Synthesis and characterization of polyacrylonitrile grafted with poly(2,6-dimethyl-1,4-phenylene oxide)

Summary Free radical copolymerization of acrylonitrile (AN, M₁) with poly(2,6-dimethyl-1,4-phenylene oxide)--vinylbenzyl ether (PPO-VBE, M₂, _n + 4200g/mol, _w/ _n + 1.04) was performed at 60°C in either a mixture of N,N-dimethylformamide/toluene or tetrahydrofuran, using 2,2-azoisobutyronitrile (AIBN) as initiator. The characterization of the resulting polyacrylonitrile grafted with poly(2,6-dimethyl-1,4-phenylene oxide) (PAN-g-PPO) was performed by 200 MHz ¹H-NMR spectroscopy and solubility.     

Birefringence of polyamide fibres of nonround cross-sectional from

Conclusions A method of determining the birefringence n of fibres having an uncomplicated profile (pentagonal, trilobal, or double rhombus) consists of the following: Over sections of the fibre one determines the ratio of the outer-contour dimensions — the diameterl of the fibre to its thickness d — the path over which the beam acquires the difference in speed ; the values of ,l, andl/d are averaged; and the calculation of n is carried out from the equation n = .This method has been tested on specimens of polyamide fibre prepared under identical melt flow rate conditions.Translated from Khimicheskie Volokna, No. 3, pp. 42–43, May–June, 1983.     

Studies concerning charged nickel hydroxide electrodes IV. Reversible potentials in LiOH,NaOH, RbOH and CsOH

The variation of reversible potential E_r with log a_moh and has been studied for several nickel hydroxide/oxyhydroxide couples in various alkali hydroxides. Both activated and deactivated -phase couples show only a small dependence ofE _r with log_moh (or where known) in LiOH, NaOH, RbOH and CsOH electrolytes. The change in MOH content on oxidation/reduction is found to be about 0.1 mol MOH per two-electron transfer and is the same as found previously in KOH. These results confirm that the bulk oxidized -phase lattice is devoid of alkali cation although a small quantity may be adsorbed by the surface. On the other hand both activated and deactivated /-phase couples show a marked dependence of 0.45 mol MOH per two-electron transfer in LiOH, NaOH and RbOH (at concentrations > 0.5 m), also in good agreement with earlier data for KOH. On the basis of these results a general stoichiometry can be inferred for the -phase, namely M_0.32NiO₂ · 0.7H₂O where M=Li⁺, Na⁺, K⁺ or Rb⁺. Measurements imply that the Cs⁺ ion or the Rb⁺ ion at low concentration (<0.5 m) do not enter the interlayer structure of the -phase. This behaviour is thought to be related to the low Rb-O and Cs-O bond strengths afforded by the -phase structure.     

Calculation of mean current densities in a two rotating disc electrodes system

A theoretical relationship for mass transfer in the laminar flow region of streaming in a rotating electrolyser was derived by the method of similarity of the diffusion layer for electrodes placed sufficiently far from the rotation axis. The obtained relationship was compared with the known equations valid for systems with axial symmetry. The mean current densities were found from the numerical solution of the convective diffusion equation by the finite-element method and were compared with experimental results.Nomenclature a constant, exponent - c concentration - c ₀ concentration in the bulk phase - C _ij matrix coefficient - D diffusion coefficient - F Faraday constant, 96487 C mol^–1 - h interelectrode distance - j current density - mean current density - J mass flux density - L _j base function - n number of transferred electrons in electrode reaction - n _r outer normal to the boundary - mass flux - N number of nodal points in an element - Q volume rate of flow - mean volume rate of flow - r radial coordinate - r ₀ inner electrode radius - r _l outer electrode radius - r _v radius of inlet orifice - r _d outer disc radius - v _r radial velocity component - v _z normal velocity component - z normal coordinate - thickness of the layer in which the equation of convective diffusion is solved - boundary of the integration domain - thickness of the diffusion layer - _N thickness of the Nernst diffusion layer - v kinematic viscosity - angular velocity - surface Criteria Re _chan channel Reynolds numberQ/hv - Re _loc local Reynolds number,Q/(r + r ₀) - local Reynolds number at mean electrode radius,Q/v(r ₁ +r ₀) - Re _rot rotation Reynolds number, r _d ² /v - modified rotation Reynolds number at mean electrode radius, (r ₁+r ₀)²/4v - Ré _rot modified rotation Reynolds number, (r+r ₀)²/4v - Sc Schmidt number,v/D - Sh _r local Sherwood number,j(r-r ₀)/nFDc _o - mean Sherwood number, - Ta Taylor number,h(/v)^1/2     

Activity and selectivity of PtNi/TiO2 catalysts for hydrogenation of crotonaldehyde

The hydrogenation of crotonaldehyde over a series of titania supported PtNi catalysts was investigated. Pt/TiO₂ had the highest activity to hydrogenate the bond of crotonaldehyde. With the addition of Ni to Pt the activity for carbonyl group hydrogenation decreased, while that for the bond hydrogenation increased. Two different types of sites were established to be active for bond hydrogenation, located at (i) the Pt-TiO₂ interface and (ii) the PtNi bimetallic phase. For the Pt-TiO₂ interface the presence of accessible Ti ^x+ cations in close distance to Pt and for the PtNi phase a slightly positively charged Ni on the surface of these alloy particles were concluded to be responsible for the enhanced selectivity to crotylalcohol. The hydrogenation of the bond occurs mainly on the clean metal surfaces of Ni and Pt.     

Flow-through and flow-by porous electrodes of nickel foam Part IV: experimental electrode potential distributions in the flow-through and in the flow-by configurations

Experimental distributions of the solution potential in flow-through and flow-by porous electrodes of nickel foam operating in limiting current conditions are presented. These are in good agreement with the corresponding theoretical distributions. In the case of a flow-by configuration used in a two-compartment cell, the experiments confirm the validity of the models, presented in Part III, which take into account the presence of a separator (ceramic porous diaphragm or ion exchange membrane).Nomenclature a _e specific surface area per unit volume of electrode - C ₀ entrance ferricyanide concentration (y=0) - D molecular diffusion coefficient of ferricyanide - E _e cathode potential - F Faraday number - mean (and local) mass transfer coefficient - L electrode thickness - L _s-L separator thickness - m number of sheets of foam in a stack - n number of terms in Fourier series - Q volumetric flow-rate - r _s ohmic specific resistance of the separator - mean flow velocity based on empty channel - V constant potential - X conversion - x coordinate for the electrode thickness - y coordinate for the electrode length - y ₀ length of the porous electrode - z number of electrons in the electrochemical reaction Greek symbols parameter - parameter - ionic electrolyte conductivity - _sc solution potential in the pores of the cathode - _M matrix potential ( _sc = constant) - parameter [=n/y ₀] - electrolyte density - mean porosity - kinematic viscosity - E _c potential drop in the porous cathode - potential drop defined in Fig. 5 Indices c cathodic - o electrolyte alone - s separator     

Generalized analytical expressions for Tafel slope,reaction order and a.c. impedance for the hydrogen evolution reaction (HER): mechanism of HER on platinum in alkaline media

Following the generally accepted mechanism of the HER involving the initial proton discharge step to form the adsorbed hydrogen intermediate, which is desorbed either chemically or electrochemically, generalized expressions for the Tafel slope, reaction order and the a.c. impedance for the hydrogen evolution reaction are derived using the steady-state approach, taking into account the forward and backward rates of the three constituent paths and the lateral interactions between the chemisorbed intermediates. Limiting relationships for the Tafel slope and the reaction order, previously published, are deduced from these general equations as special cases. These relationships, used to decipher the mechanistic aspects by examining the kinetic data for the HER on platinum in alkaline media, showed that the experimental observations can be consistently rationalized by the discharge-electrochemical desorption mechanism, the rate of the discharge step being retarded on inactive platinum compared to the same on active platinum.Nomenclature C _d double-layer capacity (µF cm^–2) - E _rev reversible electrode potential (V) - F Faraday number (96 487 C mol^–1 ) - R gas constant - T temperature (K) - Y _f Faradaic admittance (^–1 cm^–2) - Y _t Total admittance (^–1 cm^–2) - Z _f Faradaic impedance ( cm²) - i _f total current density (A cm^–2) - i _nf nonfaradaic current density (A cm^–2) - j - k ₀ ¹ rate constant of the steps described in Equations 1 to 3 (mol cm^–2 s^–1 ) - j - qmax saturation charge (µC cm^–2) - Laplace transformed expressions for i, and E - _{1 3} symmetry factors for the Equations 1 and 3 - saturation value of adsorbed intermediates (mol cm^–2) - overpotential - coverage by adsorbed intermediates - angular frequency This paper is dedicated to Professor Brian E. Conway on the occasion of his 65th birthday, and in recognition of his outstanding contribution to electrochemistry.     

Influence of molecular weight on the crystallization of poly(vinylidene fluoride)

Five samples of Poly (vinylidene fluoride) with a molecular weight from 45,000 to 260,000 were analyzed by means of FT-IR spectroscopy in order to study the influence of molecular weight on the crystallization process. The spectra of films obtained from methylethylketone solutions revealed the prevalence of form II () in the case of lower and of form III () in the higher molecular weight samples. The amount of form III was found to increase as the Mv decreased and as annealing temperatures increased. The deconvolution technique of vibrational spectra allowed detection of small amounts of other forms accompanying the prevailing one.     

Flow-through and flow-by porous electrodes of nickel foam Part III: theoretical electrode potential distribution in the flow-by configuration

This paper deals with the theoretical potential distribution within a flow-by parallelepipedic porous electrode operating in limiting current conditions in a two-compartment electrolytic cell. The model takes into account the influence of the counter-electrode polarization and of the separator ohmic resistance. The results show that the design of the porous electrode requires the knowledge of the solution potential distribution within the whole cell volume.Nomenclature a _c specific surface area per unit volume of electrode - C ₀ entrance concentration (y=0) - C _s exit concentration (y=y ₀) - E electrode potential (= _M – _S ) - E _o equilibrium electrode potential - F Faraday number - i current density - mean mass transfer coefficient - K parameter [a _ea zFi _oa/(_a RT)]^1/2 - L porous electrode thickness - n number of terms in Fourier serials - P specific productivity - Q volumetric flow-rate - mean flow velocity based on empty channel - V constant potential - V _R electrode volume - x thickness variable - X conversion - y length variable - y ₀ porous electrode length - z number of electrons in the electrochemical reaction Greek symbols parameter - parameter - ionic electrolyte conductivity in pores - _S solution potential - _M matrix potential ( _M = constant) - parameter [=n/y ₀ - parameter [=+K] - overpotential Suffices a anodic - c cathodic - eq equilibrium - s separator - S solution     

Convective Regime of Filtration Combustion of Energetic Materials in a Cocurrent Flow of Their Combustion Products

The convective regime of filtration combustion of energetic materials in a cocurrent flow of their combustion products is studied using a model with extremely simplified kinetics and heat transfer, which shows instability of the process. It is shown that the more accurate twotemperature model describes a steadystate regime. In this regime, the gas temperature on the hot boundary of the heating zone is well below the combustion temperature, and the solidphase temperature is well below the temperature proposed in recent studies on this topic. It is pointed out that the twotemperature approach is unjustified and intragranular nonisothermicity must be taken into account for convective regimes. It is shown that the threetemperature model, which takes into account this effect, does not give a stable steadystate solution.     

Quasi‐Homogeneous and Pseudospin Modes of Zirconium‐Wire Combustion in Air

A novel experimental technique is proposed for examining the transition mechanism from quasihomogeneous to heterogeneous combustion — burning of a variablepitch spring. Depending on the pitch of aircombustible zirconium springs, two combustion modes are possible. Quasihomogeneous (layerbylayer) combustion is observed in the case of smallpitch springs; as the spring pitch increases, quasihomogeneous combustion transforms into heterogeneous (pseudospin) combustion. Conditions for the occurrence of various combustion modes, depending on the spring diameter and pitch, are studied.     

Antifungal polyoxygenated fatty acids fromAeollanthus parvifolius

Two polyoxygenated fatty acids with antifungal activity have been isolated from aerial parts ofAeollanthus parvifolius (Labiatae) using bioassay-guided isolation procedures. Spectroscopic analysis was used to identify the compounds as (Z)-4,9-diacetoxy-6,7-epoxy-5-hydroxy-8-oxododeca-2-enoic acid and (Z)-4,6,7,9-tetraacetoxy-5-hydroxy-8-oxododeca-2-enoic acid. Both of these compounds inhibited spore germination ofCladosporium cucumerinum. Minimum inhibitory doses were 1 µg and 5 µg, respectively, but only the former inhibited germination ofAspergillus niger at a dose of 5 µg. Neither compound exhibited antibacterial activity. (Z)-4,9-Diacetoxy-6,7-epoxy-5-hydroxy-8-oxododeca-2-enoic acid reduced the hyphal growth ofPythium ultimum. The mode of action was not resolved but did not involve either the disruption of the cell wall membrane or the inhibition of extracellular enzymes. Application of (Z)-4,6,7,9-tetraacetoxy-5-hydroxy-8-oxododeca-2-enoic acid to seedling plants did not give any protection against fungal attack, and indeed the compound appeared to be phytotoxic.     

Critical solution point and chain dimension of branched-polystyrene solutions

Summary Critical solution point and chain dimension were measured for branched polystyrene(BPS) in solution as a function of molecular weight(M) and compared with those for linear polystyrene(LPS). The critical concentration _c of BPS was quite different from that of LPS at a fixed M, but the same at a fixed overlap-concentration ^*, i.e., plots of _c vs. ^* fall on a single straight line for both BPS and LPS (gf_c ^*). Reduced critical temperature _c defined by gt_c=(–T_c)/ [T_c: critical temperature, : the -temperature] was related to _c as _{c c} ² for BPS, whereas _{c c} for LPS.     

Synthesis of monocarboxylic polyoxyethylenes

Summary The various methods of synthesis which can be used to prepare -carboxy polyoxyethylenes are reviewed. The synthesis and the purification of -methoxy -carboxy polyoxyethylenes ( ) are reported. The process consists of the reaction of halogenoacetic acids with an -methoxy -sodium hydroxylate polyoxyethylene followed by a purification by extraction. ,-dimethoxy and -methoxy -ethyl carboxylate polyoxyethylenes were synthesized.     

Variable‐temperature IR spectroscopic studies of CO adsorbed on Na‐ZSM‐5 and Na‐Y zeolites

CO interacts with extraframework alkali metal cations (M⁺=) of zeolites to form both M⁺CO and M⁺OC species. By using variabletemperature FTIR spectroscopy, these Cbonded and Obonded species were found to be in a temperaturedependent equilibrium. For the same cation, the difference in interaction energy depends upon the zeolite framework. Thus, for the equilibrium process ZNa⁺=CO ZNa⁺OC, where Z represents the zeolite framework, H ⁰ was found to take the values 3.8 and 2.4 kJ mol^– for CO/NaZSM5 and CO/NaY, respectively. The Cbonded species show always the highest cation–CO interaction energy.     

Specific features of the phase transformations occurring during the sintering process of the beta-alumina based ceramics and their properties

Conclusions During the sintering process of beta-alumina obtained using the method of plasmochemical synthesis, the structural transformation occurs and it is accompanied by the separation of the excess Na₂O and the formation of an intergranular meltlike phase that is saturated with sodium and is characterized by high dielectric properties.The quantity of the meltlike phase and the magnitude of the /( + ) ratio determine the degree of stabilization (stability) and the final resistivity of the material and depend on the initial chemical composition and the heating rate maintained during the sintering process.It was shown that when the duration of residence of the material in the hot zone of the furnace is increased or when the specimens sintered maintaining high heating rates are subjected to additional heat treatment, one observes the occurrance of the reverse structural transformation that is characterized by an increase of the phase ratio /( + ) 1, a reduction in the quantity of the meltlike phase right up to its complete disappearance, and a decrease of the electrical resistivity of the material.In the materials having a large excess quantity of sodium oxide, the process of crystallization of the intergranular NaAlO₂ phase occurs simultaneously with the second phase transformation.The best ceramic and electrophysical parameters were obtained when sintering the material contained 7.9% Na₂O.Translated from Ogneupory, No. 3, pp. 13–18, March, 1990.     

Methane coupling at low temperatures on Ru(0001) and Ru(11¯20) catalysts

The conversion of methane to higher hydrocarbons on single crystal Ru catalysts has been investigated using combined elevated-pressure kinetic measurements/surface science studies. The reaction consists of activation of methane on Ru(0001) and Ru(11¯20) surfaces to produce carbonaceous intermediates at temperatures between 350 and 700 K and rehydrogenation of these species to ethane and propane at 370 K. It is found that under the reaction conditions employed, the maximum yield in ethane/propane production occurs at 500 K on both surfaces. Influence of the hydrogenation temperature on the production of ethane and propane is also examined. On Ru(0001), the yields of ethane and propane maximize at = 400 K, whereas no maximum yield was observed on Ru(11 0) in the 300–500 K temperature range. Under optimum reaction conditions, hydrocarbon products consist of 16% ethane and 2% propane. High-resolution electron energy-loss spectroscopy (HREELS) has been used to identify various forms of hydrocarbonaceous intermediates following methane decomposition. An effort is made to relate the hydrocarbon intermediates identified by HREELS to the gas phase products observed in the elevated pressure experiments.     

Location of Mn in MnAPO‐11: influence of synthesis from aqueous and non‐aqueous media

MnAPO11 samples were synthesized from aqueous (MnAPO11(A)) and ethylene glycol (MnAPO11(NA)) media. The crystallinity of the samples was more when the synthesis was carried out in ethylene glycol. Chemical and thermogravimetric analyses reveal greater incorporation of Mn in the framework of MnAPO11(NA) than in MnAPO11(A). At least five different types of Mn(II) species are detected in the samples by ESR. The studies suggest that Mn is more homogeneously distributed in MnAPO11(NA) than in MnAPO11(A).     

Recovery and recrystallization of electrodeposited bright copper coatings at room temperature. II. X-ray investigation of primary recrystallization

X-ray investigations of the recrystallization processes occurring at room temperature in electrodeposited bright copper coatings were carried outin situ. As a result of the orientation transformation of the growth texture with 311, 111 and 110 components, a recrystallization texture with 100, 110 and 111 components was obtained. It was established that one of the factors which influence the microhardness of copper coatings is the orientation distribution of crystallites.     

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.