Investigation on the effects of addition of SiO<Subscript>2</Subscript> nanoparticles on ionic conductivity,FTIR, and thermal properties of nanocomposite PMMA–LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>

Composite polymer electrolyte systems composed of poly(methyl methacrylate) (PMMA) as the host polymer, lithium trifluoromethanesulphonate (also known as lithium triflate; LiCF₃SO₃) as dopant salt, and a variety of different concentrations of nano-sized fumed silica (SiO₂) as inorganic filler were studied. The effect upon addition of SiO₂ on the ionic conductivity of the composite polymer electrolytes was investigated, and it was proven that the ionic conductivity had been enhanced. In addition, the interfacial stability also showed improvement. Maximum conductivity was obtained upon addition of 2 wt.% SiO₂. The complexation of PMMA and LiCF₃SO₃ was verified through Fourier transform infrared studies. The thermal stability of the polymer electrolytes was also found to improve after dispersion of inorganic filler. This was proven in the thermogravimetric studies.     

Investigation on compositional effect of PEG:BaTiO<Subscript>3</Subscript> in plasticized PVC–LiBETi polymer composite electrolytes

The blend-based polymer electrolyte comprising poly(vinyl chloride) (PVC) and poly(ethylene glycol) (PEG) as host polymer and lithium bis(perfluoroethanesulfonyl)imide as complexing salt have been prepared. Ethylene carbonate and dimethyl carbonate (50:50 v/v) are used as plasticizer for the system. The barium titanate is used as a filler, and the ratio of (PEG:BaTiO₃) is varied to study its effect on the conductivity behavior of the electrolyte. XRD and ac impedance studies are carried out on the prepared samples. The ac impedance measurements show that the conductivity of the prepared samples depends on the (PEG:BaTiO₃) ratio, and its value is higher for (15:5) wt.% of (PEG:BaTiO₃)-incorporated film. The temperature dependence of the conductivity of the polymer films obeys VTF relation. The role of ferroelectric filler in enhancing the conductivity is studied. The thermal stability of the film is ascertained from TG/DTA studies. The phase morphological study reveals that the porous nature of the polymer electrolyte membranes depends on the (PEG:BaTiO₃) ratio.     

Electrical conductivity and dielectric relaxation studies on microwave synthesized Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>·NaPO<Subscript>3</Subscript>·MoO<Subscript>3</Subscript> glasses

Electrical conductivity and dielectric relaxation studies on SO₄ ^2? doped modified molybdo-phosphate glasses have been carried out over a wide range of composition, temperature and frequency. The d.c. conductivities which have been measured by both digital electrometer (four-probe method) and impedance analyser are comparable. The relaxation phenomenon has been rationalized using electrical modulus formalism. The use of modulus representation in dielectric relaxation studies has inherent advantages viz., experimental errors arising from the contributions of electrode-electrolyte interface capacitances are minimized. The relaxation observed in the present study is non-Debye type. The activation energies for relaxation were determined using imaginary parts of electrical modulus peaks which were close to those of the d.c. conductivity implying the involvement of similar energy barriers in both the processes. The enhanced conductivity in these glasses can be attributed to the migration of Na⁺, in expanded structures due to the introduction of SO₄ ^2? ions.     

Sol–gel synthesis and characterization of Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite solid electrolytes

Composite solid electrolytes in the system (1???x)Li₂CO₃–xAl₂O₃, with x?=?0.0–0.5 (mole), were synthesized by a sol–gel method. The synthesis carried out at low temperature resulted in voluminous and fluffy products. The obtained materials were characterized by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy/energy-dispersive X-ray, Fourier transform infrared spectroscopy and AC impedance spectroscopy. Structural analysis of the samples showed an amorphous feature of Li₂CO₃ and traces of α-LiAlO₂, γ-LiAlO₂ and LiAl₅O₈. The prepared composite samples possess high ionic conductivities at 130–180 °C on account of the presence of lithium aluminates as well as the formation of a high concentration of an amorphous phase of Li₂CO₃ via this sol–gel preparative technique.     

Spin Crossover [Fe(qsal)<Subscript>2</Subscript>]X (X = Cl,SCN, CF<Subscript>3</Subscript>SO<Subscript>3</Subscript>) Complexes: EPR and DFT Study

The compounds [Fe(qsal)₂]X (X = Cl, SCN, CF₃SO₃) were synthesized and investigated by electron paramagnetic resonance (EPR). The dependence of the Fe(III) spin state on the type of counterion X and on the temperature was established. On the basis of the density functional calculations, the geometrical parameters of compounds in high- and low-spin states were optimized and the difference in their internal energies was calculated. A correlation between the experimental EPR data and the theoretically calculated energy difference between the high-spin and the low-spin states of the compounds with different anions was obtained.     

Structural and ionic conductivity studies on P(ECH-EO):γ-BL:LiClO<Subscript>4</Subscript> plasticized polymer electrolyte

The plasticized polymer electrolyte consisting of poly(epichlorohydrin-ethyleneoxide) [P(ECH-EO)], lithium perchlorate (LiClO₄) and γ-butyrolactone (γ-BL) have been prepared by simple solution casting technique. The polymer–salt–plasticizer complex has been confirmed by XRD analysis. The ionic conductivity studies have been carried out using AC impedance technique. The effect of plasticizer (γ-BL) on ionic conductivity has been discussed with respect to different temperatures. The maximum value of ionic conductivity is found to be 1.3 × 10⁻⁴ Scm⁻¹ for 70P(ECH-EO):15γ-BL:15LiClO₄ at 303 K. The temperature dependence of the plasticized polymer electrolyte follows the Vogel–Tamman–Fulcher formalism. The activation energy is found to decrease with the increase in plasticizer.     

Combined effect of CuO nanofillers and DBP plasticizer on ionic conductivity enhancement in the solid polymer electrolyte PEO–LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>

We report a new kind of polyethylene oxide, PEO–LiCF₃SO₃-based composite polymer electrolyte, containing active copper oxide (CuO) nanoparticles with dibutyl phthalate (DBP) prepared by solution-cast technique. The incorporation of 10 wt.% DBP and 5 wt.% CuO to the salted polymer showed a significant conductivity enhancement with maximum conductivity 2.62 × 10⁻⁴ Scm⁻¹ at room temperature. This could be attributed to the increasing of amorphous phase content and structural changes in the polymer electrolyte. Arrhenius plot suggest that temperature-dependent conductivity is a thermally activated process.     

Magnetic and magnetoresistive properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sr<Subscript>2</Subscript>FeMoO<Subscript>6–δ</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoheterostructures

A method has been developed for fabricating nanoporous matrices based on anodic aluminum oxide for the deposition of ferromagnetic nanoparticles in them. The modes of deposition of strontium ferromolybdate thin films prepared by the ion-plasma method have been worked out, and the magnetic and magnetoresistive properties, structure, and composition of the films have been investigated. It has been revealed that the microstructure and properties of the strontium ferromolybdate films deposited by ionplasma sputtering depend on the deposition rate and the temperature of the substrate. Based on the measurement of the electrical resistivity of nanoheterostructures in a magnetic field, it has been found that the magnetoresistance reaches 14% at T = 15 K and B = 8 T, which is due to the manifestation of tunneling magnetoresistance.     

Structural properties of composite cathode material LiFePO<Subscript>4</Subscript>–Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

Composite cathode material LiFePO₄–Li₃V₂(PO₄)₃ is synthesized through a chemical reduction and lithiation using FeVO₄·xH₂O as both iron and vanadium sources. The structural properties of LiFePO₄–Li₃V₂(PO₄)₃ are investigated. X-ray diffraction results show the composite material containing olivine type LiFePO₄ and monoclinic Li₃V₂(PO₄)₃ phases. High-resolution transmission electron microscopy and energy-dispersive X-ray spectrometry results indicate that mutual doping effects take place between the LiFePO₄ and Li₃V₂(PO₄)₃ particles with V³⁺ doping the LiFePO₄ while Fe²⁺ dopes the Li₃V₂(PO₄)₃. LiFePO₄–Li₃V₂(PO₄)₃ nanocomposites are formed in the carbon webs. There is no structural compatibility between monoclinic (Li₃V₂(PO₄)₃) and olivine (LiFePO₄) domains in composite material LiFePO₄–Li₃V₂(PO₄)₃.     

Preparation and characterization of organic–inorganic hybrid compound [N(C<Subscript>4</Subscript>H<Subscript>9</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>Cu<Subscript>2</Subscript>Cl<Subscript>6</Subscript>

Organic–inorganic hybrid sample [N(C₄H₉)₄]₂Cu₂Cl₆ was prepared via the reaction between copper chloride and tetrabutylammonium chloride. The compound was characterized by X-ray powder diffraction, IR, Raman, differential scanning calorimetry (DSC), DTA-TGA analysis and electrical impedance spectroscopy. DSC studies indicate a presence of one-phase transition at 343 K. The complex impedance of compound [N(C₄H₉)₄]₂Cu₂Cl₆ have been investigated in temperature and frequency ranges 300–380 K and 200 Hz–5 MHz, respectively. The Z′ and Z″ versus frequency plots are well fitted to an equivalent circuit model. The circuits consist of the parallel combination of bulk resistance R _p and constant phase elements CPE. The frequency dependence of the conductivity is interpreted in term of Jonscher's law: s(w) = s_dc + Awⁿ \sigma (\omega ){ } = {\sigma_{\rm{dc}}} + { }A{\omega^n} . The conductivity follows the Arrhenius relation. The variation of the value of these elements with temperatures confirmed the availability of the phase transition at 343 K detected by DSC and electrical measurements.     

Electrical switching in the MoO<Subscript>3</Subscript>–WO<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> and MoO<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

High field electrical switching on blown films of MoO₃(60%)–P₂O₅(40%), MoO₃(50%)–WO₃(10%)–P₂O₅(40%), and MoO₃(45%)–WO₃(15%)–P₂O₅(40%) having different thicknesses was studied and compared. Switching was observed using two terminal samples. S-type current–voltage characteristic (current-controlled negative resistance—CCNR) with memory was observed in molybdenum–phosphate glasses, but N-type characteristic (voltage-controlled negative resistance—VCNR) with threshold in tungsten–molybdenum–phosphate glasses was observed. The important observation was that with the addition of WO₃ to binary MoO₃–P₂O5 led to a change of I–V characteristic from CCNR with memory to VCNR with threshold. The measurements of density and molar volume showed linear relation between MoO₃ content and density which decreased with the increase of MoO₃ content. The samples’ thickness had no significant effect on threshold voltage. The attained results also indicated that the electrode material had no effect on switching property of devices. The switching behavior of the devices did not show any dependence on the polarity of the applied voltage. In terms of the effect of heat on the switching behavior of molybdenum–phosphate glasses, it was found that threshold voltage decreases with increasing of temperature. Finally, the switching phenomenon was explained by thermal (formation of crystalline filaments) and electronic models.     

Fractal magnetic microstructure in the (Co<Subscript>41</Subscript>Fe<Subscript>39</Subscript>B<Subscript>20</Subscript>)<Subscript>x</Subscript>(SiO<Subscript>2</Subscript>)<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> nanocomposite films

Magnetostructural methods are applied to determine the exchange bond percolation limit in (Co₄₁Fe₃₉B₂₀)_x(SiO₂)_1?x nanocomposites (x _c = 0.30 ± 0.02), which separates the phase plane along the metal concentration axis into a superparamagnetic region and a ferromagnetic region. It is shown that, with respect to the singularities of the magnetization up to the magnetization saturation curves, the ferromagnetic region is further subdivided into three regions differing in the character of the spatial propagation of the magnetization ripples or in the magnetic correlation function characteristics. The fractal dimension of the nanocomposite magnetic microstructure near the percolation threshold is determined.     

Specific heat of the [NH<Subscript>2</Subscript>(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> crystal in the temperature region 80–300 K

The specific heat of [NH₂(CH₃)₂]₂ZnCl₄ was measured calorimetrically in the temperature region 80–300 K. As the temperature T decreases, the C _p (T) dependence indicates a phase transition sequence, with the phase transition at T₆=151 K observed for the first time. The thermodynamic characteristics of the crystal were refined. The transformation occurring at T₂=298.3 K is shown to be an incommensurate-commensurate phase transition.     

Elastic properties of TeO<Subscript>2</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Ag<Subscript>2</Subscript>O glasses

A series of glasses [(TeO₂) _x (B₂O₃)_1−x ]_1−y [Ag₂O] _y with x = 70 and y = 10, 15, 20, 25 and 30 mol% were synthesised by rapid quenching. Longitudinal and shear ultrasonic velocity were measured at room temperature and at 5 MHz frequency. Elastic properties, Poisson's ratio, microhardness, softening temperature and Debye temperature have been calculated from the measured density and ultrasonic velocity at room temperature. The experimental results indicate that the elastic constants depend upon the composition of the glasses and the role of the Ag₂O inside the glass network is discussed. Estimated parameters based on Makishima–Mackenzie theory and bond compression model were calculated in order to analyse the experimental elastic moduli. Comparison between the experimental elastic moduli data obtained in the study and the calculated theoretically by the mentioned above models has been discussed.     

Influence of Matrix Nature on the Structural Characteristics of In<Subscript>2</Subscript>O<Subscript>3</Subscript>–CeO<Subscript>2</Subscript> and SnO<Subscript>2</Subscript>–CeO<Subscript>2</Subscript> Composites Fabricated by the Impregnation Method

The structural characteristics, valence states, and distribution of cerium ions between the components in In₂O₃–CeO₂ and SnO₂–CeO₂ nanocomposites fabricated using the impregnation method were studied. X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX) were used to show that, during impregnation, cerium ions are not included into In₂O₃ crystals and are disposed only on their surface in the form of nano-sized crystallites or amorphous clusters. On the other side, under the contact of CeO₂ clusters with a surface of SnO₂ matrix crystals, cerium ions penetrate into the surface layer of these crystals. In contrast to an In₂O₃–CeO₂ system, where the addition of CeO₂ does not affect the conduction activation energy, where cerium oxide is added to SnO₂, the observed increase in the resistance of a SnO₂–CeO₂ composite is accompanied by a sufficient increase in activation energy. These data and the XPS spectra confirm the modification of the surface layers of conductive SnO₂ crystals as, a result of the penetration of cerium ions into these layers.     

Optical Flow-Through Sensor for the Determination of Norfloxacin Based on Emission of KMnO<Subscript>4</Subscript>–Na<Subscript>2</Subscript>SO<Subscript>3</Subscript>–Tb<Superscript>3+</Superscript> System

A simple and selective method to determine norfloxacin using an optical flow-through sensor has been developed. The present sensor was prepared by packing anionic ion exchange resin in a glass tube, followed by introducing KMnO₄ solution to the glass tube for immobilization on resin. The optical sensor is based on the emission intensity from the Tb(III) solution sensitized by norfloxacin. The excitation of norfloxacin occurred by the chemiluminescence from the reaction of KMnO₄ and Na₂SO₄ solutions. The effects of pH, concentration of Tb(III) ion, KMnO₄ and Na₂SO₄ solutions and flow rate of the norfloxacin solution on the chemiluminescence intensity were studied to find the optimum experimental conditions. The emission intensity increased linearly with increasing norfloxacin concentration from 1.0 × 10⁻³ to 1.0 × 10⁻⁸ M and the detection limit (3σ) was 8.7 × 10⁻⁹. The applicability of the present method was demonstrated by determination of norfloxacin in various pharmaceutical preparations and serum sample.     

Long-range magnetic order in copper nitrate monohydrate Cu(NO<Subscript>3</Subscript>)<Subscript>2</Subscript> · H<Subscript>2</Subscript>O

The magnetic phase diagram of copper nitrate monohydrate Cu(NO₃)₂ · H₂O and the basic parameters of its magnetic subsystem have been determined by measuring the thermodynamic properties of this compound. This compound becomes antiferromagnetically ordered at T _N = 3.6 K, undergoes the spin-flop and spin-flip transitions at H _C1 ～ 0.06 T and H _C2 ～ 1.1 T, respectively, at low temperatures. The magnetization of Cu(NO₃)₂ · H₂O at T _SR = 2.7 K exhibits an additional anomaly, which is likely attributed to the spin-reorientation transition.     

<Superscript>2</Superscript>H NMR investigation of the transition to the proton glass state in the Cs<Subscript>5</Subscript>H<Subscript>3</Subscript>(SO<Subscript>4</Subscript>)<Subscript>4</Subscript> · 0.5H<Subscript>2</Subscript>O crystal

A crystal of the Cs₅H₃(SO₄)₄ · xH₂O (x ≈ 0.5) (PCHS) compound, which belongs to the family of proton conductors with a complex system of hydrogen bonds, is investigated by ²H NMR spectroscopy. The temperature and orientation dependences of the ²H NMR spectra are measured and analyzed. It is established that, upon transition to the glassy phase at the temperature T _g = 260 K, the parameters characterizing the proton exchange between positions in hydrogen bonds remain unchanged to within the limits of experimental error. The protons in the two-dimensional network of hydrogen bonds in the (001) plane are dynamically disordered over possible positions down to temperatures considerably lower than the glass transition point T _g . However, water molecules are fixed at particular structural positions in the phase transition range. In PCHS crystals with a nonstoichiometric water content, this circumstance can be responsible for the frustration that leads to the formation of the glassy state.     

Anomalous states of the structure of [Rb<Subscript>0.7</Subscript>(NH<Subscript>4</Subscript>)<Subscript>0.3</Subscript>]<Subscript>2</Subscript>SO<Subscript>4</Subscript> crystals in the temperature range 4.2–300 K

Crystals of [Rb_0.7(NH₄)_0.3]₂SO₄ solid solutions are studied using x-ray diffractometry in the temperature range 4.2–300 K. No anomalies are revealed in the temperature dependences of the lattice parameters and the volume of the host unit cell. A series of superstructure reflections observed along the basis axes corresponds to the guest lattice formed in the matrix of the host structure. From analyzing the axial ratio of these structures and their temperature dependences, it is concluded that the structure of the crystal has the form of an incommensurate composite. The guest structure of the composite at room temperature can be considered a set of chains that are not correlated along the b direction. In the plane perpendicular to the chain axes, these chains form a regular framework that is also incommensurate to the host lattice.