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.     

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.     

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     

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.     

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.     

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.     

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.     

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.     

An assessment of soil tests for phosphate for the prediction of cereal yields on a sandy soil in Western Australia

Nine soil tests for phosphate were evaluated for predicting the yield and P content of wheat, barley and oats grown on a sandy soil in Western Australia: Olsen, modified Olsen 1 (soil:solution ratio 1:5), modified Olsen 2 (soil:solution ratio 1:50), Colwell, Bray 1, Bray 2, modified Bray 2T (shaking time 10 minutes), modified Bray 2C (pH 3.7) and lactate. The soil had been fertilized 5 years previously with 20 levels each of superphosphate (OSP, range 0 to 400 kg P ha^–1) and Queensland rock phosphate (QRP, range 0 to 20 000 kg P ha^–1). For each species and fertilizer taken separately, all the tests, except for lactate, gave a good prediction of yield. When data for OSP and QRP were pooled, Bray 2 and modified Bray 2T tests were unsatisfactory predictors of both yield and P content.A linear relationship (P < 0.05) between mean soil tests value () and the standard deviation ( ) of the test value was observed for each soil test. For QRP, the results for lactate were the most variable (i.e./ was greatest) followed by modified Olsen 2 > Bray 1 > Bray 2 > Olsen > modified Bray 2C > modified Olsen 1 > modified Bray 2T > Colwell. The order for OSP fertilized soil was Bray 1 > modified Bray 2T > Bray 2 > Olsen > Colwell > modified Bray 2C > modified Olsen 1 > lactate > modified Olsen 2. For combined OSP and QRP data, the results of the Olsen 1 and Colwell extractions were the least variable.Errors in the prediction of yield ( _Y ) for all crops resulting from an error in soil test values () were calculated. For OSP-fertilized soil variability in values for the Bray-1 test provided the highest error (about 16%) in the prediction of the yield, followed by Bray 2 (12%) > Bray 2T (10%) > Olsen (8%) > Colwell (7%) > modified Bray 2C (6%) > lactate (4%). Maximum error was at yields of about 65% of maximum yield. For soil fertilized with QRP, lactate provided the highest error (about 10%) in the prediction of yield, followed by the other tests (< 6%). Maximum error was at yields of about 35% of maximum yield.The Colwell soil test gave the most accurate overall prediction of yield for both fertilizers.     

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.     

Cryochemical Synthesis of Mn-Containing Poly(p-Xylylene)

A Mn-containing polymer was produced by solid-state photopolymerization of a cocondensated mixture of p-xylylene with Mn at 80 K. It was shown that during simultaneous deposition p-xylylene and Mn formed both - and -complexes. Irradiation of the system by UV light resulted in polymerization of p-xylylene with the destruction of the unstable -complexes, while the -bonded compounds were incorporated into the polymer chains. Complexes of Mn with benzyl-type radicals of the polymerized system were also observed. Prolonged storage of the polymerized material at ambient temperature under vacuum led to the gradual decomposition of the organomanganese compounds and complexes.     

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.     

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.     

Sex pheromone chemistry of the western spruce budwormChoristoneura occidentalis Free

SCOT capillary Chromatographic and SCOT capillary chromatographic-mass spectrometic analyses of gland washes and effluvia of virgin femaleChoristoneura occidentalis Free, have been conducted with both a diapausing and nondiapausing strain of this insect. The following compounds were identified in gland washes and effluvia in both strains:E andZ11–14Ald,E andZ11–14Ac,E andZ11–14OH and 14Ald, 14Ac, and 14OH. The average aldehyde: acetate: alcohol ratio found by analysis of single glands by virgin females (nondiapausing strain) was 170.73. Analysis of virgin female effluvia gave this ratio as 1038 (diapausing strain: %Z=8, 11, 15, respectively) and 1036 (nondiapausing strain: %Z=8, 11, 12, respectively). The saturated components were generally 1–2% of theE isomer in each case. Comparisons of EAG responses of bothC. occidentalis andC. fumiferana toE11–14Ald,E11–14Ac andE11–14OH were made. Correlations with both laboratory and field data previously published were also made betweenC. fumiferana andC. occidentalis.Lepidoptera: Tortricidae.     

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.     

Electrical conductance of some cellulose derivatives

Summary The interrelation between the electrical conductance, and some chemically modified cellulose molecule produced through partial substitution of the hydroxyl groups by different groups namely, acetate, methoxyl, carboxymethyl and sodium carboxymethyl has been studied in the temperature ranges 283–333 k. The results show that of the examined samples change in the descending order: sodium carboxymethyl cellulose >carboxymethyl cellulose >methyl cellulose>cotton cellulose>cellulose acetate. The variable response of to the chemical modification and the physical changes of cellulose accompanying such modification has been discussed in terms of the molecular structure, chain flexibility and degree of polymerization of the examined samples.     

Investigation of sex pheromone components of female asian corn borer,Ostrinia furnacalis (Hübner) (Lepidoptera: Pyralidae) in Taiwan

(E)-12-Tetradecenyl acetate (E12–14OAc), (Z)-12-tetradecenyl acetate (Z12–143nOAc), and tetradecanyl acetate (14OAc) were extracted and identified as major chemical components from female tips of the Asian corn borer,Ostrinia furnacalis (Hübner) (Lepidoptera: Pyralidae) in Taiwan, with a combined wash ratio of 483715 and an individual female ratio of 453916. The average amount ofE12-,Z12–14OAc and 14OAc in each female gland was 6.6±4.6, 5.8±3.5, and 2.4±1.7 ng/female, respectively. The mixture of these three synthetic chemicals not only gave strong activities in male antennae but also could catch significantly more males than virgin females in field-trapping tests. The field test also showed no significant difference in trapping ability among the three-component Taiwan formulations, the two-component Taiwan formulation (Z12–14OAc andZ1214OAc, 5347), and the Japan formulation (Z12–14 OAc andE 12–14OAc, 3:2).     

A four-component pheromone blend for optimum attraction of redbacked cutworm males,Euxoa ochrogaster (Guenée)

Four acetates,Z-5-decenyl acetate,Z-5-,Z-7-, andZ-9-dodecenyl acetates, in microgram ratios of 120021 or 120062 were excellent, specific sex pheromone blends for capturing male redbacked cutworm moths in cone traps. Blends in ratios of 120021 and 220021 at 1000 g/ rubber septum dispenser remained highly effective for 6 weeks under field conditions. The essential minor components,Z-5-decenyl,Z-7-, andZ-9-dodecenyl acetates, became inhibitory at concentrations of about 10% in the blends, and this may be an important general phenomenon in lepidopteran pheromones. Blends involving a parapheromone,Z-5-undecenyl acetate, withZ-5-,Z-7-, andZ-9-dodecenyl acetate, in microgram ratios of 820021 or 2020062 were also excellent specific attractants for this species. TheZ-8-dodecenyl acetate had no obvious effect on the attraction of the redbacked cutworm males.     

The electrochemical quartz crystal microbalance as a sensor in the gold thiosulfate leaching process

A technique was developed for measuring the thiosulfate concentration in gold thiosulfate leaching solutions containing copper and ammonia. The method, which is based on the relationship between thiosulfate concentration and the oxidation rate of silver, was firstly studied using the rotating electrochemical quartz crystal microbalance (REQCM). It was found that the measured silver oxidation rate is directly related to the thiosulfate concentration. The silver oxidation rate was also shown to be unaffected by the presence of other species likely to be found in gold leach solutions. The technique was then evaluated for use as a method of flow injection analysis, utilizing a flow through electrochemical quartz crystal microbalance (EQCM) cell.     

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.