Studies on electrical conductivity of gamma irradiated polyaniline

Summary de electrical conductivity at surface of -irradiated polyaniline (PAn) has been studied. EPR spectroscopic results indicate that the variation of spin concentration is consistent with the increase of _de. Electrical conductivity (_de) versus temperature (T) characteristics of unirradiated and irradiated PAn were performed, which demonstrate that the unirradiated curve can fit to ln_deT₁, while the irradiated curve fit to ln_deT_1/4.     

Anisotropy in the strength of cellulosic fibres

Conclusions It is proposed to use the equation of a lemniscate, or the Cassini curve, to determine the destructive stress at break for cellulose films in any direction. Thereupon, to determine , it is necessary to know the destructive stress along two basic directions (₀ and ₉₀).To obtain cellulosic films which are isotropic in plane, a necessary and sufficient condition is ₀=₉₀.Translated from Khimicheskie Volokna, No. 6, pp. 34–35, November–December, 1987.     

Microwave absorption measurements of the electrical conductivity of small particles

A microwave absorption technique based on cavity perturbation theory is shown to be applicable for electrical conductivity measurements of both a small, single-crystal particle and finely divided powder samples when values fall in either the low (<0.1 ^–1 cm^–1) or the intermediate (0.1 100 ^–1 cm^–1) conductivity region. The results here pertain to semiconductors in the latter region. If the skin depth of the material becomes significantly smaller than the sample dimension parallel to theE-field, an appreciable error can be introduced into the calculated conductivity values; however, this discrepancy is eliminated by correcting for the field attenuation associated with the penetration depth of the microwaves. A modification of this approach utilizing the skin depth allows a first-order correction to be applied to powder samples which results in the accurate measurement of absolute values, and results with doped Si powders are compared to values obtained from one small single particle using this microwave technique as well as reported DC values determined with single crystals. The use of this microwave absorption technique with small particles having high surface/volume ratios, such as catalyst supports and oxide catalysts, under controlled environments can provide fundamental information about adsorption and catalytic processes on such semiconductor surfaces. An application to a ZnO powder demonstrates this capability.     

The impedance of the alkaline zinc-manganese dioxide cell. II. An interpretation of the data

The impedance of small alkaline zinc-manganese dioxide cells has been interpreted in terms of a controlling charge-transfer and diffusion process at the zinc electrode throughout the early stages of discharge. After about 20% of the available charge has been removed, it becomes necessary to include the manganese dioxide electrode circuit components. This network has the circuit elements for charge transfer and a proceeding chemical reaction. The Warburg component for the manganese dioxide electrode need not be considered since the effective area considerably exceeds that of the zinc. The relative areas are confirmed by the magnitudes of the circuit element components. The decomposition of the impedance data has been successfully accomplished as far as 80% discharge; after this point cells show considerable differences from cell to cell, especially in the low-frequency range, which makes a confident interpretation difficult. It is considered that this is due to the loss of the physical definition of the system.Nomenclature C _m,C _z double-layer capacitances of MnO₂ and Zn electrodes, respectively - C _X,R _X parallel branch accounting for current density varying with fractional electrode coverage - R resistance of electrolyte - V open-circuit voltage of cell - Z, Z, Z impedance of cell,resistive component ofZ and reactive component ofZ, respectively - _m, _z transfer resistance of MnO₂ and Zn electrodes, respectively - , _R, _C in Warburg equation:Z _W = ^–1/2(1–i) orZ _W = _R^–1/2– i_Cco^–1/2     

Electrical Properties and the Structure of Halogen-Containing Lead Borate Glasses: I. The PbF2–2PbO · B2O3 System

The concentration and temperature dependences of the dc electrical conductivity of glasses in the PbF₂–2PbO · B₂O₃ system is investigated. It is found that, at 20–25 mol % PbF₂, the dependences log = f([F]) and E = f([F]) exhibit kinks. The concentration dependence of the true transport number of fluorine ions _F – is studied using the Tubandt method. It is shown that the introduction of 20–25 mol % PbF₂ leads to a crossover from the protonic conductivity to the unipolar fluorine ionic conductivity ( ). The results obtained are discussed in terms of the Myuller theory of the microinhomogeneous glass structure associated with the selective interaction of the components during the synthesis.     

Thermal Conductivity of a Glass: I. Measurement by the Glass–Metal Contact

The thermal (phonon) conductivity of glass has been measured by contacting the sample with a metal at a different uniform initial temperature. The subsequent temperature response in the metal is measured by a tiny thermocouple just underneath the (contact) surface. The coefficient of heat penetration c _p follows directly from the fitted asymptotic temperature jump or drop for long times. Division by the separately measured heat capacity c _p yields the thermal conductivity . The conductivity measurement reproducibility was = 3%. The standard deviation between validation measurements and round robin test results on Pyrex glass was = 5.8%, somewhat more than the accuracy = 5.2% of the round robin test results. The measurement method is insensible for slight imperfections of the thermal contact and infrared radiation diffusion (photon conductivity) in a hot glass. The method has been used with minor modifications for solid and molten samples at temperatures of 50–850°C and conductivities of 0.1–25 W/(m K). The thermal (phonon) conductivity of the investigated soda-lime silicate glasses increases slightly (27–30%) with temperature from ambient up to around the glass transition.     

Electrical Properties and the Structure of Halogen-Containing Lead Borate Glasses: II. The PbF2–PbO · B2O3 System

The temperature and concentration dependences of the dc electrical conductivity of glasses in the PbF₂–PbO · B₂O₃ system are investigated. It is found that the dependences log = f([PbF₂]) and E = f([PbF₂]) for glasses containing 20 and 35 mol % PbF₂ exhibit kinks, which are interpreted from the standpoint of the microinhomogeneous structure associated with the selective interaction of the components during the synthesis of glasses. Analysis of the transport numbers has revealed that the unipolar fluorine ionic conductivity is observed upon introduction of more than 35 mol % PbF₂. It is shown that, in the concentration range from 0 to 35 mol % PbF₂, the electric current is provided by both protons and fluorine ions.     

On the Charge Carrier Concentration in Sodium–Calcium Aluminophosphate Glasses

The dc and ac conductivities of the xNa₂O–(35 – x)CaO–7.5Al₂O₃–57.5P₂O₅glasses (mol %) with x= 0–35 are studied in the frequency range from 20 Hz to 1 MHz at different temperatures. It is found that the dc conductivity strongly depends on xonly for glasses with x 10. For glasses with x 5, the dc conductivity is virtually composition independent. The dependence of the ac conductivity plotted on the log(()/_dc) vs. log(/_dc) coordinates is analyzed. The ac conductivity represented in these coordinates depends on xonly for glasses with x 5, in which the dc conductivity does not depend on x. For glasses with xin the range from 10 to 35, all the isotherms of the ac conductivity closely coincide with each other. This result is discussed in the framework of two hypotheses: (1) the conductivity () is determined by the dynamic polarization (of the Maxwell–Wagner type at low frequencies) of the material due to spatial fluctuations of the density of paths providing the migration of sodium ions and (2) the concentration of charge carriers is independent of x.     

AC Conductivity of Porous Silicon from Monte Carlo Simulations

The AC conductivity of a percolation model with local energetical disorder for porous Silicon in three dimensions, (), is studied by Monte Carlo simulations. The model includes both diffusion and recombination processes and () is obtained by a Fourier transform of the mean-square displacement of the carriers, where hopping diffusion of a single type of carrier (either an electron or an exciton) and two types of carriers (an electron and a hole) are considered. It is found that at low temperatures, the behavior of () depends sensitively on the type of carrier considered.     

Microcalorimetric, infrared spectroscopic and DFT studies of ethylene adsorption on Ru, Ru/Sn and Ru/Cu catalysts

Microcalorimetric measurements of the adsorption of H₂, CO and C₂H₄ were conducted on silica-supported Ru, Ru/Sn, Ru/Cu and Cu catalysts; infrared spectroscopic measurements were made of adsorbed CO and C₂H₄. The adsorption of C₂H₄ leads to formation of di--adsorbed ethylene and ethylidyne species on Ru/SiO₂ at 300 K, with an initial heat of 160 kJ/mol. Ethylene adsorption at 203 K leads to the formation of di--adsorbed ethylene, ethylidyne species and weakly adsorbed -bonded ethylene. The initial heats are 110, 95 and 75 kJ/mol on Ru/SiO₂, 5Ru/Sn/SiO₂ and Ru/Cu/SiO₂, respectively. Lower heats of CO and C₂H₄ adsorption are measured on Ru/Cu/SiO₂, primarily as a result of these adsorbates binding on both Cu and Ru. Quantum chemical calculations employing density functional theory were performed using (0001) slabs of Ru and Ru/Sn. The results of these calculations indicate that Sn weakens the interaction of -bonded ethylene, di--bonded ethylene and ethylidyne species with Ru by 41, 23 and 15 kJ/mol, respectively. This behavior is in contrast to the effect of adding Sn to Pt and Pd, for which Sn preferentially weakens the bonding of ethylidyne species to the surface.     

Role of structure and capacity for energy absorption in increasing the strength and crack resistance of refractory ceramics

Conclusions We identified the influence of the parameters of a heterogeneous structure and also of particles possessing the capacity to absorb energy of deformation on the strength _rup and the crack resistance K_lc of refractory ceramics. The proposed relationships facilitate quantitative evaluation of the influence of these factors and indicate ways of increasing the levels of _rup and K_lc. Comparison of the calculated and experimental values of _rup and K_lc obtained from tests of various types of ceramics indicate the suitability of the equations for assessing the characteristics of strength and crack resistance.Translated from Ogneupory, No. 7, pp. 8–13, July, 1987.     

Influence of static and cyclic compression on the electrical conductivity of FEF black-loaded rubbers

Summary The influence of static and cyclic compression on the temperature dependence of the electrical conductivity (T) of 100 phr FEF black-loaded rubber vulcanizates (SBR, NR, IIR, BR and NBR) has been studied. It was found that increases with static pressure for all rubber vulcanizates. The temperature coefficient of conductivity proved to be negative; its maximum value ranges between –0.1 and –0.01 deg^–1 depending upon the applied stress and type of rubber vulcanizate. The pressure coefficient of conductivity at room temperature varies with the static pressure from 0.78 to 0.04 (kg/cm²)^–1. Menwhile, a was found to decrease with the number and stress amplitude of the cyclic compressions, while increases with the number of compression cycles.     

On the nature of the ‘induction period’ during the electrowinning of zinc from nickel containing sulphate electrolytes

As a result of detailed voltammetric, impedance, electron microscopic and opticalin situ investigations of the peculiarities encountered in zinc electrowinning from nickel-containing acid electrolytes, a model for the induction period is proposed and its dependence on the process conditions is elucidated. The model is based on the screening effect of hydrogen bubbles formed on the nickel-rich regions of the cathode which give rise to local galvanic cells.Nomenclature C electrode capacitance - C _dl double layer capacitance - C _Ni volume concentration of Ni²⁺ ions - d diameter of the circle along which the hydrogen bubble is attached to the surface - D _Ni diffusion coefficient of Ni²⁺ ion - E _ze potential of zero charge - f ^* frequency at the apex of the capacitance loop - F Faraday constant - F _c capillary force - F _h hydrostatic force - g acceleration due to gravity - q specific mass of the liquid - h height of the hydrogen bubble - R electrolyte resistance - R _t charge transfer resistance - V volume of the gas phase - thickness of the diffusion layer - wetting angle at the metal-solution-gas interface - ₁₂, ₂₃, ₁₃ surface tensions between: solid-liquid, liquid-gas and solid-gas phases, respectively - kinematic viscosity - rotation speed of the cathode The first results were presented at the International Conference on Base Metals Technology, 8–10 February, 1989, Jamshedpur, India.     

Electrical conductivity of praseodymia doped ceria

The electrical conductivity () and oxide ion transference number (t ₀) of praseodymia doped ceria systems were measured. The former increased rapidly with the praseodymia content, while the latter decreased. At 600° C, for instance, CeO₂ and Ce_0.6Pr_0.4O₂ under 0.21 atm of oxygen were 2.0×10^–5 and 3.6×10^–2 S cm^–1; andt ₀ in them were 0.59 and 0.11, respectively. This mixed conductor having high electrical conductivity might be useful as a fuel cell electrode if it could be combined with a suitable solid electrolyte.     

Crack resistance of corundum refractories over a wide range of temperatures

Conclusions The ultimate bend strength _bnd and the critical stress intensity factor K_lc of a group of corundum refractories were determined over a wide range of temperatures. It was shown that the temperature dependences of _bnd and K_lc have a similar nature. In the refractories having the usual porous structure, the rate of decrease of K_lc with increasing temperature is less than that of _bnd. Owing to this, the coefficient of crack resistance K_t of the refractories increases at high temperatures.The refractories having a porous-fissured structure, exhibit an almost identical reduction of _bnd and K_lc with increasing temperature and the magnitude of K_t increases very insignificantly.Translated from Ogneupory, No. 3, pp. 8–11, March, 1987.     

Determination of the cooperativity parameter σ from viscometric data of poly-L-glutamic acid-Na

Summary Viscometry of PLGNa solutions was performed for various degrees of neutralization . The cooperativity parameter in the helix-coil transition was estimated using Ptitsyn's method with some modifications. The increase of thus obtained with decreasing is explained in terms of the a dependence of short-range interactions of PLGNa segments.     

Phenomenological model of the scale effect of the strength of polymer fibers

A new derivation of the scale effect equation for polymer fibers is proposed. The equation is: AL ^–, where is the average strength of the fiber; L is the length of the fiber; A and are coefficients. The equation was obtained from the general premises of scale effect theory without indication of the concrete form of the probability function F(S).Ukrainian Scientific-Research Institute of Polymer Fibers, Kiev. Translated from Khimicheskie Volokna, No. 4, pp. 34–36, July–August, 1992.     

Adsorption of carbon monoxide on Ni/Ti and Ni/TiO2 surfaces preparedin situ in the electron spectrometer: A combined UPS-XPS study

Adsorption of CO on a clean Ti surface is partly associative at 80 K with a 1 -4 separation of 4.2 eV, becoming dissociative at 130 K. On Ni- covered Ti surfaces, however, associative adsorption (4-1, 3.3 eV) occurs at 80 K and partial dissociation, around 200 K. TiO₂ is reduced more effectively on annealing, when it is covered with Ni. On the surfaces of Ni deposited on TiO₂, there is only dissociative adsorption, unlike on Ni/Al₂O₃ and Ni/TiO₂ (non-annealed) surfaces.Contribution No. 565 from the Solid State and Structural Chemistry Unit.     

Solutions of the general equations for the radiation dose dependence of the molecular weights of irradiated polymers with an initial Schulz-Zimm distribution

Summary The general equations for the radiation dose dependence of irradiated polymer molecular weights have been solved exactly. For an initial most probable molecular weight distribution (=1), the solutions are analytical and exact. For the general case (1) the solutions are numerical and exact. The present approach has resulted in the solutions for both =1 and 1 being incorporated into a group of FORTRAN computer programs which will solve experimental data for scission and crosslinking yields by both minimization and exact treatments. Simulated data treated using these FORTRAN programs are give. The FORTRAN programs are available from the authors.     

The impedance of the alkaline zinc-mercuric oxide cell. I. Cell behaviour and interpretation of impedance spectra

The impedances of small (2400 mA h) alkaline Zn-HgO cells have been measured in the range 10 kHz-0.001 Hz at various states of charge from fully charged to fully discharged. The behaviour of the cell conforms to that expected for rate control by charge transfer at the zinc electrode and diffusion in solution. At low frequencies there is a relaxation in the diffusive circuit elements which ultimately results in a complete suppression of the capacitative component of the impedance at zero frequency. The low-frequency behaviour is analogous to convective diffusion and is due to the effective distance between the electrodes being small compared with the characteristic length (D/)^1/2. The magnitude of the charge transfer resistance is the best measure of the state of charge.Nomenclature a effective electrode separation - C _DL double-layer capacitance of cell - C _R capacitative component of cell impedance - C concentration difference - D percentage discharge in Equation 12 - D _i diffusion coefficient of speciesi - R ohmic resistance of cell - R _R resistive component of cell Faradaic impedance - Ui constant defined by Equation 10 - Z total cell impedance - Z _F cell Faradaic impedance - Z _F cell impedance modified for porosity effect - Z _x cell impedance of Faradaic component plus double layer - cell Warburg coefficient (slope ofR _R and 1/C _Rversus su}-1/2) - _C Warburg coefficient calculated fromC _r values - _i cell Warburg coefficient for speciesi - Warburg coefficient calculated fromR _R values - dihedral angle of tail of Sluyters plot (after coming-off high-frequency semicircle) - angular frequency