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.     

Preparation, Electrical, and Dielectric Characterization of Crosslinked Polyvinyl Alcohol-Phosphotungstic Acid Nanocomposites

The work presents the electrical and dielectric characterization of proton-conducting, chemically-crosslinked nanocomposites of polyvinyl alcohol (PVA) and phosphotungstic acid (PTA). The composite membranes were prepared by in situ crosslinking of the polymer matrix in solution form, containing PTA. The electrical and dielectric properties of the membranes were investigated as a function of blending composition, crosslinking density, and temperature. The conductivity of these membranes shows a temperature dependence of Arrhenius type and highest conductivity of 3.31 × 10^-3 S cm^-1 was obtained. The activation energies for proton conduction were found to be in the range of 15.28-40.62 kJ mol^-1.     

Ozone Reaction with C70 and C60 Fullerenes: The Effect of Temperature on the Reaction Kinetics

It has been confirmed that the effect of temperature on the rate constants (k) of ozone reaction with C₇₀ and C₆₀ fullerenes follows the Arrhenius law. The experimental values of activation energy (E_a) and pre-exponential factor (A), like as those of other simple alkenes, are in the order of 2.4-2.6 kcal mol^-1 and (1.2-1.8) × 10⁷ L mol^-1 sec^-1, respectively. They are practically equal for the both fullerenes. It has also been found that the value of the rate constant k of C₇₀ fullerene ozonolysis is higher in comparison to the respective k-value of C₆₀.     

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.     

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.     

Effect of thermal treatment conditions on the properties of onion-like carbon based polymer composite

Dielectric properties of onion-like carbon (OLC) and polyurethane composite prepared using different procedures were investigated in the frequency range up to 1 MHz. We show that broadband dielectric spectroscopy is powerful tool to determine technological fingerprints in the studied materials. It is demonstrated that cured samples annealed at temperature close to the melting point (450 K) exhibit substantially higher dielectric permittivity and electrical conductivity in comparison with untreated samples. With the increase of temperature of an untreated sample, its dielectric permittivity, electric conductivity and critical frequency increase, while Maxwell–Wagner mean relaxation time and aggregate sizes of OLC decreases. Annealing of the composite at temperature close to the melting temperature produce sample with more homogeneous distribution of OLC. The temperature dependence of conductivity of the homogeneous sample is mainly caused by a weak positive temperature coefficient effect.     

Reaction Kinetics of C60 Fullerene Ozonation

It has been verified that the reaction between O₃ and C₆₀ follows the general second order reaction rate which is valid for all the reactions between ozone and unsaturated olefinic bonds: v = k[C=C][O₃]. The reaction rate constant k has been measured ≈(1.5 ± 0.3) × 10⁴ L mol^-1 s^-1. The value of this rate constant has the same order of magnitude of the rate constant measured for instance in the ozonation of 1,4-diphenylbutadiene.     

Thermodynamic Properties and Hydrogen Accumulation Ability of Fullerene Hydride C60H36

Thermodynamic properties of fullerene hydride C₆₀H₃₆ in the ideal-gas and crystal states were studied by theoretical methods. Molecular structures and vibration frequencies were calculated for 9 isomers of C₆₀H₃₆ by the density functional theory (DFT) by use of a combination of the B3LYP functional with 6-31G* basis sets. Ideal-gas thermodynamic properties were calculated based on those parameters. Enthalpies of formation of C₆₀H₃₆ isomers in the ideal-gas state were derived from homodesmic reactions involving adamantane, cyclohexane, and C₆₀ fullerene. Using the standard methods of statistical mechanics, heat capacity and derived thermodynamic properties of crystalline C₆₀H₃₆ were calculated at 340-1000 K that extended the range of experimental measurements. With a crystal-gas heat capacity difference, the experimental value of sublimation enthalpy was extrapolated to room temperature as Δ_subH_m^o (298.15 K)=(193±10) kJ · mol^-1. Combining this value with the known experimental enthalpy of formation in the crystalline state, the ideal-gas enthalpy of formation of C₆₀H₃₆ at the synthesized sample isomer composition was obtained: Δ_f H_m^o (298.15 K)=(1206±28) kJ · mol^-1. Equilibrium constants and compositions were calculated for the reactions of hydrogenation of C₆₀ fullerene in different states. It was shown that C₆₀ can act as a hydrogen accumulator.     

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.     

Morphological and electrochemical properties of boron-doped diamond films on carbon cloths with enhanced surface area

The electrochemical properties of doped diamond electrodes (10¹⁷–10¹⁹ B cm^− 3) grown on carbon fiber cloths in H₂SO₄ 0.1 mol L^− 1 electrolyte were investigated. Cyclic voltammograms of B-doped diamond/carbon fiber cloth and carbon fiber cloth electrodes showed that both kinds of electrodes possess similar working potential windows of about 2.0 V. The electrode capacitance was determined by impedance spectroscopy and chronopotentiometry measurements and very close values were obtained. The capacitance values of the diamond film on carbon fiber cloths were 180 times higher than the ones of diamond films on Si. In this paper we have also discussed the capacitance frequency dependence of diamond/carbon cloth electrodes.     

Electrically Conductive Composite Powders and Compounds Produced with Solid State Synthesis

Electrically conductive composite powders and compounds were produced using a mechanical alloying method. As starting materials, copper powder and a mixture of butadiene-acrylonitrile-copolymer and polyvinylchloride were used. After alloying, the powderlike material consisted of a mixture of fine copper powder embedded in the polymer matrix. Milling resulted in a copper powder of particle size 300 nm to 2 μm. The alloyed powders were compacted at a pressure of 0.37 GPa at 90°C with a holding time of 1 minute. The resistivity of the compound was measured to be 8.6 × 10^-4 ohm-cm. The unusual reduction in particle size to the nanometer level and formation of spherically formed copper polymer composite particles is explained by the reactions of the copper atoms with cyano and other functional groups of the polar polymers. The structurally modified polymer forms a tight encapsulation coating on the surface of the copper, and the flat-formed metal particles are recovered in spherical form due to strong interfacial forces, resulting in increased electrical conductivity.     

Mechanical Properties and Thermal Stability of Oxide Eutectic Composites at High Temperatures

New unidirectionally solidified eutectic composites such as Al₂O₃/YAG and Al₂O₃/GdAlO₃(GAP) have been fabricated by unidirectional solidification. The eutectic composites have a microstructure, in which single crystal Al₂O₃ and single crystal complex oxide compounds (YAG or GdAlO₃) are continuously connected and finely entangled in three-dimensions without grain boundaries. The eutectic composites are thermally stable and have the following properties: (1) The flexural strength at room temperature can be maintained almost up to the melting point, (2) In case of Al₂O₃/YAG composite, the compressive flow stress at 1873 K and a strain rate of 10^-4sec is about 13 times higher than that of sintered composites of the same composition, (3) Al₂O₃/YAG composite shows neither weight gain nor grain growth, even upon heating at 1973 K in an air atmosphere for 1000 hours, and (4) The Al₂O₃/GdAIO₃ eutectic composite shows substantial plastic deformation at 1873 K with a flexural yield stress of about 690 MPa, where the plastic deformation occurred by dislocation motion in each phase. Consequently, these composites can be considered for several useful applications such as new aero gas turbines and power generation systems with non-cooled turbine blades at above 1773 K.     

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.     

Characterization of deep levels in high electron mobility transistor by conductance deep level transient spectroscopy

The influence of a substrate voltage on the dc characteristics of an AlGaN/GaN high electron mobility transistor (HEMT) on silicon (111) substrate is profited to investigate traps that are located between the substrate and the two-dimensional electron gas (2DEG) channel. The transient of the drain current after applying a negative substrate voltage is evaluated in the temperature range from 77 to 600 K. With this method, known as Conductance Deep Level Transient Spectroscopy (CDLTS), majority deep levels with activation energy of 61 meV as well as minority carrier traps at 74 meV and capture cross-section respectively 2.56 × 10^− 15 cm², 2.1 × 10^− 15 cm² are identified. Finally, the correlation between the anomalies observed on the output characteristics and defects is discussed.     

Investigation of Iron-Fullerene Mixture Plasmas in ECR Discharge

Fullerene+iron (C₆₀+Fe) mixture plasmas were produced and studied in the ECR ion source of ATOMKI. The two main components of the plasma were obtained by different filament ovens. In this series of measurements we concentrated on the maximum ratio of C₅₈ (damaged fullerene) in the plasma. C₅₈ is less stable than C₆₀ and the probability to form new materials is higher. Using this method we produced molecules of mass M=752 both in single- and double-charged states with beam intensities of 8 · 10^-10A and 2 · 10^-10A, respectively. We identified this beam as a mixture of FeC₅₈, O₂C₆₀ and CO₂C₅₉, while the experiment did not give information on the exact location of the iron and oxygen in the carbon ball.     

The effect of growth temperature on the nanostructure and dielectric response of BaTiO3 ferroelectric films

BaTiO₃ ferroelectric films were grown on Si/SiO₂/Ti/Pt/Au/Pt templates at different temperatures in the range 560-680 °C by pulsed laser deposition. Cross section scanning electron microscopy images and atomic force microscopy surface morphology analysis reveal films with columnar structure and in-plane grain size distribution, in the range 10-60 nm, depending on growth temperature. Low-field dielectric measurements were performed as functions of temperature in the range 40-500 K and external dc field up to 400 kV/cm. The apparent permittivity of ferroelectric films grown at 680 °C shows Curie-Weiss behavior above 400 K with Curie temperature and Curie-Weiss constant 240 K and 1 · 10⁵ K, respectively. The films grown at lower temperatures reveal a decrease of Curie temperature down to − 80 K, reduced values of apparent permittivity and loss tangent, and broadening of maximum of temperature dependence of apparent permittivity. The film grown at 590 °C demonstrates state of the art combination of temperature stability (temperature coefficient of apparent permittivity 300 ppm/K in the range 50-350 K), high tunability of apparent permittivity (up to 60% at room temperature), and relatively low loss tangent (less than 0.05 in the frequency range up to 10 GHz). The change in apparent permittivity and its temperature dependence, with variation of growth temperature are analyzed using two different composite models. The first model assumes the film to be a composite with vertical inclusions of low permittivity dielectric material associated with grain boundaries. This model may explain the observed decrease of permittivity with decreasing growth temperature, but not the shift of Curie temperature. The second model assumes a layered type of composite with low permittivity material associated with the film/electrode interfaces, and allows explanation of the Curie temperature shift.     

Low temperature microwave characterisation of lithium fluoride at different frequencies

Precise knowledge of dielectric properties of materials is required to implement the material in high frequency devices and circuits. At microwave frequencies complex permittivity (dielectric constant and loss tangent) are the two mandatory parameters prior to any design. We have identified Lithium Fluoride as a potential candidate, which can be used in conjunction with superconducting and non-superconducting parts of several microwave communication devices. Even though dielectric constant of LiF is known at room temperature there only limited data presented at cryogenic temperatures. We have used a dielectric post resonator for the microwave characterisation of the rod shaped LiF crystal. In this paper, we have reported the dielectric constant (perpendicular component of the real part of complex permittivity) and loss tangent of two LiF crystals as a function of temperature (15–290 K) at frequencies of 8 and 16.5 GHz. We have also studied and reported the temperature coefficient of frequency and permittivity. The concept of using temperature coefficient of frequency as a standard is proved to be wrong in this paper. Microwave properties of other Fluorides are also compared with the LiF crystal.     

Influence of a Weak Magnetic Field on Photoconductivity Spectrum of C60 Single Crystal

Comparative research of the excitation photoconductivity spectra (quantum light energy 2-5 eV) of C₆₀ single crystal in and out of magnetic field at the temperature T = 250-350 K has been carried. The spectral evolution at this temperature range is described. It is shown that the spectra changes abrupt at temperature T₁ ∼ 260 K and T₂ ∼ 315 K. An increase in the photoconductivity up to 15% was observed in the magnetic field (B = 0.4 T) within the photon energy range 2.5-4.5 eV. Local photoconductivity peak's appearances in the magnetic field have been proven that the charge transfer excitons take part in a photoconductivity.     

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.     

聚苯醚/钙镧钛微波复合基板

微波复合基板兼具树脂基体的高韧性和陶瓷填料优异的介电和热学性能, 是航空航天、电子对抗、5G通讯等领域的关键材料。本工作采用螺杆造粒与注塑成型相结合的新技术制备了聚苯醚(简写为PPO)为基体、钙镧钛(Ca_0.7La_0.2TiO₃, 简写为CLT)陶瓷为填料的新型微波复合基板, 并对基板的显微结构、微波介电性能、热学性能和力学性能进行表征。结果表明, 采用这种新技术制备的微波复合基板组成均匀且结构致密。随着CLT陶瓷的体积分数从0增大至50%, 基板的介电常数从2.65提高到12.81, 介电损耗从3.5×10 ^-3降低至2.0×10 ^-3 (@10GHz); 同时热膨胀系数从7.64×10 ^-5 ℃ ^-1显著降低至1.49×10 ^-5 ℃ ^-1, 热导率从0.19 W·m ^-1·K ^-1提高至0.55 W·m ^-1·K ^-1; 此外抗弯强度从97.9 MPa提高至128.7 MPa。填充体积分数40%CLT陶瓷的复合基板综合性能优异: ε_r=10.27, tanδ=2.0×10 ^-3(@10GHz), α=2.91×10 ^-5 ℃ ^-1, λ=0.47 W·m ^-1·K ^-1, σ_s=128.7 MPa, 在航空航天、电子对抗、5G通讯等领域具有良好的应用前景。