Frequency-temperature curve of the complex dielectric constant and refractive index of water

Using a cluster-gyroscopic model of liquid water, the position of the natural frequency of rotation of dipoles of water at a given temperature in the Debye 0.15–600 frequency spectrum of external polarizing electromagnetic radiation at a temperature from 0 to 100‡C was substantiated. Inversion of the temperature curve of the absorption factor has a right-hand spiral when the frequency of the radiation is changed. In the 52.5–60.3 GHz frequency range, there is a very small change in the absorption factor in the 0–100‡C temperature range. The values of the radius vector of the diagrams of ε″(ε′) and k(n) decrease with a decrease in the amount of free water and an increase in the ion charge density at constant temperature. Translated from Khimicheskie Volokna, No. 6, pp. 25–30, November–December, 1997.     

Effect of molecular mobility on the deformation characteristics of polycaproamide fibres

The deformation characteristics of PCA fibres are a function of the deformation temperature to a significant degree. The character of the curves of E(ε), E_max(t), σ_b(t), and ε_b(t) indicate a pronounced change in the mechanical properties of PCA fibres not only in “thawing” of segmental mobility in amorphous regions of the polymer, but also in passage of crystallites into the mesomorphic state, which is characterized by pronounced weakening of interchain interactions in the crystallites. The first segment of σ(ε) is only observed in the curves for PCA fibres in the glassy state. In activation of segmental mobility, the σ(ε) curves only contain the second and third segments. St. Petersburg State University of Technology and Design. Translated fromKhimicheskie Volokna, No. 6, pp. 30–31, November–December, 1999.     

Effect of the temperature on the structure and mechanical properties of poly(ethylene terephthalate) fibres and yarns

The load—elongation diagrams were obtained for PETP yarns and monofilaments at different deformation temperatures, demonstrating the dependence of the σ(ε) curves on the testing temperature and the thermomechanical history of the samples. The dependences of the basic strain characteristics determined from the σ(ε) curves on the temperature can be used to predict the change in the mechanical properties of PETP yarns and fibres at high temperatures. In addition to the fundamental relaxation transition, the σ(ε) curves can be used to find a new transition in the 180°C region which controls the behavior of PETP yarns and fibres above the transition temperature. The thermomechanical tests and structural studies of the fibres at different temperatures allow correlating the transition found with crystallites and assigning it to an α_c transition based on the characteristic set of properties. St. Petersburg State University of Technology and Design. Translated fromKhimicheskie Volokna, No. 1, pp. 32–35, January–February, 2000.     

Increased generation of electricity in a microbial fuel cell using <Emphasis Type="Italic">Geobacter sulfurreducens</Emphasis>

The microbial fuel cell (MFC) has attracted research attention as a biotechnology capable of converting hydrocarbon into electricity production by using metal reducing bacteria as a biocatalyst. Electricity generation using a microbial fuel cell (MFC) was investigated with acetate as the fuel and Geobacter sulfurreducens as the biocatalyst on the anode electrode. Stable current production of 0.20–0.24 mA was obtained at 30–32 °C. The maximum power density of 418–470 mW/m², obtained at an external resistor of 1,000 Ω, was increased over 2-fold (from 418 to 866 mW/m²) as the Pt loading on the cathode electrode was increased from 0.5 to 3.0 mg Pt/cm². The optimal batch mode temperature was between 30 and 32 °C with a maximum power density of 418–470 mW/m². The optimal temperature and Pt loading for MFC were determined in this study. Our results demonstrate that the cathode reaction related through the Pt loading on the cathode electrode is a bottleneck for the MFC’s performance.     

Change in the structural state of grain boundaries under high-rate mechanical loading

The molecular-dynamic modeling of the behavior of a three-dimensional crystallite that contains a specific-type grain boundary under shear loading is performed. It is found that the accommodation of displacements of the material grains can be realized owing to structural changes in the intergrain boundaries. The crystal-like structure of the grains can be restored after the external action terminates. The results obtained give deeper insight into the nature of the structural response of the material under mechanical loading at the atomic level. Translated fromFizika Goreniya i Vzryva, Vol. 35, No. 6, pp. 112–114, November–December 1999.     

Electrodeposition and corrosion behaviour of a Ni–W–B amorphous alloy

Electrodeposition of Ni–W–B alloys from plating baths containing ammonia and citrate is reported. Optimum conditions for plating including current density, temperature, mechanical agitation and pH were studied. The corrosion resistance and amorphous character were also evaluated. The operational conditions for depositing the alloy with good corrosion resistance were: current density 35 mA cm⁻², bath temperature 40 °C, pH 9.0 and cathode rotation at 90 rpm. The alloy was deposited at 38% current efficiency, with an average composition of 73 wt% Ni, 27 wt% W and traces of boron and with E _corr −0.300 V and R _p 3.369×10⁴ Ω. The deposit obtained under these conditions had an amorphous character with the presence of some microcracks on its surface reaching down to the copper substrate. Electrochemical corrosion tests verified that the Ni–W–B alloy had better corrosion resistance than Co–W–B.     

Novel triazole-based aluminum complex for ring-opening polymerization of lactones

Novel triazole-based aluminum complex {O,O′-[4,5-P(O)Ph₂tz]-AlMe₂ was studied as the catalyst for the ring-opening polymerization of caprolactone (ε-CL) in chlorobenzene. In the presence of methanol, isopropanol, and bifunctional poly(ethylene glycol), the catalytic system produced polymers with high conversion (81–85 %) but broader distribution (M _w/M _n = 1.5–1.8). The system of catalyst and benzyl alcohol produced relative monodisperse PCLs (M _w/M _n ~ 1.2) with defined molecular weight at 1/1ratio, 60 °C and an initial concentration of ε-CL equal to 0.5 mol/L.     

Prediction of the effective diffusion coefficient in random porous media using the finite element method

A finite-element-based method is presented for evaluating the effective gas diffusion coefficient of porous solids. Using this method, the 3-D micro-scale geometries of the porous solids are constructed under the ANSYS platform by the parametric code; the relation between effective gas diffusivity and micro-scale features of random-distributed porous solids is established. The results show that in random-distributed pore media, there is a percolation threshold ε _p, and this percolation threshold decreases with increasing coordination number of the pore network. The relationship between the effective diffusivity and porosity is strongly nonlinear when the porosity, ε, is less than a certain value ε _L ; for ε > ε _L , the relationship becomes quasi-linear. This dividing point ε _L decreases with increasing coordination number. The larger the coordination number of the pore network, the higher the effective gas diffusivity. Based on the simulation results and observations, a formula relating the effective diffusion coefficient with porosity is proposed.     

Specific features of the nanoscopic spalling fracture near the grain boundary

The spalling fracture in a copper crystallite with a specific intergrain boundary under pulsed loading is modeled numerically. It is found that the grain boundary changes the parameters of nonlinear waves generated by loading and significantly affects the character of the spalling fracture. Translated fromFizika Goreniya i Vzryva, Vol. 36, No. 5, pp. 126–129, September–October, 2000.     

Relative contribution of trees and crops to soil carbon content in a parkland system in Burkina Faso using variations in natural 13C abundance

The origin of organic matter was studied in the soils of a parkland of karité (Vitallaria paradoxa C.F. Gaertn) and néré (Parkia biglobosa (Jacq.) Benth.), which is extensively cultivated without the use of fertilisers. In such systems, fertility (physical, chemical and biological) gradients around trees have been attributed by some authors to a priori differences in fertility, allowing for better tree establishment on richer sites. In reverse, other workers believed that these gradients are due to the contribution of trees to the formation of soil organic matter through litter and decay of roots. Measurements of the variations in the ¹³C isotopic composition allowed for a distinction between tree (C₃) derived C and crop and grass (C₄) derived C in the total soil organic C content. The organic carbon contents of the soils were recorded under the two species at two soil depths and at five distances going from tree trunk to the open area and their C isotopic signatures were analysed. The results showed that soil carbon contents under karité (6.43 ± 0.45 g kg⁻¹) and néré (5.65 ± 0.27 g kg⁻¹) were significantly higher (p<0.01) than in the open area (4.09 ± 0.26 g kg⁻¹). The δ¹³C of soil C was significantly higher (p<0.001) in the open area (−17.5 ± 0.3‰) compared with the values obtained on average with depth and distance from tree under karité (−20.2 ± 0.4‰) and néré (−20.1 ± 0.4‰). The C₄-derived soil C was approximately constant, and the differences in total soil C were fully explained by the C₃ (tree) contributions to soil carbon of 4.01 ± 0.71, 3.02 ± 0.53, 1.53 ± 0.10 g kg⁻¹, respectively under karité, néré and in the open area. These results show that trees in parklands have a directly positive contribution to soil carbon content, justifying the need to encourage the maintenance of trees in these systems in semi-arid environments where the carbon content of soil appears to be the first limiting factor for crop growth.     

Performance characteristics of heater elements made of carbon fibres

The optimum concentration of a solution of adhesive required for impregnating CF is 35±5%, which corresponds to a 45±5% content in the fibre. An electric current is transmitted in CF due to the relatively low resistance of the fibre filaments and according to a “chain” scheme. The change in the strength of CF under the effect of cyclic double bending and preliminary loading was determined. The characteristics of the increase in the electrical resistance as a function of the number of double bending cycles, correlated with breaking of the CF filaments and a decrease in the contacts between them, were established. __________ Translated from Khimicheskie Volokna, No. 3, pp. 33–35, May–June, 2006.     

Correlation between crosslinking efficiency and spatial inhomogeneity in poly(acrylamide) hydrogels

Summary Elasticity and light scattering measurements were carried out on poly(acrylamide) (PAAm) hydrogels prepared from acrylamide (AAm) and N,N’-methylenebisacrylamide (BAAm) monomers under various reaction conditions. Elasticity tests showed that the crosslinking efficiency of BAAm ε_xl, that is the fraction of BAAm forming effective crosslinks decreases as the initial monomer concentration C_o is decreased. At C_o=3%, ε_xl was found to be 10^-2–10^-3, indicating that 99 to 99.9% of BAAm used in the hydrogel preparation are wasted in elastically ineffective links. Debye-Bueche analysis of the light scattering data showed that, irrespective of the gel synthesis conditions, the correlation length ξ, that is, the extension of inhomogeneities in the hydrogels is 10¹ nm. The extent of frozen concentration fluctuations in the hydrogels represented by 〈η²〉 decreases with increasing crosslinking efficiency of BAAm. The combination of the light scattering and the elasticity data of gels shows a direct correlation between the fraction of wasted crosslinker molecules during gelation and the spatial gel inhomogeneity.     

Investigation of phase transformations in iron and cerium using a polyvinylidene fluoride pressure gauge

This paper presents results of studies of shock-induced phase transformations in iron (polymorphic α-ε transition) and cerium (isomorphic γ-α transition) using a polyvinylidene fluoride pressure gauge. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 4, pp. 121–126, July–August, 2007.     

Activated anionic ring-opening polymerization of ε-caprolactam with magnesium di(ε-caprolactamate) as initiator: effect of magnesium halides

The activated anionic ring-opening polymerization of ε-caprolactam initiated by 0.35 mol% of combined initiator, i.e., equimolar mixture of magnesium di(ε-caprolactamate) (CL₂Mg) with magnesium halides (MgCl₂, MgBr₂, and MgI₂) as well as of ε-caprolactam magnesium bromide (CLMgBr) in the presence of 0.35 mol% of N-acetyl-ε-caprolactam as an activator has been investigated in the temperature range 140–200 °C. It was found that the reaction rate increased while the apparent activation energy decreased in the following series: CL₂Mg/MgCl₂ < CL₂Mg/MgBr₂ ~ CLMgBr < CL₂Mg/MgI₂. In addition, the poly(ε-caprolactam)s prepared with CL₂Mg/MgX₂ (MgX₂ = MgCl₂, MgBr₂, and MgI₂) are characterized by slightly higher thermal stability than polymers obtained with CLMgBr as initiator. These observations were explained in terms of the coordination of Lewis acids (MgX₂, where X = Cl, Br, and I) with imide carbonyl of N-acyllactam end groups leading to the increase of their reactivity and stability.     

Effect of strain rate on the behavior of three-dimensional polymers of oligoesteracrylates under the conditions of the uniaxial elongation

For three-dimensional polymers based on the dimethacryloil derivatives adipic and sebasinoil acids and dicarbonyloxyethylene we have established the influence of the deformation velocity (V _ε) on their behaviour under the conditions of the uniaxial elongation. With the increase of V _ε up to a distinct value of V _εl , the ultimate stress σ _m for of the polymers grows, but at V _ε > V _εl the value of σ _m decreases. This phenomenon is explained. With the rise of V _ε, the module of elasticity E ₁ increases and the curves σ(ε) are shifted to the left along the ε axis. The change of the character of the structural organization of three-dimensional polymers in the deformation process of their samples was established.     

Influence of geometric and regime parameters on flame stabilization of a swirl burner

The influence of geometric and regime parameters of a swirl burner with a central body and a diffuser on flow characteristics and flame stabilization in the combustion of a premixed gas mixture was investigated using Reynolds equations and thek-ε model of turbulence. Translated fromFizika Goreniya i Vzryva, Vol. 35, No. 5, pp. 21–26, September–October 1999.     

Specific features of solid-phase reactions induced by shock waves

Kinetic and thermodynamic aspects of solid-phase reactions in recovery ampoules under shock compression are considered. Attention is paid to incompleteness of chemical conversion owing to the “cold” character of exothermic reactions in shock waves and to the dependence of the heat-release profile on the grain-size distribution of reagents. Different degrees of conversion at an identical level of pressure under loading and unloading are noted. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 2, pp. 128–132, March–April, 2006.     

Effect of the strain rate on the tensile strength of a copper shaped-charge jet

The data on the penetration depth of a rotating shaped-charge jet were used to estimate the strength of the material of a copper jet formed from a “low” conical linear with an apex angle of120° under the action of centrifugal forces. The estimates0.07–0.15 GPa obtained are close to the static yield point of deformed copper. The jet strength, which is estimated using the length of the fragments formed upon breakup of a rotation-free jet owing to the axial velocity gradient, attains1–1.5 GPa at a strain rate of ≌2·10⁴ sec⁻¹. Lavrent’ev Institute of Hydrodynamics, Siberian Division, Russian Academy of Sciences, Novosibirsk 630090. Translated from Fizika Goreniya i Vzryva, Vol. 33, No. 1, pp. 111–118, January–February, 1997.     

Electrical studies of nanocomposites consisting of MWNTs and polystyrene

Multi-wall carbon nanotubes (MWNTs)/polystyrene (PS) nanocomposites containing different concentrations of MWNTs were prepared by the solution evaporation method. Dispersion of MWNTs in PS was achieved by using ultrasonic energy. The structure of nanocomposites was investigated using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The dielectric constant (ε′), dielectric loss (ε″), and ac conductivity (σ _ac) were measured from room temperature to 100 °C over the frequency range 10³ Hz–1.2 MHz. The results show that the dielectric properties depend on both frequency and temperature and they are enhanced by increasing the MWNTs content.     

Isoconversional kinetic analysis of ring-opening polymerization of ε-caprolactone: Steric influence of titanium(IV) alkoxides as initiators

Four titanium(IV) alkoxides, namely: Ti(IV) n-propoxide (1), Ti(IV) n-butoxide (2), Ti(IV) tert-butoxide (3), and Ti(IV) 2-ethylhexoxide (4), have been used as initiators in the bulk ring-opening polymerization (ROP) of ε-caprolactone (ε-CL). The influence of the alkoxide group on the course of the ROP of ε-CL was investigated by means of ¹H-NMR and differential scanning calorimetry (DSC). The ¹H-NMR spectra confirmed that the ROP reaction of ε-CL proceeded via the widely accepted coordination-insertion mechanism for each of the four initiators. Isoconversional methods have been used to evaluate non-isothermal DSC data via the equations of Friedman, Kissinger-Akahira-Sunose (KAS) and Ozawa-Flynn-Wall (OFW). The kinetic studies showed that the polymerization rate for the four initiators (1-4) was in the order of 1 > 2 ≈ 4 > 3. The lowest activation energies (40–47, 42–44, and 49–52 kJ/mol for the Friedman, KAS and OFW methods respectively) were found in the polymerizations using Ti(IV) n-propoxide (1), while the highest activation energies (84–107, 77–87, and 80–91 kJ/mol for the Friedman, KAS and OFW methods respectively) were obtained using Ti(IV) tert-butoxide (3). Differences in the rates of polymerization and the activation energies amongst the four initiators appeared to be governed mainly by the different degrees of steric hindrance in the initiator structure. These results represent important findings regarding the steric influence of the alkoxide groups on the kinetics of the ROP of ε-CL initiated by titanium(IV) alkoxides.