Preparation and characterization of hybrid nanoparticles based on chitosan and poly(methacryloylglycylglycine)

CeO₂–MnO _x composites possessing rod-like morphology (fixed mole proportion of Ce/Mn) were synthesized through hydrothermal method and chosen as supporters to load PdO nanoparticles (PdO/Ce _x Mn_1–x ). The size of loaded PdO nanoparticles is about 2 nm. The catalytic behaviors of supported catalysts were examined through the complete catalytic oxidation of benzene. The results illustrated that the activities of supported catalysts were enhanced greatly as compared to unsupported, and the completely conversion temperature of benzene was reduced to ca. 250 °C. The effect of noble metal species (PdO) addition on the catalytic property and crystal structure of composites was researched in detail. The data revealed that the interaction between PdO and supporter, and intrinsic properties of supporter resulted in the enhancement of catalytic abilities.     

Oxidation of dodecane on vanadium-molybdenum catalysts

The catalytic oxidation of dodecane with air oxygen on individual and mixed vanadium-molybdenum (1 ? x)V₂O₅ · xMoO₃ oxide is studied over a temperature range of 250 to 400°C. It is shown that oxidation of dodecane to organic acids at 250°C produces undecylic acid C₁₁H₂₆COOH and carbon oxides, as products of the subsequent oxidation of formic acid. The most effective catalyst is a mixed oxide containing 75 mol % MoO₃ and 25 mol % V₂O₅. At 275–300°C, this catalyst provides the maximum yield of acids and a relatively low fraction of complete-oxidation products. Above 250°C, a mixture of acids and carbon oxides is formed, the yield of which increases with the temperature up to 300°C. As the temperature is increased still further, the yield of acids decreases due to their subsequent oxidation. The catalytic oxidation is accompanied by changes in the phase composition, morphology, and degree of crystallinity of the mixed-oxide catalysts. A possible mechanism of the catalytic process is considered.     

Synthesis and structural characteristics of La2 ? x Sr x NiO4 dielectric ceramics

Fine-grained single phase La_{2 ? x} Sr _x NiO_{4 + ??} powders are produced by means of self-propagating high temperature synthesis (SHS) after annealing the primary product at 670°C. Ammonium citrate was used as the reduction agent. It is shown that the reduction in unit cell volume due to lanthanum being replaced by larger strontium ions is caused by an increase in nickel oxidation.     

Optical observation of oxidation and reduction of small supported copper particles

In situ and real-time optical absorption measurements of supported copper particles (4–10 nm) at wavelengths of 300 to 800 nm are carried out under H₂, CO, and O₂ respectively as ambient gases in the temperature range of 300 to 673 K. We observe a reversible change in the optical spectra caused by oxidation of copper and reduction of copper oxide. The data strongly indicate that the oxidation of small copper particles is composed of a fast process of Cu to CuO_x (x ≈ 0.67) and a slow process of CuO_x (x≈ 0.67) to CuO.     

Oxidation of benzene and thiophene on a nanostructured vanadium-molybdenum mixed oxide

The catalytic oxidation of benzene and thiophene by air oxygen on a nanostructured vanadium-molybdenum mixed oxide with 50 mol % MoO₃ and 50 mol % V₂O₅ prepared by the solvothermal method is studied. It is shown that, in the temperature range 200–350°C, the catalyst efficiently oxidizes thiophene (with a degree of conversion of up to 40 mol %) and poorly oxidizes benzene. This enables to consider nanostructured molybdenum-vanadium oxides as promising for the low-temperature catalytic desulfurization of hydrocarbons. It is demonstrated that the reaction causes a change in the structure and morphology of the oxide system.     

Giant temperature coefficient of resistance in Co-doped ZnO thin films

A novel high-performance thermistor material based on Co-doped ZnO thin films is presented. The films were deposited by the pulsed laser deposition technique on Si (111) single-crystal substrates. The structural and electronic transport properties were correlated as a function of parameters such as substrate temperature and Co-doped content for Zn_1?x Co _x O (x=0.005,0.05,0.10 and 0.15) to prepare these films. The Zn_1?x Co _x O films were deposited at various substrate temperatures between 20 and 280 °C. A value of 20 %/K for the negative temperature coefficient of resistance (TCR) with a wide range near room temperature was obtained. It was found that both TCR vs. temperature behavior and TCR value were strongly affected by cobalt doping level and substrate temperature. In addition, a maximal TCR value of over 20 %?K^?1 having a resistivity value of 3.6 Ω?cm was observed in a Zn_0.9Co_0.1O film near 260 °C, which was deposited at 120 °C and shown to be amorphous by X-ray diffraction. The result proved that the optimal Co concentration could help us to achieve giant TCR in Co-doped ZnO films. Meanwhile, the resistivities of the films ranged from 0.4 to 270 Ω?cm. A Co-doped ZnO/Si film is a strong candidate of thermometric materials for non-cooling and high-performance bolometric applications.     

Electron magnetic resonance spectra of Fe1−x Mnx amorphous nanoparticles

Nanoparticles of Fe_1?x Mn_x (0.07 < x < 0.20) alloys are studied using electron magnetic resonance in the temperature range 295–500 K. It is found that the temperature and manganese concentration in the nanoparticles have a noticeable effect on their electron magnetic resonance spectra. It is suggested that the Fe_1?x Mn_x nanoparticles contain phases with different magnetic properties and that the relative content of the phases depends on the manganese concentration in the nanoparticles. The magnetic transition temperature lies above 500 K for one of these phases and in the temperature range 350–375 K for another.     

Ionic conductivity of Ce1−xNdxO2−x / 2

The electrical conductivity of sintered samples of Ce_1−xNd_xO_2−x / 2 (0.01 ≤ x ≤ 0.2) was investigated in air as a function of temperature between 150 and 600 °C using AC impedance spectroscopy. The individual contribution of the bulk and grain boundary conductivities has been discussed in detail. In the low temperature range (< 350 °C), the activation enthalpy for bulk conductivity exhibited a shallow minimum at 3 mol% Nd, with a value of 0.68 eV. The activation enthalpy also produced a shallow minimum at 5 mol% Nd in the high temperature range (> 350 °C), with a value of 0.56 eV. It was shown that Ce_1−xNd_xO_2−x / 2 is an electrolyte that obeys the Meyer Neldel rule. The bulk conductivity data measured by others for the same system has also been recalculated and re-evaluated to facilitate easier comparison with our own data.     

Synthesis and characterization of Ca and Sr co-doped ceria electrolytes

A series of Ce_0.85Ca_0.15?x Sr _x O_2–δ (x?=?0, 0.03 and 0.06) were synthesized via citrate–nitrate combustion method. Samples were first characterized by the X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD and SEM results showed that a complete solid solution formed in fluorite structure and Ce_0.85Ca_0.15?x Sr _x O_2?δ had homogeneous distribution of particle with grain size in the range of 2.5 to 3 μm. The electrical conductivities of Ce_0.85Ca_0.15?x Sr _x O_2?δ were evaluated for its use as a solid electrolyte in the intermediate-temperature solid oxide fuel cells by complex plane impedance measurements. Impedance measurements were made in the frequency range 1 MHz–0.1 Hz and temperature range 300–700 °C. It was found that Ce_0.85Ca_0.12Sr_0.03O_2?δ showed highest conductivity.     

Thermal conductivity and Lorentz number of the “Golden” phase of the Sm1−x GdxS system with homogeneous variable valence of samarium

The thermal conductivity and electrical resistivity are measured in the temperature range 160–300 K for two compositions of the “golden” phase of the Sm_1?x Gd_xS system with x=0.14 and 0.3, in which a homogeneous variable valence of samarium ions is observed. It is found that, in this temperature range, the experimentally obtained Lorentz number L appearing in the electron component of thermal conductivity for these compositions exceeds the theoretical Sommerfeld value L ₀=2.45×10^?8 WΩ/K² typical of metals and highly degenerate semiconductors. It is also proved that the value of L increases with temperature in the interval 160–300 K starting from 160 K. A theoretical model capable of explaining the obtained experimental results is discussed.     

Properties of the ceramic manganite (La0.65Ca0.35)1 − x Mn1 + x O3 ± Δ (x = 0.2) sintered at temperatures of 1000–1450°C

It has been shown that the ceramics (La_0.65Ca_0.35)_{1 ? x} Mn_{1 + x} O_{3 ± Δ} (x = 0.2) sintered at temperatures up to 1450°C is formed as a composite material consisting of manganite and manganese oxide grains. It has been found that, at a sintering temperature of 1450°C, the manganite grain size abruptly increases, which is accompanied by the formation of a nanometer-sized layered structure. It has been revealed for the first time that the temperature dependence of the magnetoresistance of the ceramic manganite with this structure is characteristic of single crystals.     

The plasticity of the Cu(H2O) 6 2+ Jahn-Teller complex affected by lattice strains and cooperative interactions

The EPR spectra evolution of Cs₂Zn_1?x Cu_x(ZrF₆)₂ · 6H₂O (x=0.01, 0.6, 0.8, and 1.0) in the temperature range 4.2–330 K and the x-ray structure analysis of the compound with x=1.0 in the range 150–327 K show that the Jahn-Teller (JT) complex Cu(H₂O)₆ coordination sphere undergoes a plastic deformation. The observed effect is due to the combined influence of small lattice strains existing in the paraphase and a new one appearing as a result of a ferroelastic phase transition and increasing with decreasing temperature below T _c . It is proved that both cooperative interactions between JT complexes and ferroelastic strain stabilize a certain JT configuration. The problem of instability of a JT configuration compressed at T ～ 265 K is discussed.     

Heat capacity of BiFeO3-based multiferroics

The heat capacity of Bi_{1 ? x} Re _x FeO₃ (Re = La, Eu, Ho; x = 0, x = 0.05) multiferroics has been studied in the temperature range of 120–800 K. The substitution of a small amount of rare-earth elements for bismuth leads to a significant increase in the heat capacity in the broad temperature range studied. It is established that the temperature dependence of the excess heat capacity is related to the Schottky effect for three-level states certain that appear as a result of structure distortions in the rare-earth-doped compositions.     

Magnetic ordering in Mg−Zn ferrites

The magnetic ordering of a series of magnesium-zinc ferrite, Zn_0.3Mg _x Fe_2.7?x O_4±δ (0.5≤x≤1.1; 0≤δ≤0.2) has been investigated using Mössbauer measurements in the temperature range 295–620 K. The samples were found to be magnetic at room temperature with a hyperfine field at each site which increases with iron content. The Curie temperature was also observed to increase in a similar manner. The slope of this increase forB _hf andT _c is steeper forx≤0.6 thanx≥0.7. It has also been observed that Mg²⁺ substitution by Zn²⁺ in MgFe₂O₄ affects the magnetic ordering and the internal hyperfine field. The Curie temperature decreases by ～200 K andB _hf by ～20%.     

Dielectric, modulus and impedance analysis of lead-free ceramics Ba0.8La0.133Ti1−x Sn x O3 (x=0.15 and 0.2)

Titanate barium (BaTiO₃)-type oxide ceramics Ba_0.8La_0.133Ti_1?x Sn _x O₃ (BLTS) (here x=0.15 and 0.2) have been synthesized by the standard solid-state reaction method. Preliminary room temperature X-ray study confirms the formation of single-phase compounds in a rhombohedral crystal system. The electrical properties of BLTS were studied using the ac impedance spectroscopy technique over a wide range of temperature (120–320 K) in the frequency range of 40 Hz to 10 MHz. The presence of a single arc in the complex modulus spectrum at different temperatures confirms the single-phase character of the BLTS compounds.     

Piezobirefringence in γ1-(GaxIn1−x )2Se3 single crystals

The piezobirefringence of uniaxial γ₁-(Ga_xIn_1−x )₂Se₃ crystals (x=0.3, 0.4) was investigated in the spectral range 0.6–1.1 μm at temperatures from 77 to 295 K. It is shown that uniaxial compression leads to a linear decrease in the birefringence, whereas a decrease in temperature reduces the effect of piezobirefringence. The baric changes in the birefringence are attributed to the baric changes in the contribution of the edge transitions to the total birefringence. __________ Translated from Optika i Spektroskopiya, Vol. 95, No. 3, 2003, pp. 458–461. Original Russian Text Copyright ? 2003 by Studenyak, Kran’chets, Suslikov, Kovach.     

X-ray spectroscopic investigation of some spinel structures

K-absorption edges of cations in the manganites of magnesium, nickel, copper, zinc and cadmium and ferrite samples of composition, Mg_1?x Mn_x Fe₂O₄ (x=0, 0·25, 0·50, 0·75, 1·0), have been recorded employing a 40 cm curved mica crystal spectrograph of transmission type. It is observed that the absorption edges for the specimen shift towards the shorter wavelength side of the metal edge position. Shifts of both the absorption edges and the main absorptoin peaks for ferrites and manganites have been compared with compounds in which the oxidation state of the cation is well known. It is found that the manganese ions in these ferrites and manganites exist in valence states two and three respectively while iron in the ferrite samples is present in oxidation state three. An attempt has been made to interpret the observed absorption edge features in the light of neutron and X-ray diffraction studies on the same ferrite and manganite samples.     

Visualization of the magnetic flux structure in phosphorus-doped EuFe<Subscript>2</Subscript>As<Subscript>2</Subscript> single crystals

Magnetic flux structure on the surface of EuFe₂(As_1-x P _x )₂ single crystals with nearly optimal phosphorus doping levels x = 0.20 and x = 0.21 is studied by low-temperature magnetic force microscopy and decoration with ferromagnetic nanoparticles. The studies are performed in a broad temperature range. It is shown that the single crystal with x = 0.21 in the temperature range between the critical temperatures T _SC= 22 K and T _C = (18 ± 0.3) K of the superconducting and ferromagnetic phase transitions, respectively, has the vortex structure of a frozen magnetic flux, typical for type-II superconductors. The magnetic domain structure is observed in the superconducting state below T _C. The nature of this structure is discussed.     

Effect of Cd impurity on the electrical properties of a-Se80Te20

Temperature dependence of dark and photoconductivity is studied in amorphous films of Se₈₀Te_20−xCd_x in the temperature range (300 K to 380 K) with a view to see the effect of Cd impurity on a-Se₈₀Te₂₀ binary alloy. It is observed that, at low concentration of Cd (x = 0.5), the dark and photoconductivity increase at all temperatures. However, at higher concentration of Cd (x = 10), an appreciable reduction in these parameters occurs in the same temperature range. The photosensitivity (σ_ph/σ_d) remains unchanged at x = 0.5 but decreases quite significantly at x = 10. The results are explained in terms of impurity doping at x = 0.5 and alloying effect at x = 10.     

Oxygen non-stoichiometry and electrical conductivity of Pr2−xSrxNiO4±δ with x = 0–0.5

Oxygen non-stoichiometry and electrical conductivity of the Pr_2−xSr_xNiO_4±δ series with x = 0.0–0.5 were investigated in Ar/O₂ (pO₂ = 2.5 to 21 000 Pa) within a temperature range of 20–1000 °C. The equilibrium values of oxygen non-stoichiometry and electrical conductivity of these nickelates were determined as functions of temperature and oxygen partial pressure (pO₂). The nickelates with x = 0–0.5 appear to be p-type semiconductors in the investigated temperature and pO₂ ranges. The nickelates with x = 0.3–0.5 show very feebly marked pO₂ dependencies of the conductivity. Pr_1.7Sr_0.3NiO_4±δ shows the anomalies of the conductivity versus oxygen partial pressure which can be related to the orthorhombic–tetragonal crystal structure transformations. The conductivity of the Pr_2−xSr_xNiO_4±δ samples correlates with the average oxidation state of the nickel cations. The samples with x = 0.5 have the highest nickel oxidation state (≈ 2.5+), the highest [Ni³⁺]/[Ni²⁺] ratio close to 1 and show the highest conductivity (≈ 120 S/cm) in the whole pO₂ and temperature ranges investigated.