AC Conductivity and Dielectric Response of Polycrystalline and Amorphous C70

The AC conductivity and dielectric constant of polycrystalline and amorphous C₇₀ samples were measured in the 75-300 K temperature range and in the 100 Hz to 1 MHz frequency range. For polycrystalline samples, we observe effects caused by O₂ intercalation due to prolonged exposure to ambient air. The conductivity σ of these samples around 300 K depends on the measuring frequency ν as a σ ∼ νⁿ with n ≈ 0.88, implying a strong reduction of DC conductivity to less than 10^-12 S/cm. The dielectric constant of polycrystalline samples shows an anomaly at 285 K which is interpreted as due to the transition from its intermediate rhombohedral phase into its monoclinic low-temperature phase. In contrast with the polycrystalline samples, the amorphous C₇₀ samples prepared by sublimation do not contain interstitial 0₂, their conductivity at 300 K is of about 10^-6 S/cm, is independent of frequency, and is well described by the hopping mechanism (Davis-Mott T^1/4 law) in the 200-300 K range. All evidence of phase transitions disappears in the amorphous samples.     

AC impedance spectroscopy of porous silicon thin films containing metallic cations

Thin porous silicon (PS) films were prepared by HF/HNO₃ vapor etching on silicon wafers. The infiltration of metallic cations inside the porous silicon matrix followed by slow heating in air leads to an interesting electrical and optical physical phenomena. Al³⁺, Cu⁺, K⁺, Li⁺ metallic cations as chloride or as nitrate solutions are infiltrated inside the silicon porous matrix. After annealing in air at 500 °C during 2 h a structure was achieved in order to measure the Nyquist diagram corresponding to the cations embedded in PS/silicon. The real and imaginary parts of the whole structure depend on the voltage bias and on the frequency. Those signify that the junction is a Schotky-barrier junction.

From the variation of Ln(σT) versus absolute temperature T, where σ is the conductivity, we have deduced the activation energy of the metallic impurities in the [100 °C–400 °C] temperature range. We have found that the activation energies are of about 0.19 eV, 0.25 eV, 0.49 eV and 0.71 eV for Cu⁺, K⁺, Al³⁺ and Li⁺ cations respectively. These kinds of structures are suitable for gas sensing, optical sensing or for the fabrication of fuel cell membranes.     

Dielectric Properties of (C60 + C70)—Ferroelectric Liquid Crystal Composite

A stable composite of fullerene and ferroelectric liquid crystal (FLC) has been obtained. Analysis of the frequency dependence of imaginary part of complex dielectric permittivity showed that orientation of the liquid crystal (LC) in the composite is close to homeotropic. At temperatures above 329 K, the composite conductance is determined by the conductance of fullerene. At 344 K, the composite conductance is 3.2 × 10^-8 Ω^-1 m^-1, and the activation energy for the temperature dependence of conductance is 0.99 eV. At temperatures below 329 K, the composite properties are determined by the LC, and the frequency dependences of the components of complex dielectric permittivity showed dispersion due to rotation of molecular dipoles around the helicoid (Goldstone mode) axis. The relaxation time is close to 1 msec and almost equal to the value obtained for homeotropically oriented LC.     

Crystal structure, thermal expansion and electrical conductivity of Nd0.7Sr0.3Fe1−xCoxO3 (0≤x≤0.8)

The crystal structure, thermal expansion and electrical conductivity of the solid solution Nd_0.7Sr_0.3Fe_1−xCo_xO₃ for 0≤x≤0.8 were investigated. All compositions had the GdFeO₃-type orthorhombic perovskite structure. The lattice parameters were determined at room temperature by X-ray powder diffraction (XRPD). The pseudo-cubic lattice constant decreased continuously with x. The average linear thermal expansion coefficient (TEC) in the temperature range from 573 to 973 K was found to increase with x. The thermal expansion curves for all values of x displayed rapid increase in slope at high temperatures. The electrical conductivity increased with x for the entire temperature range of measurement. The calculated activation energy values indicate that electrical conduction takes place primarily by the small polaron hopping mechanism. The charge compensation for the divalent ion on the A-site is provided by the formation of Fe⁴⁺ ions on the B-site (in preference to Co⁴⁺ ions) and vacancies on the oxygen sublattice for low values of x. The large increase in the conductivity with x in the range from 0.6 to 0.8 is attributed to the substitution of Fe⁴⁺ ions by Co⁴⁺ ions. The Fe site has a lower small polaron site energy than Co and hence behaves like a carrier trap, thereby drastically reducing the conductivity. The non-linear behaviour in the dependence of log σT with reciprocal temperature can be attributed to the generation of additional charge carriers with increasing temperature by the charge disproportionation of Co³⁺ ions.     

Microwave dielectric characteristics of Ba(Mg1/3Ta2/3)O3 ceramics sintered at low-temperatures

The microwave dielectric properties and microstructures of Ba(Mg_1/3Ta_2/3)O₃ (BMT) ceramics sintered at low temperatures with 2–3 wt.% NaF additives were investigated. BMT ceramics sintered at 1340 °C for 3–12 h showed dielectric constants (_r) of 25.5–25.7, Qf values of 41 500–50 400 GHz and temperature coefficients of the resonator frequency (τ_f) of 10.9–21.4 ppm °C⁻¹. The variation of sintering time almost had no effect on the dielectric constant. The Qf value increased and the τ_f decreased with increasing sintering time. The ordering degree of Mg²⁺ and Ta⁵⁺ at B-sites increased with increasing sintering time.     

Growth and Studies of Two New Potassium Compound Crystals

We have attempted to grow the single crystals of K₃BaCl₅·2H₂O (KBC) and K₃CaCl₅·2H₂O (KCC) from aqueous solutions by the slow evaporation method. Crystals up to a size of 1.6 × 1.1 × 0.4 cm³ were obtained. Atomic absorption spectroscopic and X-ray diffraction measurements have shown the nonstoichiometric nature of the grown crystals. Thermogravimetric measurements have confirmed the presence of water molecules. Microhardness measurements indicate that the mechanical strength is poor. DC conductivity measurements at various temperatures on these crystals indicate that KBC is a dielectric material whereas the KCC is an ionic conductor. Dielectric measurements were carried out with a fixed frequency of 1 kHz at various temperatures by the parallel plate capacitor method. The results indicate that the ionic polarization may be the dominating factor in both of the systems studied.     

Solid polymer electrolytes based on poly(vinylchloride)–lithium sulfate

Ionic conductivity studies in the temperature range 304–373 K for PVC---Li₂SO₄---dibutylphthalate polymer electrolyte systems are reported and discussed. Poly(vinylchloride) (PVC) has an electrical conductivity 10⁻⁸ S cm⁻¹. The prepared films were studies by X-ray diffraction, Fourier transformation infrared, scanning electron microscopy and thermal analysis. The temperature dependence of the conductivity of the polymer films obeys the Vogel–Tammann–Fulcher relation.     

Liquid-Liquid Extraction, Separation, Preconcentration, and ICP-AES Determination of Lanthanum and Cerium with N-Phenyl-(1,2-methanofullerene C60)61-formohydroxamic Acid

A novel method for liquid-liquid extraction, separation, preconcentration, and simultaneous trace determination of cerium(IV) and lanthanum(III) with N-phenyl-(1,2-methanofullerene C₆₀)61-formohydroxamic acid (PMFFA) is reported. Lanthanum and cerium are extracted at pH 8.5 and 9.5, respectively in chloroform and recovered from monazite sands in the presence of thorium, uranium, and large number of cations and anions in high purity (99.98%). The extraction mechanism is investigated. The influence of PMFFA, pH, diverse ions, and temperature on the distribution constants of lanthanum and cerium was examined. The overall stability constants (log β₂K_e) and extraction constants (K_ex) for lanthanum(III) are 22.50 and 5.0 × 10^-9, respectively and for cerium(IV) are 21.51 and 3.9 × 10^-9, respectively. Lanthanum(III) gives a colourless complex with PMFFA which is extracted into chloroform having molar absorptivity 5.5 × 10⁴ L mol^-1 cm^-1 at 395 nm, and Beer's law 0.12-2.52 µg mL^-1, while cerium(IV) forms a red coloured complex, λ_max 460 nm, molar absorptivity 1.5 × 10⁴ L mol^-1 cm^-1, and Beer's law 0.46-9.26 µg mL^-1. For trace determination the extracts were directly inserted into the plasma for inductively coupled plasma atomic emission spectrometry ICP-AES measurements of lanthanum and cerium which increases the sensitivity 60 folds and obey Beer's law in the range, 2.1-37.5 ng mL^-1 for lanthanum and 9.2-186.4 ng mL^-1 for cerium. The method is applied for the determination of lanthanum and cerium in real and standard samples, sea water, and environmental samples.     

Extrusion Processing of High-Strength Al Alloy 7055

The effects of a combination of extrusion processing parameters and aging schedules on the microstructure and mechanical properties of the 7055 Al alloy were investigated. A safe extrusion processing zone is determined through a limit diagram constructed over the experimental initial billet temperature ranging from 380° to 420°C, extrusion ratio from 10:1 to 40:1, and the ram speed ranging from 1 to 15 mm s^-1. Microstructural characterization of as-extruded, solution-treated, and artificially-aged materials was carried out using polarized light microscopy (for grain structure) and transmission electron microscopy (for precipitate morphology). A combination of hardness and tensile tests was used to evaluate mechanical properties. It is shown that in 7055 Al alloy, the optimization of alloy composition, extrusion processing parameters, and peak aging treatment results in reproducible tensile properties of 0.2% P.S. = 725 MPa, UTS = 750 MPa, and % elongation = 12.9. In order to improve the stress-corrosion resistance of peak aged material, retrogression and reaging (RRA) temper was established. A strength-electrical conductivity relationship has been established for the RRA temper between 36% and 37% International Annealed Copper Standard (IACS) electrical conductivity to enable selection of suitable combination of properties.     

A Novel Fullerene Hydroxamic Acid for the Liquid-Liquid Extraction, Separation, Preconcentration, and Spectrophotometric and ICP-AES Determination of Vanadium

A new reagent N-phenyl-(1,2 methanofullerene C₆₀)61-formohydroxamic acid (PMFFA) is reported for extraction and trace determination of vanadium(V) in nutritional and biological substrates. The extraction mechanism of vanadium from 6 M HCl media is investigated. The influence of PMFFA, diverse ions, and temperature on the distribution constant of vanadium examined. The over all stability constant (log β₂K_e) and extraction constant (K_ex) are 20.89 ± 0.02 and 8.0 ± 0.02 × 10^-15, respectively in chloroform. The thermodynamics parameters are calculated and kinetics of vanadium transport is discussed. The system obeys Beer's law in the range of 3.2-64.0 ng mL^-1 of vanadium(V). The molar absorptivity is 7.96 × 10⁵ L mol^-1 cm^-1, at 510 nm. The PMFFA-vanadium(V) complex chloroform extract in chloroform was directly inserted into plasma for ICP-AES measurement, which increases the sensitivity by 50 folds and obey Beer's law in the range of 50-1200 pg mL^-1 of vanadium(V). The method is applied for determination vanadium in real standard samples, sea water, and environmental samples.     

Development of matrix patches for transdermal delivery of a highly lipophilic antiestrogen

The aim of this study was to develop matrix-type transdermal systems (TDSs) containing the highly lipophilic (log P = 5.82) antiestrogen (AE) and the permeation enhancers propylene glycol and lauric acid. For that purpose, permeation of AE from various adhesive matrices through excised skin of hairless mice was evaluated. It was found that pretreatment of the skin with permeation enhancers raised the transdermal flux of subsequently applied antiestrogen. Highest steady-state transdermal fluxes (1.1 µg cm^-2 h^-1) were obtained from Gelva®, polyacrylate adhesive, followed by 0.55 µg cm^-2 h^-1 from Oppanol® polyisobutylene, 0.31 µg cm^-2 h^-1 from BIO-PSA® silicone, and 0.12 µg cm^-2 h^-1 from Sekisui polyacrylate matrices. In order to develop TDS with high content of fluid permeation enhancer propylene glycol, two different strategies were investigated. One strategy was the addition of hydroxypropyl cellulose (HPC) as thickening agent to Gelva matrices. This allowed for propylene glycol loading levels of up to 30%, resulting in transdermal AE fluxes of 0.09 µg cm^-2 h^-1. On the other hand, a fleece-laminated backing foil was loaded with the described permeation enhancer formulation and laminated with polyacrylate adhesive layer, resulting in transdermal AE fluxes of 0.06 µg cm^-2 h^-1. However, application of these TDSs on skin pretreated with permeation enhancers raised the fluxes to 2.6 µg cm^-2 h^-1 from Gelva/HPC and 0.46 µg cm^-2 h^-1 from fleece/Sekisui.     

硫化物固态电解质Li6PS5Cl的球磨-固相烧结制备与性能

硫银锗矿结构的硫化物固态电解质Li₆PS₅Cl（LPSC）具有离子电导率高（>3×10^-3 S·cm^-1）和对锂稳定性良好等特点,是构建全固态锂离子电池的理想电解质材料之一,具有良好的发展前景。本工作采用高能球磨和惰性气氛固相烧结相结合的方法制备硫银锗矿型固态电解质LPSC,并采用粉末X射线衍射（XRD）、拉曼光谱（Raman spectra）和扫描电子显微镜（SEM）等对其进行表征,探究制备工艺对LPSC结构、成分和电学性质等的影响。结果表明：高能球磨会破坏原料的晶粒,降低晶粒尺寸,延长球磨时间有利于LPSC前驱体粉末的非晶化和后续烧结,提高烧结温度将促进制备的LPSC电解质的物相变纯和离子电导率升高,但烧结温度过高会导致LPSC的分解。综合考虑球磨时间和烧结温度对材料离子电导率和电子电导率的影响,经8 h球磨和500℃烧结制备的LPSC在室温下具有最高的离/电子电导率比（2.091×10⁵）,其离子电导率高达4.049×10^-3 S·cm^-1,而电子电导率仅为1.936×10^-8 S·cm^-1。利用该电解质制备的712 NCM/LPSC/In-Li全固态电池在0.1 C的充放电倍率下首周放电比容量高达151.3 mAh·g^-1,且具有优良的循环稳定性。     

MWCNTs改善WS2/三元乙丙橡胶复合材料的非线性电导特性与热导性能

通过在一定量的纳米WS₂中添加极少量的多壁碳纳米管（MWCNTs）,形成MWCNTs-WS₂复配填料,采用双辊开炼机将三元乙丙橡胶（EPDM）与不同配比的复配填料混合制备了不同MWCNTs含量的MWCNTs-WS₂/EPDM复合材料。并研究了极少量的MWCNTs添加对MWCNTs-WS₂/EPDM复合材料非线性电导性能、直流击穿性能和导热性能的影响。结果表明,极少量的MWCNTs对MWCNTs-WS₂/EPDM复合材料在25℃时的非线性电导特性起到明显的增强作用,且随着MWCNTs含量的增加,复合材料非线性电导特征有明显的规律性变化;由于MWCNTs自身的高电导率和电导正温度系数效应,MWCNTs-WS₂/EPDM复合材料电导率随电场强度的变化趋势在80℃时不再表现非线性特征。另外,极少量的MWCNTs对MWCNTs-WS₂/EPDM复合材料的热导率有明显地改善。      

Piroxicam benzoate--synthesis,HPLC determination,and hydrolysis

An improved method of piroxicam benzoate synthesis was described, and an isocratic reversed-phase high-performance liquid chromatography method for its determination was developed and fully validated. The method was found to be specific, precise (relative standard deviation 0.3%), accurate (mean recovery 99.9%), and robust. Limit of detection was estimated at 0.055 µg mL^-1 and limit of quantification at 0.185 µg mL^-1. The kinetics of piroxicam benzoate hydrolysis in aqueous buffer solutions (pH 1.1 and 10), simulated gastric and intestinal fluids was studied. The hydrolysis followed first-order kinetics. The following rate constants were obtained at pH 10: k = 1.8 × 10^-3 hr^-1 at 37°C and k = 3.4 × 10^-2 hr^-1 at 60°C. In acidic media, no significant hydrolysis was observed after 24 hr. During the 24-hr period in simulated intestinal fluid, only 10.9% of the starting ester was hydrolyzed.     

Dielectric properties of AlN films prepared by laser-induced chemical vapour deposition

The dielectric properties and electrical conductivity of AlN films deposited by laser-induced chemical vapour deposition (LCVD) are studied for a range of growth conditions. The static dielectric constant is 8.0 ± 0.2 over the frequency range 10²−10⁷ Hz and breakdown electric fields better than 10⁶ V cm⁻¹ are found for all films grown at temperatures above 130°C. The resistivity of the films grown under optimum conditions (substrate temperature above 170°C, NH₃/TMA flow rate ratio greater than 300 and a deposition pressure of 1–2 Torr) is about 10¹⁴ Ω cm and two conduction mechanisms can be identified. At low fields, F < 5 × 10⁵ V cm⁻¹ and conductivity is ohmic with a temperature dependence showing a thermal activation energy of 50–100 meV, compatible with the presumed shallow donor-like states. At high fields, F > 1 × 10⁶ V cm⁻¹, a Poole-Frenkel (field-induced emission) process dominates, with electrons activated from traps at about 0.7–1.2 eV below the conduction band edge. A trap in this depth region is well-known in AlN. At fields between 4 and 7 × 10⁵ V cm⁻¹ both conduction paths contribute significantly. The degradation of properties under non-ideal growth conditions of low temperature or low precursor V/III ratio is described.     

Transparent conducting F-doped SnO2 thin films grown by pulsed laser deposition

Transparent conducting fluorine-doped tin oxide (SnO₂:F) films have been deposited on glass substrates by pulsed laser deposition. The structural, electrical and optical properties of the SnO₂:F films have been investigated as a function of F-doping level and substrate deposition temperature. The optimum target composition for high conductivity was found to be 10 wt.% SnF₂ + 90 wt.% SnO₂. Under optimized deposition conditions (T_s = 300 °C, and 7.33 Pa of O₂), electrical resistivity of 5 × 10^− 4 Ω-cm, sheet resistance of 12.5 Ω/□, average optical transmittance of 87% in the visible range, and optical band-gap of 4.25 eV were obtained for 400 nm thick SnO₂:F films. Atomic force microscopy measurements for these SnO₂:F films indicated that their root-mean-square surface roughness ( 6 Å) was superior to that of commercially available chemical vapor deposited SnO₂:F films ( 85 Å).     

Structural, electrical, and optical studies on rapid thermally processed ferroelectric BaTiO3 thin films prepared by metallo-organic solution deposition technique

Polycrystalline BaTiO₃ thin films having the perovskite structure were successfully produced on platinum coated silicon, bare silicon, and fused quartz substrate by the combination of the metallo-organic solution deposition technique and post-deposition rapid thermal annealing treatment. The films exhibited good structural, electrical, and optical properties. The electrical measurements were conducted on metal-ferroelectric-metal (MFM) and metal-ferroelectric-semiconductor (MFS) capacitors. The typical measured small signal dielectric constant and dissipation factor at a frequency of 100 kHz were 255 and 0.025, respectively, and the remanent polarization and coercive field were 2.2 μC cm⁻² and 25 kV cm⁻¹, respectively. The resistivity was found to be in the range 10¹⁰–10¹² Ω·cm, up to an applied electric field of 100 kV cm⁻¹, for films annealed in the temperature range 550–700 °C. The films deposited on bare silicon substrates exhibited good film/substrate interface characteristics. The films deposited on fused quartz were highly transparent. An optical band gap of 3.5 eV and a refractive index of 2.05 (measured at 550 nm) was obtained for polycrystalline BaTiO₃ thin film on fused quartz substrate. The optical dispersion behavior of BaTiO₃ thin films was found to fit the Sellmeir dispersion formula well.     

Characterization of FeS2-pyrite thin films synthesized by sulphuration of amorphous iron oxide films pre-deposited by spray pyrolysis

FeS₂-thin films with good crystallinity were synthesized by a simple method which consists of sulphuration, under vacuum, of amorphous iron oxide thin films pre-deposited by spray pyrolysis of FeCl₃·6H₂O (0.03 M)-based aqueous solution onto glass substrates heated at 350 °C. At optimum sulphuration temperature (450 °C) and duration (6 h), black green layers having granular structure and high absorption coefficient (5.10⁴ cm⁻¹) were obtained. The study of the electrical properties of the as-prepared films vs. the temperature variations showed three temperature domain dependence of the conductivity behaviour. The first one corresponds to the high temperature range (330 K–550 K) for which an Arrhenius plot type was obtained. The activation energy value was estimated at about 61.47 meV. The second domain corresponding to the intermediate temperature range (80 K–330 K) showed a variable activation energy between the grain boundaries. The barrier height, q¯, was estimated to 27±0.5 meV, and the standard deviation, qσ, was evaluated at about 14±0.5 meV. We found that at lower temperatures (20 K–80 K), the conductivity is governed by two conduction types. The density of localised states, was about 2.45×10²⁰ eV⁻¹ cm⁻³.     

KD-II型碳化硅纤维热输运性质的实验研究

SiC纤维是复合材料SiC_f/SiC中的组分材料, 其力学性能已经得到实验验证, 但热学性能尚未见报道。本研究采用综合T型法测量了不同温度热处理的KD-II型SiC纤维在80~300 K温度范围内的电导率、热导率和塞贝克系数, 热处理温度分别为1400、1500和1600℃。研究发现, 在实验设定的热处理温度范围内, SiC纤维电导率不随热处理温度改变而改变, 但其热导率随热处理温度升高有显著的变化。在环境温度为290 K时, 1600℃热处理的SiC纤维热导率为11.6 W•m^-1•K^-1, 比未热处理的材料提高了42%以上。     

LASER INDUCED MICROCRYSTALLIZATION OF BULK AMORPHOUS Ge15Se85-xTex

Bulk amorphous samples of Ge₁₅Se_85-xTe_x (x = 10,15,20,25) were prepared by a rapid quenching. X-ray diffraction analysis revealed that the as-grown samples were amorphous. In order to understand the laser induced changes, the samples were irradiated with Q-switched Nd: YAG laser pulses of various energy densities (2-50 mJ/cm²). These studies showed that low energy pulses (≤10 mJ/cm²) have no influence on the structure and the transport properties of the samples whereas energy pulses (≥ 10 mJ/cm²) resulted in microcrystallization of the samples. Electrical transport properties such as d.c. electrical conductivity and thermoelectric power were measured as a function of temperature (200 -350 K) and composition. Results were analysed in terms of Small polaron model and two carrier model respectively. The electrical conduction, interestingly, was observed as intrinsic in the entire temperature range of measurements for both as-grown and irradiated samples.