions are low temperature methods (50 °C), whereas a thermal decomposition of organo-metallic complexes was performed at elevated temperature of 290 °C. The X-ray diffractometry (XRD) showed spinel structure, and the high-resolution transmission electron microscopy (HRTEM) a good crystallinity of all the nanoparticles. Energy-dispersive X-ray spectroscopy (EDS) showed the composition close to stoichiometric (~CoFe₂O₄) for both co-precipitated nanoparticles, whereas the nanoparticles prepared by the thermal decomposition were Co-deficient (~Co_0.6Fe_2.4O₄). The X-ray absorption near-edge structure (XANES) analysis showed Co valence of 2+ in all the samples, Fe valence 3+ in both co-precipitated samples, but average Fe valence of 2.7+ in the sample synthesized by thermal decomposition. The variations in cation distribution within the spinel lattice were observed by structural refinement of X-ray absorption fine structure (EXAFS). Like the bulk CoFe₂O₄, the nanoparticles synthesized at elevated temperature using thermal decomposition displayed inverse spinel structure with the Co ions occupying predominantly octahedral lattice sites, whereas co-precipitated samples showed considerable proportion of cobalt ions occupying tetrahedral sites (nearly 1/3 for the nanoparticles synthesized by co-precipitation from aqueous solutions and almost 1/4 for the nanoparticles synthesized in microemulsions). Magnetic measurements performed at room temperature and at 10 K were in good agreement with the nanoparticles’ composition and the cation distribution in their structure. The presented study clearly shows that the distribution of the cations within the spinel lattice of the ferrite nanoparticles, and consequently their magnetic properties are strongly affected by the synthesis method used.     

Suppression of the exaggerated growth of barium ferrite nanoparticles from solution using a partial substitution of Sc<Superscript>3+</Superscript> for Fe<Superscript>3+</Superscript>

The effect of the substitution of Sc³⁺ for Fe³⁺ in barium ferrite on the size of the resulting nanoparticles was studied. These nanoparticles, with the nominal compositions BaFe₁₂O₁₉ and BaFe_11.5Sc_0.5O₁₉, were synthesized hydrothermally at 90–240 °C or by coprecipitation under reflux at 140 °C. The precursors were obtained using (co)precipitation at room temperature. The sizes and morphologies of the precursors and nanoparticles were inspected with transmission electron microscopy, while their structures were confirmed with a combination of X-ray powder and electron diffraction. The samples’ compositions were analyzed with energy-dispersive X-ray spectroscopy. The evolution of the particle size and its distribution with the synthesis temperature and time were studied in pure and Sc-substituted barium ferrite and correlated with the evolution of the magnetic properties. The Sc substitution in the barium ferrite results in the formation of magnetic nanoparticles with applicable magnetic properties and in a significant reduction of the exaggerated particle growth. This was explained on the basis of the reaction kinetics.     

Variety of LaSrMnO structures induced by growth conditions and laser irradiation

Crystallographic phase transitions in perovskite-like LaSrMnO metallic oxides are studied. The transitions are induced when internal stresses generated during film synthesis (at temperatures between 450 and 730°C) vary (decrease or increase) upon subsequent irradiation by a KrF laser emitting in the UV range. As the synthesis temperature T _s grows, the rhombohedral-to-orthorhombic phase transition occurs at 650–670°C. The resistivity is shown to be either temperature-independent, ρ(T)=const, at T<T _crit, or varies and reaches a maximum, ρ(T)=ρ_max, at the Curie temperature T _c. Optical transmission spectra taken at photon energies ℏω=0.5–2.5 eV exhibit both a high (0.8–0.9) and low (0.1–0.3) transmission coefficient t, depending on the synthesis temperature. As follows from X-ray diffraction data, the laser irradiation causes a phase transition only in LaSrMnO films grown at T _s<650°C. Phases of different size scales appear: the long-range-order orthorhombic matrix and mesoscopic-range-order rhombohedral clusters are observed in the films grown at T _s=450–550°C and the rhombohedral matrix with orthorhombic clusters, in the films grown at T _s=550–650°C.     

Structural, calorimetric and magnetic properties study of the Cu0,91Fe0,09O system

In this work the Cu_0.91Fe_0.09O nanocrystalline system was prepared via the co-precipitation method. Using Mössbauer Spectrometry, X-Ray Diffraction, Vibrating Sample Magnetometry, Thermogravimetry and Differential Scanning Calorimetry, we study the magnetic behavior, and the structural and calorimetric properties of this system. X-ray diffraction shows only the presence of the CuO structural monoclinic phase, suggesting that Cu atoms are substituted by Fe ones. This hypothesis was confirmed by Mössbauer spectrometry at room temperature, because it shows that the spectrum is formed by two doublets, which correspond to Fe^?+?2 and Fe^?+?3 sites. Hysteresis cycles obtained by vibrating sample magnetometry detect a soft ferromagnetic behavior at room temperature with coercive fields between 8 and 20 Oe. At T = 20 K the sample shows a hard-magnetic behavior. The thermogravimetry results show a Néel temperature (T _N > 440 °C). The differential scanning calorimetry curve show two endothermic peaks in the 90–120 °C range.     

Pulsed laser deposition conditions and superconductivity of FeSe thin films

We report the effects of growth conditions on the superconducting properties of FeSe films epitaxially grown on LaAlO₃ substrates by pulsed laser deposition (PLD). Customary materials characterization techniques [X-ray diffraction (XRD), in-situ X-ray photoelectron spectroscopy (XPS), in-situ ultra-violet photoelectron spectroscopy (UPS), and scanning electron microscopy (SEM)] revealed the films had a c-axis oriented tetragonal structure with lattice constants dependent on the growth temperature (varied from 100 to 600°C). The standard four-point probe method was used to measure the resistivity and superconducting transitions. Films grown at 400–550°C showed a clear superconducting onset but no zero resistance down to 2 K. The highest superconducting onset temperature (T_c^onsetT_{\mathrm{c}}^{\mathrm{onset}}) of 8 K was observed in films grown at 500°C and the onset temperature was clearly correlated to the ratio of the lattice constants (c/a). As the thickness of the FeSe films increased from 27 nm to 480 nm, T_c^onsetT_{\mathrm{c}}^{\mathrm{onset}} also increased as the strain in the system was relaxed.     

Thermal conductivity at the amorphous-nanocrystalline phase transition in beech wood biocarbon

High-porosity samples of beech wood biocarbon (BE-C) were prepared by pyrolysis at carbonization temperatures T _carb = 650, 1300, and 1600°C, and their resistivity ρ and thermal conductivity κ were studied in the 5–300 and 80–300 K temperature intervals. The experimental results obtained were evaluated by invoking X-ray diffraction data and information on the temperature dependences ρ(T) and κ(T) for BE-C samples prepared at T _carb = 800, 1000, and 2400°C, which were collected by the authors earlier. An analysis of the κ(T _carb) behavior led to the conclusion that the samples under study undergo an amorphous-nanocrystalline phase transition in the interval 800°C < T _carb < 1000°C. Evaluation of the electronic component of the thermal conductivity revealed that the Lorentz number of the sample prepared at T _carb = 2400°C exceeds by far the classical Sommerfeld value, which is characteristic of metals and highly degenerate semiconductors.     

Role of salt concentration on conductivity optimization and structural phase separation in a solid polymer electrolyte based on PMMA-LiClO4

Although a large number of ionic conductors based on poly(methyl-methacrylate) (PMMA) are reported in literature, an optimization of salt concentration with respect to conductivity and stability properties remains by and large neglected. We report, perhaps for the first time, such an optimization of salt (LiClO₄) concentration on structural, morphological, electrical, and ion–polymer interaction in PMMA-based solid polymer films. The active coordination site for the cation (Li⁺), out of the two possible electron donating functional groups (i.e. C=Ö and Ö–CH₃) in PMMA, has been ascertained on the basis of evidences recorded in Fourier transform infrared spectrum. The results suggested C=Ö as the only possible site in PMMA matrix for coordination with Li⁺ cation. The X-ray diffraction results have clearly indicated an optimum limit of salt dissolution in PMMA matrix corresponding to O/Li = 4 (i.e., ~21wt.%) above which “phase-separation” occurs distinctly. The effect of salt concentration on amorphous → crystalline phase changes in PMMA and its correlation to morphology have been clearly observed in terms of their impact on electrical properties. An optimum electrical conductivity of ~7.2 × 10^?5S cm^?1 has been recorded at 100°C (~PMMA glass transition). The temperature dependence of conductivity follows typical Vogel–Tamman–Fulcher behavior.     

Kinetic study of the thermal transformation of limonite to hematite by X-ray diffraction, ��-Raman and M?ssbauer spectroscopy

A kinetic study about the phase limonite (FeO(OH)-nH₂O) was performed through X-ray diffraction, ??-Raman spectroscopy and Mössbauer spectroscopy. The oxide powder sample was extracted from Taraco district, Huancané province of Puno (Peru). X-ray diffraction identified the phase goethite as the main mineralogical component, and then the sample was subjected to in-situ heat treatment in the temperature range: 100 to 500°C in oxidizing (air) and inert (nitrogen) atmospheres. The goethite phase remains stable in this range: room temperature to 200°C. Between 200°C to 250°C there is a phase transition: ??-Fe^3?+?O(OH) ?? ??-Fe₂O₃, i.e., from goethite to hematite phase, taking as evidence the evolution of the diffraction profiles. At 200°C spectra shows the start of broadened magnetic component and it was adjusted through of a magnetic distribution giving a mean field of 38.6T and a relative area of 52.9%, which is a characteristic of goethite. Also, it is noticed the presence of a small amount of hematite with a mean field of 49.0T linked with a superparamagnetic broadened doublet of relative area of 47.1% where the domains of the particles have sizes smaller than 100 Å and it is evidence the superparamagnetic limit; i.e., the superparamagnetic effect tends toward a distribution of magnetic fields. Moreover, the Raman spectra of the in-situ thermal treatment, support the transition at 290°C through the transformation of characteristic bands of goethite to hematite phase at the frequency range from 200 to 1,800 cm^???1.