Impregnation of polymers with 2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxyl (TEMPONE) paramagnetic probe in sub- and supercritical CO<Subscript>2</Subscript>

The spin probe method is used to study the impregnation of polycarbonate (PC) based on bisphenol A, polyethylene oxide (PEO), and crosslinked acrylamide–acrylic acid copolymer (PAA) with organic molecules in sub- and supercritical CO₂ media. Electron spin resonance (EPR) data show that, at 196 bar and 307 K, 2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxyl (TEMPONE) paramagnetic spin probe molecules penetrate into the PC and PEO matrices, which are, respectively, in the glassy and elastic states under normal conditions. The degree of impregnation of PAA under these conditions is negligibly small. Estimates of the local concentration of probe molecules show that, in the PEO matrix, TEMPONE is distributed much more uniformly than in the PC matrix. Analysis of the effect of temperature on the shape of the EPR spectra of the radical in the polymer matrix shows that, under the same conditions, the mobility of TEMPONE molecules in the PEO matrix is much higher than in the PC matrix. The results suggest that the spin probe method is promising for studying the characteristics of macro- and micro-processes in polymer–supercritical fluid solvent–organic molecule ternary systems.     

EPR Study of Sc<Subscript>2</Subscript>SiO<Subscript>5</Subscript>:Nd<Superscript>143</Superscript> Isotopically Pure Impurity Crystals

The Sc₂SiO₅ single crystals doped with 0.001 at.% of the ¹⁴³Nd³⁺ ion were studied by continuous-wave and pulse electron paramagnetic resonance methods. The g-tensors and hyperfine structure tensors for two magnetically non-equivalent Nd ions were obtained. The spin–spin and spin–lattice relaxation times were measured at 9.82 GHz in the temperature range from 4 to 10 K. It was established that three relaxation processes contribute to the spin–lattice relaxation processes. There are one-phonon spin–phonon interaction, two-phonon Raman interaction and two-phonon Orbach–Aminov relaxation processes. It was established that spin–spin relaxation time is of the same magnitude for neodymium ion doped in Sc₂SiO₅ and in Y₂SiO₅.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanofiller on the electrical,thermal and structural properties of PEO:PPG based nanocomposite polymer electrolyte

A new series of nanocomposite polymer electrolyte (NCPE) system comprising of polyethylene oxide (PEO) and polypropylene glycol (PPG) as blended polymer host, zinc trifluoromethanesulfonate [Zn(CF₃SO₃)₂] as dopant salt and nanocrystalline alumina [Al₂O₃] as filler was prepared by solution casting technique. The present system consisting of five different compositions of 87.5 wt% (PEO:PPG)–12.5 wt% Zn(CF₃SO₃)₂ + x wt% Al₂O₃ [where x = 1, 3, 5, 7 and 9, respectively] has been thoroughly characterized by various analytical techniques such as electrical impedance spectroscopy, X-ray diffraction (XRD) studies, differential scanning calorimetry (DSC), scanning electron microscopic (SEM) analysis and linear sweep voltammetry (LSV). The maximum room temperature ionic conductivity exhibited by the NCPE was found to be 2.1 × 10^?4 S cm^?1 for 3 wt% loading of Al₂O₃ which is an order higher than that of the optimized filler-free zinc salt doped polymer electrolyte system at 298 K. The evidence of a decrease in the degree of crystallinity responsible for the enhanced conductivity was revealed by the XRD data and further confirmed by DSC and SEM results. Moreover, the electrochemical stability window of the highly conducting electrolyte matrix has been experimentally determined by linear sweep voltammetry and found to be 3.6 V which is fairly adequate for the construction of zinc primary batteries as well as zinc-based rechargeable batteries at ambient conditions.     

The evolution of electronic configuration and magnetic characterization of Fe<Subscript>9</Subscript>Ni<Subscript>1</Subscript>, Fe<Subscript>8</Subscript>Ni<Subscript>2</Subscript> alloy in theoretical calculation

To analyze the origin of the magnetic enhancement of Fe-Ni alloy, the electronicconfigurations and magnetic properties were investigated using density functional theorybased on the first-principle. The supercell (5 × 1 × 1) of Fe,Fe₉Ni₁ and Fe₈Ni₂ were constructed. Thedefect formation energy, band structure, density of states and electron density differencewere calculated. The results showed that Ni doping changed the electronic configuration ofFe atoms, resulting in the enhancement of spin polarization of Fe and the larger Bohrmagnetic moment in Fe-Ni alloys (Fe₉Ni₁). The results showed thatthe charge transfer and the atomic spacing between Fe atoms and the dopant Ni atoms playedan important role in determination of magnetic moment. The value of Fe supercell(5 × 1 × 1), Fe₉Ni₁ and Fe₈Ni₂ were 23.14,23.34 and 22.61μ _B, respectively.     

Influence of K<Subscript>2</Subscript>Ti<Subscript>6</Subscript>O<Subscript>13</Subscript> on dielectric and barrier properties of polymer

Polymer composite comprising polyvinylidene fluoride (PVDF) and potassium hexatitante (K₂Ti₆O₁₃) was synthesized by solution casting. The effect of K₂Ti₆O₁₃ on surface, thermal, and electrical properties of polymer composite were investigated. The addition of K₂Ti₆O₁₃ with polymer leads to thermal degradation and transition of polymer composite from semi-crystalline to amorphous phase. The optimum results of contact angle for different loading wt% of K₂Ti₆O₁₃ were directly correlated with the surface morphology. Our experimental results confirmed the incorporation of K₂Ti₆O₁₃ in polymer by SEM micrographs. The evaluated dielectric properties (ε' = 424; tan δ = 2.14 at 130 °C and 100 Hz frequency for 20 wt% loading of K₂Ti₆O₁₃) for polymer composite are higher in compared to pure polymer. The enhancement in dielectric constant and changing the surface properties of polymer composite can be used for the development of electrochemical storage device applications.     

Effect of molybdenum on Li<Subscript>2</Subscript>Mn<Subscript>4</Subscript>O<Subscript>9</Subscript> for rechargeable lithium ion batteries

Li₂Mn₄O₉ and molybdenum-doped Li₂Mn₄O₉ have been prepared by simple solid-state method. Molybdenum is used as a dopant since it is resistant to both corrosion and high-temperature creep deformation. The structural, morphological, and electrical performances of the samples have been analyzed. The material exhibits a cubic structure with the fd3m space group. Using EDAX, the chemical compositions of the samples have been identified. The dc electrical conductivity of the Mo-doped (LM2) sample is found to be increased to 7.44?×?10^?6 S cm^?1 at 393 K. The enhanced electrical property of the molybdenum-doped Li₂Mn₄O₉ reveals it as a feasible cathode material for rechargeable Li-ion batteries.     

Structure,thermal behavior,and dielectric properties of new cesium hydrogen sulfate arsenate: Cs<Subscript>2</Subscript>(HSO<Subscript>4</Subscript>)(H<Subscript>2</Subscript>AsO<Subscript>4</Subscript>)

Synthesis and structural characterization by single-crystal X-ray diffraction method, thermal behavior, and electrical proprieties are given for a new compound with a superprotonic phase transition Cs₂(HSO₄)(H₂AsO₄). The title compound crystallizes in the monoclinic system with the P2₁/n space group. The structure contains zigzag chains of hydrogen-bonded anion tetrahedra that extend in the [010] direction. Each tetrahedron is additionally linked to a tetrahedron neighboring chain to give a planar structure with hydrogen-bonded sheets lying parallel to (10ī). The existence of O–H and (S/As)–O bonds in the structure at room temperature has been confirmed by IR and Raman spectroscopy in the frequency ranges 4000–400 cm^?1and 1200–50 cm^?1, respectively. Differential scanning calorimetry analysis of the superprotonic transition in Cs₂(HSO₄)(H₂AsO₄) showed that the transformation to high temperature phase occurs at 417 K by one-step process. Thermal decomposition of the product takes place at much higher temperatures, with an onset of approximately 534 K. The superprotonic transition was also studied by impedance and modulus spectroscopy techniques. The conductivity in the high temperature phase at 423 K is 1.58 × 10^?4 Ω^?1 cm^?1, and the activation energy for the proton transport is 0.28 eV. The conductivity relaxation parameters associated with the high disorder protonic conduction have been examined from analysis of the M”/M”_max spectrum measured in a wide temperature range. Transport properties of this material appear to be due to the proton hopping mechanism.     

Preparation of metallic Pd nanoparticles using supercritical CO<Subscript>2</Subscript> deposition: An efficient catalyst for Suzuki cross-coupling reaction

Ligand-free palladium nanoparticles supported on multi-walled carbon nanotubes (Pd/MWCNT) were prepared by the supercritical carbon dioxide (scCO₂) deposition method using a novel scCO₂-soluble Pd organometallic complex as a precursor. The precursor with the perfluoroalkyl chain group was synthesized and identified by microanalytic methods. The deposition was carried out at the temperature of 363.15 K and pressure of 27.6 MPa CO₂. The prepared metallic nanoparticles were obtained with an average size of 2 nm. Pd/MWCNT was utilized as a heterogeneous catalyst in Suzuki cross-coupling reaction. The nanocatalyst was found very effective in Suzuki reaction and it could also be recovered easily from the reaction media and reused over several cycles without significant loss of catalytic activity under mild conditions.

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Graphical Abstract Pd/MWCNT was prepared by the scCO2 deposition method using a new synthesized perfluroalkylated vic-dioxime Pd complex as the precursor. The prepared nanoparticle was very effective as catalyst and reusable for Suzuki cross coupling reaction under mild conditions.

     

Impedance spectroscopy of vanadium modified BaBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

In recent years a wide range of Aurivillius layered materials have been introduced. These novel materials are produced in many various forms such as fibers, thin films as well as bulk by using a number of processing routes. As advanced materials they are they have many interesting properties which include a number of useful electrical properties related to separated grain and grain boundary conductivity, impedance, activation energies, etc. In this paper these properties are described and discussed in detail. The electrical properties of the vanadium doped BaBi₂Nb₂O₉ ceramic was measured over a wide range of temperatures by impedance spectroscopy (IS). The separated grain activation energy, calculated from Arrhenius characteristics at temperatures between room temperature and 600 °C, was 1 eV for 0 at.% of vanadium dopant and 1.2 eV for 10 at.%, whereas the activation energies in the grain boundary region were 0.97 and 1.15 eV, respectively. The obtained results suggest the significant role of vanadium dopant, causing ordering the crystalline structure.     

Phase transition and electrical investigation in lithium copper pyrophosphate compound Li<Subscript>2</Subscript>CuP<Subscript>2</Subscript>O<Subscript>7</Subscript> using impedance spectroscopy

Lithium pyrophosphate compound Li₂CuP₂O₇ has been synthesized through solid state reaction method. FTIR and XRD results, realized at room temperature, indicate respectively the dominant feature of pyrophosphate anion (P₂O₇)^4? and a pure monoclinic phase with I2/a space group. Electrical and dielectric properties have been studied using impedance spectroscopy complex over a wide temperature (576–710 K) and frequency (209 Hz–1 MHz) range. From the direct and alternative conductivities (DC and AC), electrical conduction is found to be thermally activated process. The frequency-dependent AC conductivity obeys Jonscher’s universal power law σ_AC~Aω^s. The differential scanning calorimetry spectrum discloses phase transition at 622 K.     

Structural Phase Transition of Perovskite-Type N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>CdBr<Subscript>3</Subscript> Studied by MAS NMR and Static NMR

The structural geometry change in the perovskite-type N(CH₃)₄CdBr₃ single crystal near the phase transition temperature of T _C = 390 K was investigated using magic angle spinning nuclear magnetic resonance techniques. For ¹H and ¹³C nuclei, the temperature dependences of their chemical shift, spectral intensity, and spin–lattice relaxation time (T _1ρ) in the rotating frame were obtained and analyzed. While the chemical shift and T _1ρ of ¹H showed change near T _C, those of ¹³C did not. In addition, the ¹¹³Cd spin–lattice relaxation time T ₁ in the laboratory frame near T _C show no evidence of anomalous change near the phase transition temperature, which coincides with the measured changes in the ¹H T _1ρ. The driving force for this phase transition was connected to the ¹H in the CH₃ groups.     

Enhanced electrochemical,structural, optical,thermal stability and ionic conductivity of (PEO/PVP) polymer blend electrolyte for electrochemical applications

This paper reports the polyethylene oxide/polyvinylpyrrolidone (PEO/PVP) blend with cobalt chloride (CoCl₂) films prepared using spin coating method on blue star glass substrate. The XRD analysis shows the decrease in the crystallinity nature of the CoCl₂ with addition of the dopant. The FT-IR analysis reveals that interaction between cobalt ions with polymer blend confirms the complexation. The maximum ionic conductivity 0.65?×?10^?4 S cm^?1 was observed for PEO (45 %)/PVP (45 %)/CoCl₂ (10 %) at 30 °C. The optical energy band gaps decreases and Urbach energy were observed increases with increasing the dopant concentration. The DSC/TGA results showed that thermal stability of films enhanced with dopant concentration. Cyclic voltammogram (CV) study shows that the electrochemical strength improves with dopant concentration. These obtained results imply that polymer blend electrolytes are suitable candidature for various applications such as electronic and optical devices like electro-chromic display, fuel cells, gas sensors and solid state batteries.     

An Electron Paramagnetic Resonance Study of the Orbital Ordering Compound MgTi<Subscript>2</Subscript>O<Subscript>4</Subscript>

We report the electron paramagnetic resonance (EPR) studies of MgTi₂O₄ in the 300–140 K range. Above the transition temperature T _t (~258 K), the EPR results indicate that MgTi₂O₄ is paramagnetic. The parameters of the EPR spectra show an anomalous change at T _t. The clear EPR lines can be observed in temperature between T _t and 220 K. Besides that the EPR intensity, g value, and EPR linewidth increase with decreasing temperature; in temperature range below 220 K, no clear EPR line can be detected. The EPR spectra results demonstrate that magnetic spin-singlet state and the orbital density wave of MgTi₂O₄ system are formed gradually with decreasing temperature at low temperature range.     

Synthesis,thermal and electrical behavior of the superprotonic conductor phase in Rb<Subscript>3</Subscript>(HSeO<Subscript>4</Subscript>)<Subscript>2.5</Subscript>(H<Subscript>2</Subscript>PO<Subscript>4</Subscript>)<Subscript>0.5</Subscript> compound

The Rb₃(HSeO₄)_2.5(H₂PO₄)_0.5 compound was prepared and its thermal behavior and electric properties were investigated. The thermogravimetry (TGA) analysis and the differential scanning calorimetric (DSC) show the presence of a structural phase transition of the title compounds at 374 K which is confirmed by the variation of fp and σ_dc as a function of temperature. The complex impedance of the Rb₃(HSeO₄)_2.5(H₂PO₄)_0.5 compound has been investigated in the temperature range of 295–453 K and in the frequency range 209 Hz–1 MHz. The impedance plots show semicircle arcs at different temperatures, and an electrical equivalent circuit has been proposed to explain the impedance results. The circuits consist of the parallel combination of bulk resistance Rp and constant phase elements CPE₁ in series with fractal capacity CPE₂. The frequency dependence of the conductivity is interpreted in terms of Jonscher’s law. The conductivity dc follows the Arrhenius relation. The near value of activation energies obtained from the analysis of modulus, conductivity data, and circuit equivalent confirm that the transport is through the ion hopping mechanism, dominated by the motion of the H⁺ proton in the structure of the investigated materials.     

Synthesis and electrochemical properties of P2-Na<Subscript>2/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>2/3</Subscript>O<Subscript>2</Subscript>

The pure phase P2-Na_2/3Ni_1/3Mn_2/3O₂ was synthesized by a solid reaction process. The optimum calcination temperature was 850 °C. The as-prepared product delivered a capacity of 158 mAh g^?1 in the voltage range of 2–4.5 V, and there was a phase transition from P2 to O2 at about 4.2 V in the charge process. The P2 phase exhibited excellent intercalation behavior of Na ions. The reversible capacity is about 88.5 mAh g^?1 at 0.1 C in the voltage range of 2–4 V at room temperature. At an elevated temperature of 55 °C, it could remain as an excellent capacity retention at low current rates. The P2-Na_2/3Ni_1/3Mn_2/3O₂ is a potential cathode material for sodium-ion batteries.     

Li<Superscript>+</Superscript> ion conductivity and transport properties of LiYP<Subscript>2</Subscript>O<Subscript>7</Subscript> compound

A lithium yttrium diphosphate LiYP₂O₇ was prepared by a solid-state reaction method. Rietveld refinement of the X-ray diffraction pattern suggests the formation of the single phase desired compound with monoclinic structure at room temperature. The infrared and Raman spectrum of this compound was interpreted on the basis of P₂O₇ ^4? vibrations. The AC conductivity was measured in the frequency range from 100 to 10⁶ Hz and temperatures between 473 and 673 K using impedance spectroscopy technique. The obtained results were analyzed by fitting the experimental data to the equivalent circuit model. The Cole–Cole diagram determined complex impedance for different temperatures. The angular frequency dependence of the AC conductivity is found to obey Jonscher’s relation. The temperature dependence of σ _AC could be described in terms of Arrhenius relation with two activation energies, 0.87 eV in region I and 1.36 eV in region II. The study of temperature variation of the exponent(s) reveals two conduction models: the AC conduction dependence upon temperature is governed by the correlated barrier hopping (CBH) model in region I (T < 540 K) and non-overlapping small polaron tunneling (NSPT) model in region II (T > 540 K). The near value of activation energies obtained from the equivalent circuit and DC conductivity confirms that the transport is through ion hopping mechanism dominated by the motion of the Li⁺ ion in the structure of the investigated material.     

Modification research of LiAlO<Subscript>2</Subscript>-coated LiNi<Subscript>0.8</Subscript>Co<Subscript>0.1</Subscript>Mn<Subscript>0.1</Subscript>O<Subscript>2</Subscript> as a cathode material for lithium-ion battery

The LiNi_0.8Co_0.1Mn_0.1O₂ with LiAlO₂ coating was obtained by hydrolysis–hydrothermal method. The morphology of the composite was characterized by SEM, TEM, and EDS. The results showed that the LiAlO₂ layer was almost completely covered on the surface of particle, and the thickness of coating was about 8–12 nm. The LiAlO₂ coating suppressed side reaction between composite and electrolyte; thus, the electrochemical performance of the LiAlO₂-coated LiNi_0.8Co_0.1Mn_0.1O₂ was improved at 40 °C. The LiAlO₂-coated sample delivered a high discharge capacity of 181.2 mAh g^?1 (1 C) with 93.5% capacity retention after 100 cycles at room temperature and 87.4% capacity retention after 100 cycles at 40 °C. LiAlO₂-coated material exhibited an excellent cycling stability and thermal stability compared with the pristine material. These works will contribute to the battery structure optimization and design.     

Thermal properties and ionic conductivity of Li<Subscript>1,3</Subscript>Ti<Subscript>1,7</Subscript>Al<Subscript>0,3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> solid electrolytes sintered by field-assisted sintering

Li_1,3Ti_0,7Al_0,3(PO₄)₃ (LATP) powder was obtained by a conventional melt-quenching method and consolidated by field-assisted sintering technology (FAST) at different temperatures. Using this technique, the samples could be sintered to relative densities in the range of 93 to 99 % depending on the sintering conditions. Ionic and thermal conductivity were measured and the results are discussed under consideration of XRD and SEM analyses. Thermal conductivity values of 2 W/mK and ionic conductivities of 4?×?10^?4 Scm^?1 at room temperature were obtained using relatively large particles and a sintering temperature of 1000 °C at an applied uniaxial pressure of 50 MPa.     

Conductivity behavior of the new pyrophosphate NaNi<Subscript>1.5</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

NaNi_1.5P₂O₇ compound was obtained by the classic ceramic method at high temperature and was characterized by XRD. It was found to crystallize in the triclinic symmetry with the P-1 space group. The electrical conductivity and modulus characteristics of the system have been investigated in the temperature and the frequency range 586–723 K and 200 Hz–1 MHz, respectively, by means of impedance spectroscopy. The ac conductivity for grain contribution was interpreted using the universal Jonscher’s power law. The exponent s decreased with increasing temperature revealing that the conduction inside the studied material is insured by the correlated barrier hopping (CBH) model. The conduction mechanism was explained with the help of Elliot’s theory, and the Elliot’s parameters were determined. Thermodynamic parameters such as the free energy for dipole relaxation ΔG, the enthalpy ΔH, and the change in entropy ΔS have been calculated.     

Studies on structural and electrical properties of Mg<Subscript>0. 5+y</Subscript> (Zr<Subscript>2-y</Subscript>Fe<Subscript>y</Subscript>) <Subscript>2</Subscript> (PO<Subscript>4</Subscript>) <Subscript>3</Subscript> ceramic electrolytes

The sample of Mg_{0. 5+y} (Zr_1-y Fe_y) ₂ (PO₄) ₃ (0.0 ≤y ≤0.5) was synthesized using the sol-gel method. The structures of the samples were investigated using X-ray diffraction and Fourier transform infrared spectroscopy measurement. XRD studies showed that samples had a monoclinic structure which was iso-structured with the parent compound, Mg_0.5Zr (PO₄) ₃. The complex impedance spectroscopy was carried out in the frequency range 1–6 MHz and temperature range 303 to 773 K to study the electrical properties of the electrolytes. The substitutions of Fe³⁺ with Zr⁴⁺ in the Mg_0.5Zr (PO₄) ₃ structure was introduced as an extrainterstitial Mg²⁺ ion in the modified structured. The compound of Mg_0.5+y (Zr_1-y Fe_y)₂(PO₄)₃ with y?=?0.4 gives a maximum conductivity value of 1.25?×?10^?5 S cm^?1 at room temperature and 7.18?×?10^?5 S cm^?1 at 773 K. Charge carrier concentration, mobile ion concentration, and ion hopping rate are calculated by fitting the conductance spectra to power law variation, σ _ac (ω)?=?σ _o ? +?Aω ^α . The charge carrier concentration and mobile ion concentration increases with increase of Fe³⁺ inclusion. This implies the increase in conductivity of the compounds was due to extra interstitial Mg²⁺ ions.