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.     

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.     

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.     

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.     

Prospects for strengthening fibres and films

Conclusions A model of the orientation strengthening of polymers which is based on the concept of the existence of a network of nodes which rearrange during the stretching process has been used to calculate the limiting values of degree of stretch, , and the strength, , of fibres of polyethylene, polycaproamide, polyvinyl alcohol, polypropylene, polyacrylonitrile, and poly-p-phenyleneterephthalamide.According to calculation, increasing the molecular weight of the polymer and decreasing the concentration of the solution being spun should lead to an increase in and ; for Terlon with a molecular weight of about 250,000, =100 and =10 GPa.Translated from Khimicheskie Volokna, No. 5, pp. 33–34, September–October, 1983.     

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.     

Surface characterization of zirconium titanate (ZrTiO4) powder by measurements of electrical photoconductance and photoassisted oxygen isotope exchange

The photosensitivity of a ZrTiO₄ sample (33 m²/g) prepared by a sol-gel method has been assessed in the presence of O₂ by both photoconductance and oxygen isotope exchange (OIE) measurements at room temperature at wavelengths > 290 nm. For oxygen pressures < ca. 13.3 Pa, the steady-state photoconductance of ZrTiO₄ was unaffected by , which indicated that the direct recombination of the photoproduced charges played the dominant role. At higher pressures, varied as the reciprocal of , which was consistent with the fact that the electronic equilibrium was then governed by O₂ + e^– O ₂ ^– . OIE over ZrTiO₄ occurred predominantly via the overall mechanism which involves the exchange of two surface oxygen atoms for each exchange act. It was very slow as compared with OIE over photocatalytically active anatase samples which, in addition, occurs via another mechanism. These results allow one to predict that this ZrTiO₄ sample is a poorly active photocatalyst for oxidations involving gaseous oxygen, and further illustrate the interest of and OIE measurements to evaluate the photosensitivity of semiconductor oxide samples.     

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     

Microcalorimetric, reaction kinetics and DFT studies of Pt–Zn/X-zeolite for isobutane dehydrogenation

Microcalorimetric measurements of the adsorption of H₂ and C₂H₄ were carried out at 300 K on a Pt–Zn/X-zeolite catalyst (Pt:Zn atomic ratio equal to 1:1). The initial heats of H₂ and C₂H₄ adsorption were equal to 75 and 122 kJ/mol, respectively, and these values are weaker than the values of 90 and 155 kJ/mol typically observed for supported Pt catalysts. Reaction kinetics measurements for isobutane dehydrogenation over the Pt–Zn/X-zeolite catalyst were carried out at temperatures from 673 to 773 K, at isobutane pressures from 0.01 to 0.04 atm, and at hydrogen pressures from 0.1 to 0.7 atm. The catalyst shows high activity and selectivity for dehydrogenation of isobutane to isobutylene. The reaction kinetics can be described with a Horiuti–Polanyi reaction scheme. DFT calculations were carried out for the adsorption of ethylene on slabs of Pt(111), Pt₃Zn(111) and PtZn(011). Results from these calculations indicate that addition of Zn to Pt weakens the binding energies of -bonded ethylene, di--bonded ethylene, and ethylidyne species on atop, bridged, and three-fold Pt sites, respectively. These effects are most significant for the bonding of ethylidyne species, and they are least significant for -bonded ethylene species. Results from DFT calculations for the adsorption of formaldehyde show that addition of Zn to Pt weakens the di--bonding at Pt–Pt sites; however, this weakening effect of Zn on formaldehyde adsorption is less significant than the effect on ethylene adsorption. Moreover, the preferred location for adsorption of formaldehyde on PtZn(011) is a Pt–Zn site, whereas the preferred location for adsorption of ethylene is a Pt–Pt site. Thus, formaldehyde is adsorbed more strongly by 53 kJ/mol on PtZn(011) compared to the di--adsorption of ethylene, whereas formaldehyde and ethylene adsorb in the di--forms with comparable energies on Pt(111). This preferred adsorption of formaldehyde compared to ethylene on PtZn(011) may be at least partially responsible for the enhanced selectivity of Pt–Zn-based catalysts for hydrogenation of C=O groups compared to C=C bonds in ,-unsaturated aldehydes.     

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.     

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.     

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     

Fundamentals of lead-acid cells. XVII. The a.c. impedance of lead dioxide formed in sulphuric acid on some lead alloys

The impedances of PbO₂ formed on lead and some lead alloys have been measured over a wide range of potential. Conditions were chosen so that well-defined electrode states were obtained. Considerable differences were observed in the behaviour of alloys containing antimony and bismuth. The latter alloying ingredient appears to contribute some semiconducting properties to lead sulphate films formed on PbO₂ by polarizing them at potentials negative to the reversible potential in sulphuric acid.Nomenclature C _L double-layer capacitance - C _X series capacitance - D diffusion coefficient - E potential - R _CT charge-transfer resistance - R electrolyte resistance - Z _D impedance as defined by Equation 1 - Z _F impedance as defined by Equation 2 - Z impedance as defined by Equation 3 - Warburg coefficient - angular frequency     

The application of Taft-Hancock steric constants to the free-radical initiated copolymerization of N-alkylmaleimides with α-methylstyrene

Summary The rates of free-radical initiated alternating copolymerization of -methylstyrene with N-alkylmaleimides (RMI) decrease in the following order: Me>Et>n-Prn-Bun-Hex>iso-Pr>tert-Bu. A linear relationship was established in the plots of log(k_R/k_Me) against polar substituent constants ^*, true steric factors E_S and corrected steric factors E_S ^C. The best fit was obtained in plots of log (k_R/k_Me) against ^* and E_S ^C while a large scattering of results was observed in the plot of log(k_R/k_Me) against E_S.     

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.     

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.     

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.     

A model for peak and width of signaling windows: Ips duplicatus and Chilo partellus pheromone component proportions--does response have a wider window than production?

Pheromone communication systems have a reliable signal with a restricted window of amounts and ratios released and perceived. We propose a model based on a Gaussian response profile that allows a quantification of the response peak (location of optimum) and a measure of the peak width (response window). Interpreting the Gaussian curve, fitted by nonlinear regression (NLR), as a standard normal distribution, the peak location equals the mean () and the window width equals 2× the standard deviation (2). The NLR procedure can provide an objective measure for both peak location and width for a wide range of data sets. Four empirical data sets as well as 10 literature data sets were analyzed. The double-spined spruce engraver, Ips duplicatus, was field tested in four populations to find the optimum proportion for attraction to the two male aggregation pheromone components, ipsdienol (Id) and (E)-myrcenol (EM), ranging from 0 to 100% of Id. Tests in Norway and the Czech Republic confirmed the preference of western populations for a blend between 50 and 90% Id. A population in Inner Mongolia showed a preference for traps with the 10 and 50% Id baits. The NLR fitted values for response peak and width (; 2) were: Norway 0.64, 0.73; Czech Republic 0.53, 0.73; NE China 0.77, 0.29; and Inner Mongolia 0.33, 0.50. The signal produced by Norwegian field-collected males had a narrower window width (2 = 0.12). Males of the maize stem borer, Chilo partellus, were tested in a flight tunnel for their response to variation in the two major female sex pheromone gland components, (Z)-11-hexadecenal and the corresponding alcohol (OH). Variation of the alcohol in seven levels from 2 to 29% OH showed the highest male response for 17% OH. For all behavioral steps, the peak of male response was near = 0.14, while the window width fell from 2 = 0.5 to 0.2 for eight sequential behavioral steps from take-off to copulation. Female production had a similar peak location ( = 0.13) but a narrower width, 2 = 0.14. Literature data from other moth species showed similar patterns, with a wider male response relative to the female production windows. Literature data on response to enantiomer ratios in a hymenopteran and to pheromone amounts in a dipteran were also described by our model. In a bark beetle population (Ips pini), with two hybridizing enantiomeric strains, the production peaks were narrower (0.1) than the response peaks (0.5). Thus, it in general, seems that in the pheromone systems analyzed, the width of the response window (2 = 0.1 to 0.8) is larger than that of the production window (2 = 0.03 to 0.14), irrespective of the sex of the sender.     

Influence of certain additions on the strength of dinas parts

Conclusions The addition of TiO₂ and S to the quartzite base makes it possible to increase the strength of dinas parts while the addition of Al₂O₃ and MgO decreases it.The maximum value of _comp, calculated using Eq. (6), is obtained at the boundary of the investigated area with an addition content of 1.5% TiO₂ and 0.5% S and is 75.9 MPa. From the results of a control test at this point _comp=77.1 MPa. The value of _comp for parts of a quartzite mixture with a lime-iron mixture without the additions was 51.2 MPa in tests and 60.6 MPa calculated using Eq. (4).A production lot of coke dinas parts with additions of Portland cement and TiO₂ was produced. The compressive strength of the parts was 80 MPa.Translated from Ogneupory, No. 5, pp. 7–9, May, 1984.