Mg substitution in CuCrO2 delafossite compounds

A detailed investigation of the series CuCr_1−xMg_xO₂ (x=0.0-0.05) has been performed by making high-temperature resistivity and thermopower measurements, and by performing a theoretical analysis of the latter. Microstructure characterization has been carried out as well. Upon Mg²⁺ for Cr³⁺ substitution, a concomitant decrease in the electrical resistivity and thermopower values is found, up to x∼0.02-0.03, indicating a low solubility limit of Mg in the structure. This result is corroborated by scanning electron microscopy observations, showing the presence of MgCr₂O₄ spinels as soon as x=0.005. The thermopower is discussed in the temperature-independent correlation function ratio approximation as based on the Kubo formalism, and the dependence of the effective charge carrier density on the nominal Mg substitution rate is addressed. This leads to a solubility limit of 1.1% Mg in the delafossite, confirmed by energy dispersive X-ray spectroscopy analysis.     

Sol–gel auto-combustion synthesis,structural and enhanced magnetic properties of Ni substituted nanocrystalline Mg–Zn spinel ferrite

Nanocrystalline arrays of Ni²⁺ substituted Mg–Zn spinel ferrite having a generic formula Mg_0.7−xNi_xZn_0.3Fe₂O₄ (x=0.0, 0.2, 0.4 and 0.6) were successfully synthesized by sol–gel auto-combustion technique. The fuel used in the synthesis process was citric acid and the metal nitrate-to-citric acid ratio was taken as 1:3. The phase, crystal structure and morphology of Mg–Ni–Zn ferrites were investigated by X-ray diffraction, scanning electron microscopy, and Fourier transformer infrared spectroscopy techniques. The lattice constant, crystallite size, porosity and cation distribution were determined from the X-ray diffraction data method. The FTIR spectroscopy is used to deduce the structural investigation and redistribution of cations between octahedral and tetrahedral sites of Mg–Ni–Zn spinel structured material. Morphological investigation suggests the formation of grain growth as the Ni²⁺ content x increases. The saturation magnetization and magneton number were determined from hysteresis loop technique. The saturation magnetization increases with increasing Ni²⁺ concentration ‘x’ in Mg–Zn ferrite.     

Coating formation by plasma electrolytic oxidation on ZC71/SiC/12p-T6 magnesium metal matrix composite

Plasma electrolytic oxidation (PEO) of a ZC71/SiC/12p-T6 magnesium metal matrix composite (MMC) is investigated in relation to coating growth and corrosion behaviour. PEO treatment was undertaken at 350 mA cm⁻² (rms) and 50 Hz with a square waveform in stirred 0.05 M Na₂SiO₃.5H₂O/0.1 M KOH electrolyte. The findings revealed thick, dense oxide coatings, with an average hardness of 3.4 GPa, formed at an average rate of ∼1 μm min⁻¹ for treatment times up to 100 min and ∼0.2 μm min⁻¹ for later times. The coatings are composed mainly of MgO and Mg₂SiO₄, with an increased silicon content in the outer regions, constituting <10% of the coating thickness. SiC particles are incorporated into the coating, with formation of a silicon-rich layer at the particle/coating interface due to exposure to high temperatures during coating formation. The distribution of the particles in the coating indicated growth of new oxide at the metal/coating interface. The corrosion rate of the MMC in 3.5% NaCl is reduced by approximately two orders of magnitude by the PEO treatment.     

On the superconductivity in in situ synthesized MgB2 tapes

Single core stainless steel (SS) sheathed MgB₂ tapes have been made by the powder-in-tube (PIT) method using commercial Mg and B powders in two series, one with nominal composition and the other with excess Mg. The electrical resistivity and susceptibility measurements have been carried out to evaluate residual resistivity ratio (RRR), the coherence length ξ(0) and critical current density J_C(T) in these tapes. Detailed structural analysis of the core material has been carried out to correlate the superconducting properties with the crystallinity. In the optimized growth condition the MgB₂ tapes exhibited an estimated J_C of ∼1.4×10⁷ A/m² at 39.45 K in zero field and the zero temperature coherence length is found to be ∼68 Å. MgB₂ tapes fabricated from starting powders having nominal Mg-composition have been shown to exhibit higher J_C than those fabricated from excess magnesium composition of the starting powders. The strained lattice together with the presence of nanosized MgO inclusion having size smaller than the coherence length, are shown to be responsible for the observed higher J_C.     

Substitutional effect of Cr ions on the properties of Mg–Zn ferrite nanoparticles

The effect of Cr³⁺ substitution in Mg–Zn ferrite, with a chemical formula Mg_0.5Zn_0.5Cr_xFe_2−xO₄ (x=0.0–1.0), synthesized by a sol–gel auto-combustion reaction is presented in this paper. The resultant powders were investigated by various techniques, including X-ray diffractometry (XRD), transmission electron microscopy (TEM), infrared spectroscopy (IR), vibrating sample magnetometry (VSM), and DC resistivity. The XRD pattern revealed that the cubic spinel structure is maintained for the all the compositions. The particle sizes measured from XRD and TEM are in good agreement with each other. The cation distribution suggests that Mg²⁺, Cr³⁺ and Fe³⁺ have strong preference towards octahedral B-site. The theoretical lattice constant and experimental lattice constant match each other very well. The IR analysis supports the presently accepted cation distribution. The saturation magnetization decreases linearly with increasing Cr³⁺ content. Curie temperatures are obtained by the Laoria and AC susceptibility techniques. The dc resistivity has been investigated as a function of temperature and composition.     

Synthesis and magnetic properties of Au-coated amorphous Fe20Ni80 nanoparticles

Gold-coated nanoparticles of Fe₂₀Ni₈₀ (permalloy) have been synthesized by a microemulsion process. The as-prepared samples consist of ∼5 nm diameter particles of amorphous Fe₂₀Ni₈₀ that are likely encapsulated in B₂O₃. One or more Fe₂₀Ni₈₀@B₂O₃ particles are subsequently encapsulated in 8-20 nm gold nanospheres, as determined by TEM and X-ray powder diffraction (XRD) line broadening. The gold shells were found to be under expansive strain. Magnetic data confirm the existence of a superparamagnetic phase with a blocking temperature, T_B, of ∼33 K. The saturation magnetization, M_S, of the as-prepared, Au-coated sample is ∼65 emu g⁻¹ at 5 K and ∼16 emu g⁻¹ at 300 K. The coercivity, H_C, is ∼280 Oe at 5 K.     

Ionic conductivity and electrochemical stability of poly(methylmethacrylate)-poly(ethylene oxide) blend-ceramic fillers composites

The role of inorganic ceramic fillers namely nanosized Al₂O₃ (15-25 nm) and TiO₂ (10-14 nm) and ferroelectric filler SrBi₄Ti₄O₁₅ (SBT CIT) (0.5 μm) synthesized by citrate gel technique (CIT) on the ionic conductivity and electrochemical properties of polymer blend 15 wt% PMMA+PEO₈:LiClO₄+2 wt% EC/PC electrolytes were investigated. Enhancement in conductivity was obtained with a maximum of 0.72×10⁻⁵ S cm⁻¹ at 21 °C for 2 wt% of SrBi₄Ti₄O₁₅ (SBT CIT) composite polymer electrolyte. The lithium-ion transport number and the electrochemical stability of the composite polymer electrolytes at ambient temperature were analyzed. An enhancement in electrochemical stability was observed for polymer composites containing 2 wt% of SrBi₄Ti₄O₁₅ (SBT CIT) as fillers.     

A comparative study of the electrical and the magnetic properties and Mössbauer studies of normal and hot pressed MgxMn1−xFe2O4 ferrites

Modifying the proportion of the base composition by substituting with suitable dopants and improving the preparation conditions is expected to change the performance of ferrites. In the present study, Mg_xMn_1−xFe₂O₄ series of ferrites were prepared by, the conventional ceramic technique and the hot-pressed ceramic technique. Hot pressing of Mg–Mn ferrites results in an improvement of their magnetic and micro-structural properties as it controls simultaneously grain growth and porosity. Hot pressing of the Mg–Mn ferrites, however, results in a deterioration of their DC resistivity. The cation distribution has been studied by X-ray analysis and magnetisation. The variation of the saturation magnetisation and Curie temperature with increasing concentration of the Mg²⁺ ions can be explained on the basis of cation distribution and Neel's two sub-lattice models. The observed Mössbauer spectra show two hyperfine split sextets with an absence of magnetic relaxation indicating an absence of domain wall oscillations. The variations of the internal magnetic field have been qualitatively explained by taking into account, the predominant super-transferred hyperfine interactions (STHI).     

Preparation of alkaline solid polymer electrolyte based on PVA-TiO2-KOH-H2O and its performance in Zn-Ni battery

A novel composite alkaline polymer electrolyte based on poly(vinyl alcohol) (PVA) polymer matrix, titanium dioxide (TiO₂) ceramic fillers, KOH, and H₂O was prepared by a solution casting method. The properties of PVA-TiO₂-KOH alkaline polymer electrolyte films were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and AC impedance techniques. DSC and XRD results showed that the domain of amorphous region in the PVA polymer matrix augmented when TiO₂ filler was added. The SEM result showed that TiO₂ particles dispersed into the PVA matrix although some TiO₂ aggregates of several micrometers were formed. The alkaline polymer electrolyte showed excellent electrochemical properties. The room temperature (20 °C) ionic conductivity values of typical samples were between 0.102 and 0.171 S cm⁻¹. The Zn-Ni secondary battery with the alkaline polymer electrolyte PVA-TiO₂-KOH had excellent electrochemical property at the low charge-discharge rate.     

Chemical spray pyrolysis deposition and characterization of p-type CuCr1−xMgxO2 transparent oxide semiconductor thin films

A chemical spray pyrolysis technique for deposition of p-type Mg-doped CuCrO₂ transparent oxide semiconductor thin films using metaloorganic precursors is described. As-deposited films contain mixed spinel CuCr₂O₄ and delafossite CuCrO₂ structural phases. Reduction in spinel CuCr₂O₄ fraction and formation of highly crystalline films with single phase delafossite CuCrO₂ structure is realized by annealing at temperatures ?700 °C in argon. A mechanism of synthesis of CuCrO₂ films involving precursor decomposition, oxidation and reaction between constituent oxides in the spray deposition process is presented. Post-annealed CuCr_0.93Mg_0.07O₂ thin films show high (?80%) visible transmittance and sharp absorption at band gap energy with direct and indirect optical band gaps 3.11 and 2.58 eV, respectively. Lower (∼450 °C) substrate temperature formed films are amorphous and yield lower direct (2.96 eV) and indirect (2.23 eV) band gaps after crystallization. Electrical conductivity of CuCr_0.93 Mg_0.07O₂ thin films ranged 0.6-1 S cm⁻¹ and hole concentration ∼2×10¹⁹ cm⁻³ determined from Seebeck analysis. Temperature dependence of conductivity exhibit activation energies ∼0.11 eV in 300-470 K and ∼0.23 eV in ?470 K region ascribed to activated conduction and grain boundary trap assisted conduction, respectively. Heterojunction diodes of the structure Au/n-(ZnO)/p-(CuCr_0.93Mg_0.07O₂)/SnO₂ (TCO) were fabricated which show potential for transparent wide band gap junction device.     

Synthesis and gas sensing characteristic based on metal oxide modification multi wall carbon nanotube composites

A new type of gas sensing material based on metal oxide modification multi wall carbon nanotube (MO/MWCNT) composites is presented since the interface between the composites enhance the carrier density so as to improve the gas sensitivity. Three kinds of MO/MWCNT composite materials, such as ZnO/MWCNT, SnO₂/MWCNT and TiO₂/MWCNT, have been acquired in situ growth using catalytic pyrolysis method. The MO nano particles have decorated on side of MWCNTs, whereas the introduction of SnO₂ nano particles makes part of MWCNT showing two-dimensional form of carbon nano-wall structure. Among four kinds of cathode of ZnO/MWCNTs, SnO₂/MWCNTs, TiO₂/MWCNTs and pure MWCNT composite film, TiO₂/MWCNTs composite has the lowest threshold electric field required to draw current of 12 μA has been found to be ∼1.2 V/μm, and also TiO₂/MWCNTs composite has the highest sensitivity of 16% to ethanol. The TiO₂/MWCNTs composite is superior to the others both in vacuum electron transportation and gas sensitivity.     

The effect of Fe substitution on the electrical and thermal conductivity and thermopower of Ca3(FexCo1−x)4O9 synthesised by a sol–gel process

The effect of Fe substitution for Co on direct current (DC) electrical and thermal conductivity and thermopower of Ca₃(Co_1−xFe_x)₄O₉ (x = 0, 0.05, 0.08), prepared by a sol–gel process, was investigated in the temperature range from 380 down to 5K. The results indicate that the substitution of Fe for Co results in an increase in thermopower and DC electrical resistivity and substantial (14.9–20.4% at 300K) decrease in lattice thermal conductivity. Experiments also indicated that the temperature dependence of electrical resistivity ρ for heavily substituted compounds Ca₃(Co_1−xFe_x)₄O₉ (x = 0.08) obeyed the relation lnρ ∝ T^−1/3 at low temperatures, T < ~55K, in agreement with Mott’s two-dimensional (2D) variable range hopping model. The enhancement of thermopower and electrical resistivity was mainly ascribed to a decrease in hole carrier concentration caused by Fe substitution, while the decrease of thermal conductivity can be explained as phonon scattering caused by the impurity. The thermoelectric performance of Ca₃Co₄O₉ was not improved in the temperature range investigated by Fe substitution largely due to great increase in electrical resistivity after Fe substitution.     

Fluorophosphate glasses containing manganese

New fluorophosphate glasses based on MnF₂, NaPO₃ and MF_n (M=Zn²⁺, Sr²⁺, Mg²⁺, Ba²⁺, Li⁺, Na⁺ and K⁺) have been synthesised and characterized. Large vitreous areas were observed. Samples of 4 mm in thickness have been obtained. These glasses are easy to prepare and stable in ambient air. Depending on the composition and the nature of the M cation, glass transition temperature, T_g, lies between 230 and 314 °C, crystallisation temperature, T_x is between 320 and 475 °C. These glasses are pink coloured, and infrared transmission extends up to 4.5 μm with extrinsic OH⁻ absorption band at 3200 cm⁻¹ and other bands around 2200 and 1600 cm⁻¹ that relate to PO₄ tetrahedron vibration. Other physical properties including density, microhardness, Young modulus, thermal expansion and refractive index were investigated and correlated to composition.     

OH impurities in co-doped LiNbO3:Cr :ZnO congruent crystals

Infrared optical absorption has been used to study OH⁻impurities into congruent co-doped LiNbO₃:Cr³⁺:ZnO crystals doped with different Zn²⁺ concentration. The OH⁻ IR absorption spectra present three bands that can be associated with different OH⁻ complex centres available in the lattice. For crystals with lower Zn²⁺ concentrations (<4.7%) only one IR absorption band centred at 2867 nm (3490 cm⁻¹) is reported which is associated with the OH⁻ unperturbed vibration. For crystals with higher Zn²⁺ concentrations (>4.7%), two new bands associated with OH⁻vibration in distortion environment are reported. These bands are centred at 2827 nm (3537 cm⁻¹) and 2847 nm (3512 cm⁻¹) and can be associated with OH⁻-Zn²⁺ and Cr³⁺(Li⁺)-OH⁻-Zn²⁺(Int.) complex centres, respectively. Electron paramagnetic resonance (EPR) has been used to identify the Cr³⁺ centres in the lattice of the doped LiNbO₃:ZnO crystals.     

Studies on hydrogen diffusivity in iron aluminides using the Devanathan–Stachurski method

An electrolytic method for cathodic hydrogen saturation developed by Devanathan and Stachurski was successfully used to study hydrogen diffusivity in iron aluminides. Both an appropriate electrolyte and a saturating current density are required for this method. A proper form of the saturation curve was only obtained with 35% NaCl electrolyte, which removed the oxide film blocking hydrogen penetration without further corrosive destruction of the iron aluminide. The optimum saturation current density for determining the most reliable diffusivity was 1.91 A/cm², yielding D_eff,H = 4.81 × 10⁻⁶ cm²/s for Fe–40 at.% Al.     

Physical properties of the delafossite LaCuO2

High-quality LaCuO₂, elaborated by solid-state reaction in sealed tube, crystallizes in the delafossite structure. The thermal analysis under reducing atmosphere (H₂/N₂: 1/9) revealed a stoichiometric composition LaCuO_2.00. The oxide is a direct band-gap semiconductor with a forbidden band of 2.77 eV. The magnetic susceptibility follows a Curie-Weiss law from which a Cu²⁺ concentration of 1% has been determined. The oxygen insertion in the layered crystal lattice induces p-type conductivity. The electrical conduction occurs predominantly by small polaron hopping between mixed valences Cu^+/2+ with an activation energy of 0.28 eV and a hole mobility (μ_300 K=3.5×10⁻⁷ cm² V⁻¹ s⁻¹), thermally activated. Most holes are trapped in surface-polaron states upon gap excitation. The photoelectrochemical study, reported for the first time, confirms the p-type conduction. The flat band potential (V_fb=0.15 V_SCE) and the hole density (N_A=5.8×10¹⁷ cm⁻³) were determined, respectively, by extrapolating the curve C⁻² versus the potential to their intersection with C⁻²=0 and from the slope of the linear part in the Mott-Schottky plot. The valence band is made up of Cu-3d orbital, positioned at 4.9 eV below vacuum. An energy band diagram has been established predicting the possibility of the oxide to be used as hydrogen photocathode.     

Dielectric, ferroelectric, magnetic and magnetoelectric properties of PMN-PT based ME composites

A systematic study of magnetoelectric composite system (x) CoFe₂O₄+(1−x) Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ with x=0, 0.15, 0.30, 0.45 and 1 was carried out. The lattice strain was calculated using Williamson and Hall equation, which depends on the content of constituent phases in composites. The microstructure was studied using scanning electron microscopy. The ferroelectric transition temperature was independent of the content of individual phases, suggesting that the ferroelectric character is maintained in the composite. Observed P–E and M–H loops indicate that the multiferroic nature of magnetoelectric ceramics is dependent on the content of individual phases. The variation of magnetostriction with dc magnetic field was studied. The maximum magnetoelectric voltage coefficient of 7.2 mV/cm Oe is obtained for the synthesized composites. The magnetoelectric measurements are well explained with magnetostrictive behavior of the magnetic phase.     

Synthesis, physical and photo electrochemical characterization of La-doped SrSnO3

The transport properties of Sr_0.98La_0.02SnO_3−δ in the system Sr_1−xLa_xSnO_3−δ, after which the pyrochlore La₂Sn₂O₇ appears, were investigated over the temperature range 4.2-300 K. The oxide was found to be n-type semiconductor with concomitant reduction of Sn⁴⁺ into Sn²⁺. The magnetic susceptibility was measured down to 4.2 K and is less than 3×10⁻⁵ emu cgs mol⁻¹ consistent with itinerant electron behavior. The electron is believed to travel in a narrow band of Sn:5s character with an effective mass ∼4 m_o. The highest band gap is 4.32 eV and the optical transition is directly allowed. A further indirect transition occurs at 4.04 eV. The electrical conductivity follows an Arrhenius-type law with a thermal activation of 40 meV and occurs by small polaron hopping between nominal states Sn^4+/2+. The linear increase of thermo-power with temperature yields an electron mobility μ_300 K (2×10⁻⁴ cm² V⁻¹ s⁻¹) thermally activated. The insulating-metal transition seems to be of Anderson type resulting from random positions of lanthanum sites and oxygen vacancies. At low temperatures, the conduction mechanism changes to a variable range hopping with a linear plot Ln ρ⁻¹ vs. T⁻⁴. The photo electrochemical (PEC) measurements confirm the n-type conductivity and give an onset potential of −0.46 V_SCE in KOH (1 M). The Mott-Schottky plot C⁻²-V shows a linear behavior from which the flat band potential V_fb=+0.01 V_SCE at pH 7 and the doping density N_D=1.04×10²¹ cm⁻³ were determined.     

Enhancement of electrical properties due to Cr substitution in Co-ferrite nanoparticles synthesized by two chemical techniques

Nanocrystalline cobalt ferrites with nominal composition CoCr_xFe_2−xO₄ ranging from x=0.0 to 0.5 with step increment of 0.25 were prepared by sol–gel auto combustion and chemical co-precipitation techniques. A comparative study of structural, electrical and magnetic properties of these ferrites has been measured using different characterization techniques. Structural and micro-structural studies were measured using X-ray diffraction, Fourier transform infra-red spectroscopy (FTIR), scanning electron microscopy and atomic force microscopy. Crystallite sizes of the series are within the range of 12–29±2 nm. Lattice parameters decrease by increasing Cr³⁺ concentration. FTIR confirms the presence of two lattice absorption bands. DC electrical resistivity increases to a value of ∼10¹⁰ Ω-cm with increase in Cr³⁺ concentration, but the most significant increase is in samples prepared by sol–gel combustion. Dielectric properties have been measured as a function of frequency at room temperature. Dielectric loss decreases to 0.1037 and 0.0108 at 5 MHz for chemical co-precipitation and sol–gel combustion, respectively. Impedance measurements further helped in analyzing the electrical properties and to separate the grain and grain boundary resistance effects using a complex impedance analysis. Magnetic parameters were studied using a vibrating sample magnetometer in the applied field of 10 kOe. The saturation magnetization decreased from 63 to 10.8 emu/gm with increase in Cr³⁺ concentration.     

Preparation and properties of a gel polymer electrolyte system based on poly-ε-caprolactone containing 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Gel polymer electrolytes (GPE) obtained by immobilizing a solution of zinc triflate (ZnTr) in an ionic liquid, namely 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [emim][Tf₂N] within a biodegradable polymeric matrix of poly-ε-caprolactone (PCL) were prepared by a simple solvent cast technique for different concentrations of the ionic liquid. The electrolyte with the composition 75 wt% PCL: 25 wt% ZnTr+100 wt% [emim][Tf₂N] showed the highest ionic conductivity of 1.1×10⁻⁴ S cm⁻¹ at 25 °C and favored by the rich amorphous phase of the GPE as confirmed from room temperature X-ray diffraction analysis (XRD). The morphology of the GPE was examined using scanning electron microscopy (SEM) which revealed the homogeneity of the prepared GPE system. The temperature dependence of electrical conductivity of the GPE followed the Arrhenius behavior. The Zn²⁺ ionic transport number has been determined to be ~0.62 which denotes the predominant contribution of zinc ion towards total ionic conductivity. The electrochemical stability window of GPE is found to be 2.5 V with a thermal stability upto 200 °C. This eco-friendly and safe electrolyte may be used to fabricate compostable batteries, in future, with a suitable selection of other components of the battery system.