Preparation,structural characterization and conductivity of LiZr2(PO4)3

Amorphous LiZr₂(PO₄)₃ has been prepared at room temperature starting from aqueous solutions of ZrOCl₂, H₃PO₄, and LiOH and then crystallized by heating at temperatures between 600 and 900°C. The material obtained at 900°C has been characterized by X-ray powder diffractometry, DSC analysis, and ac conductivity. It is monoclinic from 20 up to about 300°C and orthorhombic at higher temperatures. A change in the activation energy for conduction (from 0.79 to 0.43 eV) and a weak endothermic effect (0.9–1.7 cal/g) are associated with the phase transition. The ac conductivity of sintered pellets is, on average, 7×10⁻⁴ S cm⁻¹ at 300°C.     

N-乙酰化壳聚糖的FTIR和XRD研究

壳聚糖分子的脱乙酰度(DD)是影响壳聚糖性质的主要因素之一。文章通过壳聚糖的N-乙酰化反应制备了不同脱乙酰度的壳聚糖。采用傅里叶变换红外光谱(FTIR)和X射线衍射(XRD)分别研究了由N-乙酰化反应得到的不同脱乙酰度的壳聚糖的红外光谱特性和晶体结构,并由此分别计算确定了样品的脱乙酰度和结晶度,探讨了N-乙酰化程度对壳聚糖脱乙酰度以及结晶度的影响。 由FTIR可知,随N-乙酰程度的增加,壳聚糖分子中剩余氨基的反应速度变慢。另外XRD也表明,伴随N-乙酰反应,壳聚糖分子的结晶区被破坏,规整度下降,并逐渐形成新的结晶区。     

Ionic conductivity of isostructural crystals of the superionic conductors Li3Fe2(PO4)4 and Li3Sc2(PO4)3

The results of measurements of the ionic conductivity σ in Li₃M₂(PO₄)₃ (M=Fe, Sc) single crystals along various crystallographic directions are analyzed. Possible causes of the different behavior of σ in the isostructural crystals are discussed: a jump of the conductivity in the transition to the superionic phase in Li₃Sc₂(PO₄)₃ and its absence in Li₃Fe₂(PO₄)₃; the existence of a conductivity maximum in different crystallographic directions (along the c axis in Li₃Sc₂(PO₄)₃ and along the a axis in Li₃Fe₂(PO₄)₃). Fiz. Tverd. Tela (St. Petersburg) 39, 83–86 (January 1997)     

Theoretical studies of the spin Hamiltonian parameters and local structures for WO3 doped Zn3(PO4)2ZnO nanopowders

The spin Hamiltonian parameters (SHPs) and the local structures for impurity W⁵⁺ in the Zn₃(PO₄)₂ZnO nanopowders doped with WO₃ under different concentrations are theoretically investigated using the perturbation calculations of these parameters. The exponential functions of the related quantities (cubic field parameter Dq, covalency factor N, relative tetragonal compression ratio τ and core polarisation constant κ) of concentration x with totally four adjustable coefficients a, b, c and d are adopted to fit the concentration dependences of the experimental d-d transition bands and SHPs. The impurity W⁵⁺ centres demonstrate moderate tetragonal compression ratios τ (～3.1%) due to the Jahn–Teller effect. With the increase of WO₃ concentration, Dq and N show moderately decreasing rules, while τ and κ exhibit slightly and moderately increasing tendencies with x, respectively. The mechanisms of the above concentration dependences of these quantities are analysed from the modifications of the local crystal-field strength and electron cloud density around the impurity W⁵⁺ with the variation of x. Present theoretical studies would be useful to the exploration of the structural properties and optical applications for WO₃ doped Zn₃(PO₄)₂ZnO nanopowders.     

Properties of B_4C-TiB_2 ceramics prepared by spark plasma sintering

By doping titanium hydride(TiH2) into boron carbide(B4C), a series of B4C + x wt% TiH2(x = 0, 5, 10, 15, and 20)composite ceramics were obtained through spark plasma sintering(SPS). The effects of the sintering temperature and the amount of TiH2 additive on the microstructure, mechanical and electrical properties of the sintered B4C-TiB2 composite ceramics were investigated. Powder mixtures of B4C with 0–20 wt% TiH2 were heated from 1400℃ to 1800℃ for 20 min under 50 MPa. The results indicated that higher sintering temperatures contributed to greater ceramic density. With increasing TiH2 content, titanium diboride(TiB2) formed between the TiH2 and B4C matrix. This effectively improved Young’s modulus and fracture toughness of the composite ceramics, significantly improving their electrical properties: the electrical conductivity reached 114.9 S·cm-1 at 1800℃ when x = 20. Optimum mechanical properties were obtained for the B4C ceramics sintered with 20 wt% TiH2, which had a relative density of 99.9±0.1%, Vickers hardness of 31.8 GPa,and fracture toughness of 8.5 MPa·m1/2. The results indicated that the doping of fine Ti particles into the B4C matrix increased the conductivity and the fracture toughness of B4C.     

Optical bandgap and electrical conductivity studies on near stoichiometric LiNbO3 crystals prepared by VTE process

Vapour transport equilibrium (VTE) technique was used to prepare near stoichiometric LiNbO₃ (NSLN) crystals. Simultaneous occurrence of reduction has been observed during the Li-enrichment that results in the weak absorption bands centred at 1.7, 2.6 and 3.7 eV in the absorption spectrum. Annealing in oxygen atmosphere resulted in decrease in the intensity of these bands. The indirect and direct band-gap energies for NSLN crystals evaluated from absorption studies are reported. The energy of the phonon involved in the indirect transition is ～85 meV (685 cm^?1). Near room temperature ac-conductivity measurements reveal lower conductivity for oxygen annealed NSLN crystal in comparison to as prepared NSLN and CLN specimens. The activation energies for ac-conductivity along the z-direction for NSLN and CLN crystals in the temperature range 500–1100 K are 1.03 eV and 0.96 eV, respectively.     

XPS and ionic conductivity studies on Li1.3Al0.15Y0.15Ti1.7(PO4)3 ceramics

Li_1.3Al_0.15Y_0.15Ti_1.7(PO₄)₃ compound was synthesized by solid-state reaction, and ceramics were sintered. The surfaces of the ceramics were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. Li_1.3Al_0.15Y_0.15Ti_1.7(PO₄)₃ samples were tested in solid galvanic cells Ag|O₂+CO₂|Li₂CO₃|Li_1.3Al_0.15Y_0.15Ti_1.7(PO₄)₃|LiMnO₂+Mn₂O₃|O₂|Ag. The electromotive force measurements of this cell indicated that investigated samples are practically pure Li-ion conductors. Impedance spectroscopy studies have been performed in the frequency range 10^?2–3·10⁹ Hz and temperatures from ?57 °C to 334 °C. Three dispersion regions related to Li⁺ ionic transport in bulk, grain boundaries of the ceramics and to polarization of electrodes have been found. Total conductivity changes according to Arrhenius law in the studied temperature range, but an anomalous behavior was observed for the bulk conductivity of the ceramics.     

Superprotonic conductivity in Cs5(HSO4)2(H2PO4)3 single crystal

The conductivity of cesium hydrosulfate-phosphate single crystals obtained for the first time has been studied. It has been shown that these single crystals undergo a phase transition to a state with superprotonic conductivity. It has been found that the state with high proton conductivity is retained during thermal cycling for a long time and has a quasi-reversible nature.     

Proton conductivity and low temperature structure of In-doped BaZrO3

The proton conductivity and structural features of In³⁺ substituted BaZrO₃ samples, i.e., BaZr_1−xIn_xO_3−δ, were investigated. Rietveld analysis of low temperature (10 K) neutron powder diffraction data collected on as-prepared and deuterated samples confirmed cubic symmetry (space group Pm-3m) for all compositions. The level of oxygen vacancies refined in the as-prepared samples were in good agreement with the values expected to conserve charge neutrality, whilst an increase in oxygen occupancy, reflecting the incorporation of OD⁻ species, was obtained for the deuterated materials. An expansion of the unit cell parameter, a, was observed as a function of In³⁺ doping as well as after the deuteration reaction. The conductivity of pre-hydrated and dry samples was measured using impedance methods. For 25% In-doped BaZrO₃, the low T (300 °C) conductivity of the heating cycle of the dried sample was greater than that of the cooling cycle of the pre-hydrated sample indicating a greater number of protons in the nominally dry sample. In contrast, the conductivity values were similar at higher temperatures e.g. T > 500 °C where proton conduction is not dominant.     

Electrical conductivity relaxation in PVOH+LiH2PO4+Al2O3 polymer composites

Low-frequency conductivity measurements have been performed in solid polymer electrolyte composites based on the anhydrous PVOH–LiH₂PO₄–Al₂O₃ system. A typical power law dependency in the real part of the conductivity, at higher frequencies, of the form ω ⁿ is observed, with an exponent n that depends on the alumina content and nearly independent of temperature. An analysis of the frequency dependence of the electrical susceptibility is conducted to obtain relaxation functions of the form exp[?(t/τ) ^β ], with an exponent β?≈?n???1. Correlation times, τ, and parameters characterizing the electrical relaxation in time and frequency domains are compared to show the equivalence of these representations. The anhydrous dc conductivity of the electrolytes increases with increasing lithium salt content, becoming of the order of 10^?5 S/cm for a salt molar fraction of x?=?0.14. This conductivity value increased by about one order of magnitude by addition of nanoporous particles of Al₂O₃. The temperature dependence of the samples conductivity was well described by the Vogel–Tammann–Fulcher’s equation indicating the effect of the polymer chains flexibility on ion migration. Although all membranes exhibited a “universal dynamic response” associated to the random hopping of the mobile carriers, variations in the measured relaxation parameters with alumina content indicate an increase of ionic correlations when adding the nonporous particles to the polyelectrolyte.     

Structure,defect chemistry,and proton conductivity in nominally Sr-doped Ba3La(PO4)3

The AC conductivity of eulytite-structured Ba₃La(PO₄)₃ with 2 mol% Sr substituted for La has been investigated in the range 300–1300 °C at different oxygen and water vapor (H₂O or D₂O) partial pressures. The overall sample impedance has contributions from bulk (grain interior) and grain boundaries. It is concluded from the H/D isotope effect that the bulk conductivity is mainly protonic. The defect chemistry leading to a content of protons is discussed.     

EDXRF,FTIR, and XRD characterization of low calcium oxalate urinary stones collected from arid area

Low calcium oxalate urinary stones from the kidney, bladder, and ureter have been collected from the arid area (Taif, Saudi Arabia). After careful washing and drying of the collected stones, the samples were converted into a contamination-free homogenous fine powder with a particles' size smaller than 50 μm. The processed urinary stone powders were studied using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), laboratory setup and synchrotron radiation X-ray diffraction (XRD), and energy-dispersive X-ray fluorescence (EDXRF). The activated function groups, quantitative phase analysis, and the semi-quantitative elemental analysis of the present urinary stones were identified. Seventeen elements were measured in most of the urinary stone samples. The significant elements are Ca, P, S, Cl, Zn, K, Fe, and Cu, whereas other elements were found alternatively in a few number of urinary stone samples. It was recognized that Ca exists with low concentration, which indicates the presence of different calcium phases even with low percentages. In 33% of the urinary stones, the phosphorus (P) was not measured, but there were high concentrations of sulfur (S) and low concentrations of Ca up to 2.15 ± 0.05%. The ATR-FTIR results indicate that the most compounds of the present urinary stones were urea and cystine combined with low ratios of calcium oxalate and calcium phosphate compounds. The quantitative phase analysis of the XRD of selected samples proves the presence of the cystine, urea, and calcium oxalate phases with different weight percent.     

Synthesis of Fe2O3 concentrations and sintering temperature on FTIR and magnetic susceptibility measured from 4 to 300 K of monolith silica gel prepared by sol–gel technique

Nano-crystalline ferric oxide was synthesized inside an amorphous silica matrix by the sol–gel method. The formation of ferric oxide can be detected, giving fine particles around 5–10 nm crystallite sizes calculated from win-fit program. This is associated with a specific role of the silica matrix, which facilitates the diffusion of the reacting cations, enhancing the ferric oxide formation. γ- to α- and/or ε-Fe₂O₃ transformations take place by increasing the Fe₂O₃ concentration for samples sintering at constant-heat treatment temperature. The dried monolith gel materials were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), as well as by scanning electron microscopy (SEM). The magnetic susceptibility at zero-field cooling (M_ZFC) of the prepared samples was evaluated using superconducting quantum interference device (SQUID) magnetometer in temperature range from 4 to 300 K at 1 T.     

Magnetic studies on synthetic phosphoferrite Fe 3 2+ (H2O)3(PO4)2

Synthetic crystals of phosphoferrite were studied by Mössbauer spectroscopy for temperatures ranging from 4.2 to 17.5 K. The analysis of the behaviour of the hyperfine fields for the two unequivalent sites near the Néel temperature (17.4 K) allowed the determination of the critical exponent for each site as ₁=0.171 and ₂=0.314.     

Composition, XRD and morphology study of laser prepared LiNbO3 films

LiNbO₃ films were deposited by PLD from LiNbO₃ crystalline or from three different stoichiometric or Li-enriched LiNbO₃ targets. Polycrystalline films were prepared on SiO₂/Si or sapphire substrates at temperatures T _S ～650–750 °C. Main attention was paid to the influence of targets preparation and the deposition conditions on films composition, morphology and crystallinity. The thin-film morphology was determined by SEM microscopy. The composition was measured by SIMS, RBS, PIXE and PIGE methods. Highly oriented, smooth and stoichiometric LiNbO₃ films were synthesized.     

AC impedance, FTIR and XRD investigations of poly acrylonitrile complexed with LiCF3SO3

Solid polymer electrolytes of high ionic conductivity are prepared using poly acrylonitrile (PAN), propylene carbonate (PC), ethylene carbonate (EC) and LiCF₃SO₃. The polymer films are characterised by X-ray diffraction, FTIR and a.c. impedance spectroscopic techniques. The conductivity studies of PAN-LiCF₃SO₃-PC-EC polymer electrolyte systems are carried out in the temperature range 301–373 K. The temperature dependence of the conductivity of the polymer films obeys the VTF relation. The conductivity values are presented and the results are discussed.