85 resultados para THERMAL RATE COEFFICIENT
Resumo:
The thermal properties of ethylene propylene copolymer-grafted-acrylic acid (EP-g-AA) were investigated by using differential scanning calorimetry (DSC). Compared with the ethylene propylene copolymer (EP), the peak values of the melting temperature (T-m) of the propylene sequences in the grafted EP changed a little, the crystallization temperature (T-c) increased about 8-12 degrees C, and the melting enthalpy (Delta H-m) increased about 4-6 J/g. The isothermal crystallization kinetics of grafted and ungrafted samples was carried out by DSC. Within the scope of the researched crystallization temperature, the Avrami exponent (n) of the ungrafted sample was 1.6-1.8, and that of grafted samples were all above 2, which indicated that the grafted monomer could become the crystal nuclei for the crystallization of propylene sequence. With increasing grafted monomer content, the crystallization rate of propylene sequence in grafted EP increased; it might be the result of rapid nucleation rate and crystal growth rate.
Resumo:
The steady state voltammogram at a microdisk electrode is used to measure the diffusion coefficient and standard heterogeneous rate constant (k(s)) of ferrocene in polyelectrolyte PEG + LiClO4. The k(s) obtained is smaller in polyelectrolyte than in liquid medium. It is proposed that the polymer solvent electron transfer dynamics are affected by the relaxation rates of the ether dipole sites on the polymer chains, which are in turn constrained by the rates of polymer chain segment, or local structure, relaxations. The dependence of k(s) on temperature is observed. The k(s) increases with increasing temperature.
Resumo:
Steady-state voltammograms at a microdisk electrode are used to measure the diffusion coefficient (D) and standard heterogeneous rate constant (k(s)) of ferrocene in polyelectrolyte PEG.MClO(4). The diffusion coefficient and standard heterogeneous rate constant of ferrocene are both smaller in polymer solvents than in monomeric solvents. The D and k(s) of ferrocene have been estimated in PEG containing different concentrations and cations of supporting electrolytes, and the dependencies of D and k(s) on temperature have been observed. These results show that the D and k(s) of ferrocene increase with increasing temperature in polyelectrolyte, and with increasing cation radius of supporting electrolyte, eg D and k(s) increase in the order Bu(4)NClO(4) > NaClO4 > LiClO4. On the other hand, D and k(s) increase with decreasing concentration of supporting electrolyte. The dependence of the half-wave potential (E(1/2)) on the concentration of the supporting electrolyte is also observed. E(1/2) shifts in the negative direction as the concentration of supporting electrolyte increases. (C) 1997 Elsevier Science Ltd.
Resumo:
The thermal properties of ethylene-propylene copolymer grafted with glycidyl methacrylate (EP-g-GMA) were investigated by using differential scanning calorimetry (DSC). Compared to the plain ethylene-propylene copolymer (EP), peak values of melting temperature (T-m) of the propylene sequences in the grafted EP changed a little, crystallization temperature (T-c) increased about 8-12 degrees C, and melting enthalpy (Delta H-m) increased about 4-6 J/g. The isothermal and nonisothermal crystallization kinetics of grafted and ungrafted samples was carried out by DSC. Within the scope of the researched crystallization temperature, the Avrami exponent (n) of ungrafted sample is 1.6-1.8, and those of grafted samples are all above 2. The crystallization rates of propylene sequence in EP-g-GMA were faster than that in the plain EP and increased with increasing of grafted monomer content. It might be attributed to the results of rapid nucleation rate. (C) 1996 John Wiley & Sons, Inc.
Resumo:
The electrocatalytic oxidation of NADH by ferrocene derivatives and the influence of complexation with beta-cyclodextrin (beta-CD) were investigated at a microdisk electrode in a buffer solution. The cyclic voltammetric behavior of the ferrocene derivatives on the microdisk electrode was used to determine the electron-transfer rate constant from NADH to the ferricinium species. The heterogeneous rate constants and the diffusion coefficient of ferrocene derivatives were determined with the microdisk electrode. The effect of temperature and pH on the electrocatalytic oxidation of NADH were assessed.
Resumo:
A strong strain-rate and temperature dependence was observed for the fracture toughness of phenolphthalein polyether ketone (PEK-C). Two separate crack-blunting mechanisms have been proposed to account for the fracture-toughness data. The first mechanism involves thermal blunting due to adiabatic heating at the crack tip for the high temperatures studied. In the high-temperature range, thermal blunting increases the fracture toughness corresponding to an effectively higher test temperature. However, in the low-temperature range, the adiabatic temperature rise is insufficient to cause softening and Jic increases with increasing temperature owing to viscoelastic losses associated with the p-relaxation there. The second mechanism involves plastic blunting due to shear yield/flow processes at the crack tip and this takes place at slow strain testing of the single-edge notched bending (SENB) samples. The temperature and strain-rate dependence of the plastic zone size may also be responsible for the temperature and strain-rate dependence of fracture toughness.
Resumo:
The rapid scan spectrometer was used to determine the heterogeneous electron transfer rate parameters for the oxidation of Biliverdin in DMF by single potential step thin layer spectroelectrochemical techniques and yielded an average formal heterogeneous electron transfer rate constant K(s, h)0' = 2.45 (+/-0.12) x 10(-4) cm s-1, electrochemical transfer coefficient alpha = 0.694+/-0.008. The oxidation process of Biliverdin was also studied and the formal potential E0 = 0.637 V (vs. Ag/AgCl) was obtained.
Resumo:
Bagnold-type bed-load equations are widely used for the determination of sediment transport rate in marine environments. The accuracy of these equations depends upon the definition of the coefficient k(1) in the equations, which is a function of particle size. Hardisty (1983) has attempted to establish the relationship between k(1) and particle size, but there is an error in his analytical result. Our reanalysis of the original flume data results in new formulae for the coefficient. Furthermore, we found that the k(1) values should be derived using u(1) and u(1cr) data; the use of the vertical mean velocity in flumes to replace u(1) will lead to considerably higher k(1) values and overestimation of sediment transport rates.
Resumo:
The South China Sea (SCS) is one of the largest marginal seas in the western Pacific, which is located at the junction of Eurasian plate, Pacific plate and Indian-Australian plate. It was formed by continent breakup and sea-floor spreading in Cenozoic. The complicated interaction among the three major plates made tectonic movement complex and geological phenomena very rich in this area. The SCS is an ideal place to study the formation and evolution of rifted continental margin and sea-floor spreading since it is old enough to have experienced the major stages of the basin evolution but still young enough to have preserved its original nature. As the demand for energy grows day by day in our country, the deep water region of the northern continental margin in the SCS has become a focus of oil and gas exploration because of its huge hydrocarbon potential. Therefore, to study the rifted continental margin of the SCS not only can improve our understanding of the formation and evolution processes of rifted continental margin, but also can provide theoretical support for hydrocarbon exploration in rifted continental margin. This dissertation mainly includes five topics as follows: (1) Various classic lithosphere stretching models are reviewed, and the continuous non-uniform stretching model is modified to make it suitable for the case where the extension of lithopheric mantle exceeds that of the crust. Then simple/pure shear flexural cantilever model is applied to model the basement geometries of SO49-18 profile in the northern continental margin of the SCS. By fitting the basements obtained by using 2DMove software with modeling results, it is found that the reasonable effective elastic thickness is less than 5km in this region. According to this result, it is assumed that there is weak lower crust in the northern continental margin in the SCS. (2) We research on the methods for stretching factor estimation based on various lithosphere stretching models, and apply the method based on multiple finite rifting model to estimate the stretching factors of several wells and profiles in the northern continental margin of the SCS. (3) We improve one-dimension strain rate inversion method with conjugate gradient method, and apply it to invert the strain rate of several wells in the northern continental margin of the SCS. Two-dimension strain rate forward modeling is carried out, and the modeling results show that effective elastic thickness is a key parameter to control basin’s geometry. (4) We simulate divergent upwelling mantle flow model using finite difference method, and apply this newly developed model to examine the formation mechanism of the northwest and central sub-basin in the SCS. (5) We inverse plate thickness and basal temperature of oceanic lithosphere using sea-floor ages and bathymetries of the North Pacific and the North Atlantic based on varied-parameters plate model, in which the heat conductivity, heat capacity and coefficient of thermal expansion depend on temperature or depth. A new empirical formula is put forward based the inversed parameters, which depicts the relation among sea-floor age, bathymetry and heat flow. Then various similar empirical formulae, including the newly developed one, are applied to examine the sea-floor spread issue in the SCS based on the heat flow and bathymetry data of the abyssal sub-basin.
Resumo:
Highly reactive magnesium powder of nanometric size, which was generated by the thermal decomposition of magnesium anthracene . 3THF under vacuum, can react with N-2 under atmospheric pressure, even at 300 degrees C, to form magnesium nitride. The rate and extent of the reaction can be improved effectively by doping the magnesium powder with a small amount of nickel or titanium compounds.