Palladium-Mediated Ring-Opening Reactions of Strained Cyclotetrasilanes

Room-temperature ring-opening polymerization of the strained monomer 1,2,3,4-tetramethyl-1,2,3,4-tetraphenylcyclotetrasilane mediated by palladium complexes was attempted. Examination of the reaction products between the cyclotetrasilane and the metal complex at high concentrations indicated that insertion of one cyclotetrasilane molecule between the ligand–palladium bond was followed by reductive elimination of the tetrasilane. Among the palladium complexes examined were (³-allyl)PdCp [Cp=⁵-cyclopentadienyl], [(³-allyl) PdCl]₂, (³-allyl)PdCl(PPh₃), (³-allyl)PdCl(PPh₃)₂, (³-allyl)Pd(PPh₃)₃ and PdCl₂(PPh₃)₂. Reaction of 1,1,2,3,4-pentamethyl-2,3,4-triphenylcyclotetrasilane with (³-allyl)PdCp provides similar products.     

[η]-M-relationship for polyacrylamide in aqueous 0.1 M Na2SO4 solution

Summary The intrinsic viscosity [] and the molecular weight M_W of 8 pure, unbranched polyacrylamide (PAAm) samples — prepared in our laboratory — were determined and lead to the following formula [] = 0,0194 · M_W ^0,70(cm³/g) Solvent: aqeous 0.1 M Na₂SO₄ solution; T=298K; M_W/M_n-2,5 . In addition a comparison to the []-M-relationships of PAAm in other solvents is given.     

Structure and thermal stability of zinc–nickel electrodeposits

ZnNi alloys were electrodeposited from a chloride bath on steel substrates. The effect of nickel bath concentration on chemical composition, structure and microstructure of the deposits is demonstrated. From 0 to 13 nickel, the phases obtained do not correspond to that reported on the thermodynamic phase diagram. It is shown that the substitution of zinc by nickel is responsible for the formation of distorted _d and _d phases corresponding to the supersaturated hexagonal phase of zinc and to the unsaturated cubic phase of Zn–Ni alloy, respectively. Differential scanning calorimetry indicates that the thermal instability of the alloys containing up to 13 wt of nickel, results from the crystallization of the phase from the _d and _d phases at around 200 °C and 250 °C, respectively.     

Comparison of the critical conditions for initiation of dendritic growth and powder formation in potentiostatic and galvanostatic copper electrodeposition

Critical current densities for the initiation of dendrite growth and powder formation in potentiostatic and galvanostatic deposition are determined. Induction times for dendritic growth formation in potentiostatic and galvanostatic deposition are discussed.Nomenclature C ₀ bulk concentration - D diffusion coefficient - F Faraday constant - h height of a protrusion - h _i height of ith protrusion - h ₀ initial height of a protrusion - i current density - i _c current density at which dendrites appear instantaneously - i _i minimal current density at which dendritic growth becomes possible - i _L limiting current density - i ⁰ initial current density - i ₀ exchange current density - k proportionality factor - n number of electrons - N number of protrusions - R _t tip radius - S electrode surface area - S ₀ initial electrode surface area - t time - t _i induction time - V molar volume - thickness of the diffusion layer - overpotential - _c critical overpotential of instantaneous dendritic growth - _c,t critical overpotential of dendritic growth following non-dendritic roughness amplification - _i critical overpotential for the initiation of dendritic growth - ₀ initial overpotential - 2.3 ₀ slope of the Tafel line - quantity defined by Equation 3 - surface tension - time constant     

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.     

On the possibility of estimating weak interactions of macromolecules in solutions from the experimental viscous flow activation energies data

Summary The initial viscosity and activation energy in viscous flow of the systems: water(W)-casein(C)-polysaccharide(PS) (gum arabic(G),de-xtran(D), extran sulfat (DS)) have been determined for various ionic strengths corresponding to total or limited thermodynamic compatibility of macrocomponents. Excess activation energy H ^E due to the protein-polysaccharide interactions has been calculated. It is positive for systems with total compatibility and negative for systems with limited compatibility. Moreover, it yields information on type of the protein-polysaccharide interactions. Negative H ^E means that repulsive forces are dominant, while positive H ^E means that attractive forces are dominant. Since the properties of the systems W-C-D and W-C-DS are similar, it is believed that C-D complexes can possibly be formed with an energy 2 kT(10 mJ/g).The authors express their sincere graditude to Konstantinov A.A., Kondratev V.P., Chernysh M.M. (Special Design Bureau of the Institute of Petroleum Chemical Synthesis, The USSR Academy of Sciences) and Dmitrienko A.P. (Institute of Organoelement compounds, The USSR Academy of Sciences) for their invaluable help.     

Electrodeposition, composition and structure of Zn—Cr alloys

The effect of polyethylene glycol (PEG 1500) as additive and of deposition conditions on Zn—Cr alloy electrodeposition from an acidic sulfate electrolyte at room temperature, without agitation was investigated. PEG polarizes the overall cathodic reaction and inhibits Zn deposition. Cr codeposition with Zn starts at a cathodic potential of about –1,95 V vs Hg/Hg₂SO₄, which is reached at current density of about 20 A dm^–2 in galvanostatic conditions. Zn—Cr alloy coatings containing up to 28 at % Cr were obtained depending on the plating conditions. SEM observations showed an island-like structure, formed by the local growth of crystals, which covered the surface during further deposition. In the first stages of electrodeposition the powder diffraction spectra contain lines of b.c.c. -(Zn,Cr) phase (a 3.02 Å). After 30 s deposition time weak lines of Zn-based phase (a 2.67 Å, c 4.90 Å) appear, and become clearly visible in coatings deposited for 90 s. The average Cr content in the alloy coatings decreases with advancing deposition. The as-plated surface contains C in organic compounds and Zn(OH)₂. After 50 min sputtering, Zn and a mixture of Cr, Cr₂O₃ and Cr₇C₃ were found. The presence of organic C and O, probably from inclusions of PEG, were also detected.     

Correlation between configuration/conformation of zirconocenes on the stereoselectivity of the propylene polymerization reaction

Summary The catalytic performance (activity and polymer properties) of metallocenes with different symmetries in combination with methylaluminoxane (MAO) in the polymerization of propylene has been investigated at different temperatures, under standardized reaction conditions. The zirconocene rac-ethylene (⁵-1-indenyl) zirconium (IV) dichloride, with C₂ symmetry, produces isotatic polypropylene and isopropylidene(⁵-cyclopentadienyl (⁵-9-fluorenyl) zirconium (IV) dichloride, with C _S symmetry, syndiotactic polypropylene. The degree of the tacticity of these polymers increases with decreasing polymerization temperature. Only atactic polypropylene was formed with the unbridged zirconocenes bis(⁵-cyclopentadienyl) zirconium (IV) dichloride and bis(⁵-indenyl zirconium (IV) dichloride at any temperature investigated (10–60°C).     

High resolution transmission electron microscopic (HRTEM) determination of the preferentially exposed faces onγ-Al2O3 andη-Al2O3

High resolution transmission electron microscopy has been used to examine the crystallites in -Al₂O₃ and -Al₂O₃. -Al₂O₃ has been found to be nearly hexagonally shaped crystallites whose identity distances and angles of fringe patterns indicate that (110) planes are preferentially exposed. -Al₂O₃ showed preferentially exposed surfaces of (100), (110) and super imposed (111)/(211). This information is valuable to the catalyst researcher trying to model the surfaces of these two supports.     

Phase-structure analysis of brass by anodic linear-sweep voltammetry

Anodic linear-sweep voltammetry (ALSV) was applied to electrodeposited alloy layers and to metallurgically obtained Cu–Zn alloys of different composition and structure. Metallurgically obtained samples covered the range of composition in which , (+), and (+) intermediate phases were detected by X-ray. The ALSV of samples containing less than 30 wt % Zn exhibited a single peak at –0.08 to –0.1 V/SCE before massive dissolution, starting at about –0.05 V/SCE. The presence of the -phase gave another peak at a significantly more negative potential (–0.25 to –0.35 V/SCE). The ALSV of electrodeposited alloys were significantly more complex than the former, depending on the deposition potentials, with peaks attributable to pure Zn, to the -phase, to the -phase as well as to the -phase, present in most cases and dissolving at potentials similar to that of pure Cu. ALSV was shown to be a reliable and practical method for a fast determination of both the composition and the phase structure of electrodeposited brass.     

Investigation of water electrolysis by spectral analysis. I. Influence of the current density

The potential (or current) fluctuations observed under current (or potential) control during gas evolution were analysed by spectral analysis. The power spectral densities (psd) of these fluctuations were measured for hydrogen and oxygen evolution in acid and alkaline solutions at a platinum disk electrode of small diameter. Using a theoretical model, some parameters of the gas evolution were derived from the measured psd of the potential fluctuations, such as the average number of detached bubbles per time unit, the average radius of the detached bubbles and the gas evolution efficiency. The influence of the electrolysis current on these parameters was also investigated. The results of this first attempt at parameter derivation are discussed.Nomenclature b Tafel coefficient (V^–1), Equation 46 - C electrode double layer capacity (F) - e gas evolution efficiency (%) - f frequency (Hz) - f _p frequency of the peak in the psd _v and _i (Hz) - F Faraday constant, 96 487 C mol^–1 - l electrolysis current (A) - J electrolysis current density (mA cm^–2) - k slope of the linear potential increase (V s^–1), see Fig. 1 - n number of electrons involved in the reaction to form one molecule of the dissolved gas - r _b radius of a spherical glass ball (m) - r _e radius of the disk electrode (m) - R _e electrolyte resistance () - R _p polarization resistance () - R _t charge transfer resistance () - u ₁ distribution function of the time intervals between two successive bubble departures (s^–1) - v _g mean volume of gas evolved per unit time (m³ s^–1) - v _t gas equivalent volume produced in molecular form per unit time (m³ s^–1) - V ₀ gas molar volume, 24.5×10^–3 m³ at 298 K - x ₀ time pseudoperiod of bubbles evolution (s) - Z electrode electrochemical impedance () Greek characters _e dimensionless proportional factor (Equation 19) - slope of log /logJ and loge/logJ curves - number of bubbles evolved per unit time (s^–1) - _a activation overpotential (V) - _ci concentration overpotential of reacting ionic species (V) - _cs concentration overpotential of dissolved molecular gas (V) - _ohm ohmic overpotential (V) - _t total overpotential (V) - v parameter characteristic of the gas evolution pseudoperiodicity, Equation 13 (s^–1) - time constant of the double layer capacity change (s) - _v power spectral density (psd) of the potential fluctuations (V² Hz^–1) - _i power spectral density (psd) of the current fluctuations (A² Hz^–1) Special symbols spatial average of the overpotential _j over the electrode surface - time averaged value of - _j fluctuation of around - <> mean value of the total overpotential jump amplitude due to a bubble departure - <I> mean value of the current jump amplitude due to a bubble departure Paper presented at the 2nd International Symposium on Electrolytic Bubbles organized jointly by the Electrochemical Technology Group of the Society of Chemical Industry and the Electrochemistry Group of the Royal Society of Chemistry and held at Imperial College, London, 31st May and 1st June 1988.     

Extrapolation method of determining relative viscosity of polycaproamide in sulfuric acid

Conclusions A linear dependence of the relative viscosity of polycaproamide on sulfuric acid concentration has been confirmed.Regression equations have been found which make it possible to reduce the obtained using 93.5–96.5% sulfuric acid by wt. and using a variable sample weight of polycaproamide to a standardized relative viscosity st.Metrological certification of the extrapolated st method has been performed; the attainable accuracy is 0.010–0.015 when the number of determinations is 2.Inclusion of this procedure in the branch standard will make it possible to sharply reduce labor cost for analytical control.Translated from Khimicheskie Volokna, No. 4, pp. 58–60, July–August, 1988.     

Electron diffraction determination of an orientation-relationship for iridium-on-η-alumina

An iridium-on-alumina catalyst used for the spontaneous ignition of the decomposition of hydrazine in spacecraft position control thrusters exhibits nearly complete matching of the selected area electron diffraction patterns in the [110] orientation for iridium crystallites and for the support -alumina. The orientation-relationship is referred to the porous character of the -alumina skeleton favoring an oriented nucleation and growth of iridium crystallites in the pore mouths.     

Calculation of Temperature Dependences of the Viscosity and Volume Relaxation Time for Oxide Glass-Forming Melts from Chemical Composition and Dilatometric Glass Transition Temperature

The relaxation parameter K _sthat is equal to the ratio of the viscosity to the Kohlrausch volume relaxation time _s is analyzed. It is shown that this parameter can be evaluated from the temperature T ₁₃(corresponding to a viscosity of 10¹³P) and the glass transition temperature T ₈ ⁺determined from the dilatometric heating curve. The maximum error of the estimate with due regard for experimental errors is equal to ±(0.4–0.5)logK _sfor strong glasses and ±(0.6–0.8)logK _sfor fragile glasses, which, in both cases, corresponds to a change in the relaxation times with a change in the temperature by ±(8–10) K. It is revealed that the viscosity, the Kohlrausch volume relaxation time _s , and the shear modulus Gof glass-forming materials in silicate, borate, and germanate systems satisfy the relationship log( _s G/) 1. The procedure for calculating the temperature dependences of the viscosity and the relaxation times in the glass transition range from the chemical composition and the T ₈ ⁺temperature for glass-forming melts in the above systems is proposed. The root-mean-square deviations between the calculated and experimental temperatures T ₁₁and T ₁₃are equal to ±(6–8) K for all the studied (silicate, borate, germanate, and mixed) oxide glass-forming systems. The proposed relationships can be useful for evaluating the boundaries of the annealing range and changes in the properties and their temperature coefficients upon cooling of glass-forming melts.     

A model of the electrochemical behaviour within a stress corrosion crack

A mathematical model of the electrochemical behaviour within a stress corrosion crack is proposed. Polarization field, crack geometry, surface condition inside the crack, electrochemical kinetics, solution properties and applied stress can be represented by the polarization potential and current, the electrochemical reactive equivalent resistance of the electrode, the change in electrolyte specific resistance and surface film equivalent resistance, respectively. The theoretical calculated results show that (i) when anodic polarization potential is applied, the change in the crack tip potential is small; (ii) when cathodic polarization potential is applied, the crack tip potential changes greatly with the applied potential; (iii) the longer the crack, the smaller the effect of the applied potential on the crack tip potential in both anodic polarization and cathodic polarization conditions. The calculated results are in good agreement with previous experimental results.Notation coordinate, from crack mouth (on the metal surface) to crack tip (cm) - y y = s _L L/(s ₀ – s _L) + L – , function of (cm) - y ₀ y ₀ = s _L L/(s ₀ – s _L) + L (cm) - V polarization potential (V) - galvanic potential of electrode (V) - ₁ galvanic potential of electrolyte (V) - t sample thickness (cm) - w sample width (cm) - S _L crack tip width (cm) - S _o crack mouth width (cm) - L crack length (cm) - s() crack width at position (cm) - _lo specific resistance of electrolyte, as a constant ( cm) - _s specific resistance of metal ( cm) - (, y) specific resistance of electrolyte, varies with potential and crack depth ( cm) - R _b (, y) electrochemical reactive equivalent resistance of electrode, varies with potential and crack depth () - R ₁ electrolyte resistance () - R _s metal resistance () - r(, y) surface film equivalent resistance, varies with potential and crack depth () - r _o surface film equivalent resistance, as a constant () - I _o total polarization current (A) - I net polarization current from integrating 0 to in Fig. 2 (A) - polarization overpotential (V) - _a anodic polarization overpotential (V) - _c cathodic polarization overpotential (V) - Euler's constant     

Mark-Houwink-Sakurada coefficients for conventional poly(methyl methacrylate) in tetrahydrofuran

Summary Intrinsic viscosities [] in tetrahydrofuran (THF) at 30°C are reported for ten narrow molecular weight distribution poly(methyl methacrylate) (PMMA) samples covering nearly two orders of magnitude in molecular weight. By combining the viscosity results with absolute weight-average molecular weights determined via low-angle laser light scattering (LALLS) experiments, we have accurately determined the Mark-Houwink-Sakurada (MHS) parameters for this polymer-solvent pair (K=7.56x10⁵ and a=0.731, when [] is in dL g^-1).     

Application of the accelerated Tafel plot technique to corrosion kinetics: Role of double layer through simulation

Results on the simulated -t transient response of an actively corroding system under accelerated Tafel plot (ATP) conditions have revealed the influence of input parameters (i, ) and system parameters (C _dl,i _corr andb) and explained the observed dependence of kinetic parameters (arrived at on the basis of the intercept-slope method) on in certain time domains. New improved methods, which eliminate such dependence and give uniform corrosion rate data over all time domains, are described in the paper.Nomenclature ATP accelerated Tafel plot - transfer coefficient - b Tafel slope (V) - C _d double layer capacitance (F cm^–2) - i initial value of the exponentially decaying current (A) - E _c corrosion potential (V) - overpotential (V) - n overpotential corresponding to maximum in -t transient (V) - F Faraday constant (C mol^–1) - i _corr corrosion current density (A cm^–2) - n number of electrons involved in charge transfer step - p intercept of ATP (V) - R gas constant (JK^–1 mol^–1) - R _p polarization resistance ( cm²) - S slope of ATP, i.e. d/dt (V) - S _av average of theS values at > _el (V) - S _meas slope of the linear -t region, i.e. d/dt (Vs^–1) - T temperature (K) - t time (s) - t _m time corresponding ton _m in the -t transient (s) - time constant of the exponentially decaying current pulse (s) - _el electrode time constant given byR _p C _d (s)     

Investigations of polyelectrolyte-transition metal ion association in mixed solvents

Summary Association between a typical polyelectrolyte, e.g. poly-(acrylic acid), and a divalent metal ion (e.g. Cu(II)) has been studied using different water-methanol mixtures. Preferential solvation coefficients (/c) have been calculated for various solvent compositions. Excellent agreement has been observed between minimum (/c), lowest [] and reduced viscosity (sp/c) of the complexes at a specific composition of the solvent. Interpretations have been sought in terms of polyelectrolyte conformational change at this solvent composition.     

Ferrocenylenesilylene Polymers as Coatings for Tapered Optical-Fiber Gas Sensors

In this paper we report the use of ferrocenylenesilylene polymers as coatings for tapered optical-fiber sensors. The principle of operation of this device is based upon environmentally induced changes in the refractive index of the polymer layer which change the power transmitted through the tapered fiber. The results for two sensor arrays fabricated using the ferrocenylenesilylene polymer [( ⁵-C₅H₄)Fe( ⁵-C₅H₄)MePhSi] _m and copolymer {[( ⁵-C₅H₄)Fe( ⁵-C₅H₄)SiPhMe] _n [( ⁵-C₅H₄)Fe( ⁵-C₅H₄)Me₂Si] _m are presented. We also show that the sensitivity of this device is a function of the taper beat length.     

Calculation of the Viscosity of Glass-Forming Melts: VI. The R2O–B2O3–SiO2and RO–B2O3–SiO2Ternary Borosilicate Systems

A method for calculating the viscosity from composition and temperature for melts in the R _m O _n –B₂O₃–SiO₂systems is proposed. The change in the concentrations of structural groups depending on the melt composition is taken into account in calculations. The results of calculations are compared with the experimental data available in the literature on the viscosity of 1200 melts with the use of the SciGlass information system. The root-mean-square deviation between the experimental and calculated characteristic temperatures varies from 30 K (for the glass transition temperature and the Littleton point) to 50 K (for a viscosity of 10⁴P).