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.     

Effects of crystallinity and supermolecular formations on the interfacial shear strength and adhesion in GF/PP composites

Aim of this study was to screen the morphological effects on the interfacial shear strength (i) in glass fibre (GF) reinforced isotactic polypropylene (iPP) model composites. i was determined by a modified single fibre pull-out technique. It was established that the relation between i (5–6 MPa) and the yield stress of the iPP (y30 MPa) is at about 1:6 and that the i values were not influenced by the mophological superstructure set under isothermal crystallization conditions. Increased i was only observed when specimens were produced non-isothermally, by quenching (i9 MPa). This improvement could not be related to thermal shrinkage stresses. The enhancement in i was attributed to better wetting and improved adhesion due to the enlarged amorphous PP (aPP)-phase. A schematic adhesion model considering the wetting behaviour of aPP and iPP was proposed.     

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.     

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.     

Relationship between preferential adsorption coefficient and intrinsic viscosity in ternary systems

Summary The relation proposed between the preferential adsorption coefficient, , and the intrinsic viscosity, ¦¦ ¦¦=¦¦+AK has been applied in this paper to previously published data. This equation is found to be valid in theta condi tions and far away from them. The obtained results are compared to the ones calculated with the Dondos-Benoit equation.     

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.     

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.     

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.     

Thermophysical and elastomechanical properties of grainy corundum-zircon refractories and the effect of these properties on the thermal-shock resistance

Conclusions The thermophysical properties (l/l ₀ and ) and the elastomechanlcal properties (E, G, _bend) of corundum-zircon specimens in the 20–1200°C interval with various concentrations and grain sizes of zircon and different grain sizes and types of the corundum and zircon components in the grain and bondings have been investigated. It is established that in particular temperature regions there is a connection between the criteria R and R calculated from the values of the properties and the number of heat changes before the onset of primary cracking and total destruction of the specimens.Translated from Ogneupory, No. 1, pp. 56–60, January, 1980.     

Stress and recovery maxima in LDPE melt elongation

Summary By means of a new tensile rheometer for polymer melts, stress-strain curves () and the elastic recovery _R() of a low density polyethylene melt were measured up to total strains =7, i.e. stretch =1097, at 150°C and two strain rates, =0.03 and 0.1 s^–1. Tensile tests up to very high strains e give relevant results only if the test performance is characterized by quality parameters which are defined and given in this paper. The test results show a maximum in a as well as in _R at about =5.5. Hence, in the range of investigated, a rheologically steady-state of flow does not exist.     

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.     

Anionic synthesis of ω-1,1-diphenylethylene-terminated polystyrene macromonomers. Rational synthesis of ABC hetero three-armed-star-branched polymers

Summary Polystyrene macromonomers with terminal 1,1-diphenylethylene functionality were prepared by the reaction of one equivalent of poly(styryl)lithium with 1,4-bis (l-phenylethenyl)benzene (PDDPE). The macromonomer functionalities were determined by ¹H NMR [(vinyl CH₂)=5.4 ppm] and UV spectroscopy (_max=260 nm). The stoichiometric linking reaction of poly(styryl)lithium (M_n=15.3x10³ g/mol) with an -1,1-diphenylethylene-terminated polystyrene macromonomer (M_n=5.4x10³ g/mol) followed by addition of styrene monomer has been used to prepare a hetero three-armed, star-branched polymer with M_n=5.8x10⁴ g/mol (5,400-15,300-37,300). The g value ([]b/[]l) was equal to 0.92.     

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.     

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.     

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.     

The estimation of the residual capacity of sealed lead-acid cells using the impedance technique

The problem of estimating the residual usable energy of a lead-acid cell has been intensified by the introduction of fully sealed units. These rely on the recombination of gaseous oxygen produced during overcharge at the positive electrode with the active material at the negative electrode. This introduction has removed the possibility of electrolyte density measurements, third electrode measurements and restricted residual capacity assessments to the two cell terminals. A method for this process is described using a parameter based on a characteristic frequency. The parameter is also a useful measure of cell ageing.Nomenclature R _SOL Ohmic resistance of cell () - Charge-transfer resistance of positive and negative electrodes () - CL Double-layer capacitance of both positive and negative electrodes (F) - Warburg diffusion (S^–1/2) - C _EXT External series capacitor in analogue Fig. 5 (F) - R _EXT External resistor in parallel withC _EXT in the anologue circuit Fig. 5 () - IND Inductor in Fig. 5 representing the geometrical effects of the cell at high frequencies (Henries) - R _IND External resistor in parallel with IND in the analogue circuit Fig. 5 () - Roughness factor allowing for the porosity of both electrodes     

Changes in optical properties of poly(phenylsilyne) films by photooxidation

We studied the chemical and optical changes in poly(phenylsilyne) films induced by irradiation at >350 nm and >320 nm. An increase in the number of SiOSi and SiOH groups is observed by FTIR measurements after irradiation. The presence of refractive index and relief modulations in these films is reported.     

High-Performance Directional Metallopolyamides. II. Optical Spectroscopic Studies of Metal Chelation

The chelating interaction between metal ions and 4,4-disubstituted-2,2-bipyridyl-containing high-performance polymeric ligands prepared from 2,2-bipyridyl-4,4-dicarboxylic acid and a series of primary aromatic diamines was investigated by optical spectroscopy. Optical spectroscopic studies of the chelation of ruthenium ions by the 2,2-bipyridyl-containing polyamides revealed the formation of distinct ruthenium(II) complexes [Ru^II(poly)L₄] ( _max=530 nm), [Ru^II(poly)₂L₂] ( _max=584 nm), and [Ru^II(poly)₃]²⁺ ( _max=476 nm), while iron(II) ions formed only one complex ( _max=569 nm). The diverse functional features of the polymer repeat unit directly influences the chelation of metal ions.     

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.