Isothermal and nonisothermal transition kinetics of trans-1,4-polybutadiene

Analysis of the isothermal and nonisothermal transitions of hexagonal crystal formation from the melt (transition 1) and of monoclinic crystal formation from hexagonal crystals (transition 2) for trans-1,4-polybutadiene (TPBD) was carefully carried out by differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). Isothermal transitions I and 2 are described by Avrami exponents (n) of approximate to1, whereas nonisothermal transitions I and 2 are described by n approximate to 4. These different eta values indicate that different crystallization mechanisms took place for different crystallization driving forces under isothermal and nonisothermal crystallization. The Ozawa equation was also used to analyze the nonisothermal crystallization data. For transition I at lower temperature, the Ozawa equation fits the data well; however, at higher temperature, there is an inflection that shifts to lower crystallinity with increasing temperature. Inflections are also observed with the Ozawa analysis for transition 2. Furthermore, the crystallinities at the turning points are almost in the same range as those determined by Avrami analysis for nonisothermal transitions I and 2, which suggests that the Ozawa analysis inflections are due to secondary crystallization. However, TEM revealed no morphology discrepancy between the TPBD hexagonal crystals formed from melt by isothermal and nonisothermal crystallization.

Johnson-Segalman流体剪切流动的相平面分析与数值模拟

研究Johnson-Segalman流体的剪切流动行为.首先分析该模型的定常解,从稳定的总剪切应力曲线上可见,当稳定总剪切应力T取值足够大或足够小时,方程有惟一定常解;当T取中间值时,方程定常解不惟一.最后,采用向后差分格式对该模型进行数值模拟.

The glass transition temperatures of PS/PPO blends: Couchman volume-based equation and its verification

The glass transition temperatures (T-g) of PS/PPO blends with different compositions were studied under various pressures by means of a PVT-100 analyzer. A general relation of T-g and pressure of the PS/PPO system was deduced by fitting the experimental T-g's. Couchman volume-based equation was testified with the aid of those data. It was found that the experimental T-g's do not obey the Couchman equation of glass transition temperature based on thermodynamic theory. According to our studies, the major reason of the deviation is caused by the neglect of DeltaV(mix). (C) 2001 Published by Elsevier Science Ltd.

Nonisothermal crystallization behavior of a novel poly(aryl ether ketone): PEDEKmK

Nonisothermal melt crystallization kinetics of PEDEKmK linked by meta-phenyl and biphenyl was investigated by differential scanning calorimetry (DSC). A convenient and reasonable kinetic approach was used to describe the nonisothermal melt crystallization behavior, and its applicability was verified when the modified Avrami analysis by the Jeziorny and Ozawa equation were applied to the crystallization process. The crystallization activation energy was estimated to be -219 kJ/mol by Kissinger method while crystallizing from the PEDEKmK melt nonisothermally. These observed crystallization characteristics were compared to those of the other members of poly(aryl ether ketone) family. (C) 1998 John Wiley & Sons, Inc.

Crystallization behavior of a novel poly(aryl ether ketone): PEDEKmK

Isothermal melt and cold crystallization kinetics of PEDEKmK linked by meta-phenyl and biphenyl were investigated by differential scanning calorimetry in two temperature regions. Avrami analysis is used to describe the primary stages of the melt and cold crystallization, with exponent n = 2 and n = 4, respectively. The activation energies are -118 kJ/mol and 510 kJ/mol for crystallization from the melt and the glassy states, respectively. The equilibrium melting point T-m(0) is estimated to be 309 degrees C by using the Hoffman-Weeks approach, which compares favorably with determination from the Thomson-Gibbs method. The lateral and end surface free energies derived from the Lauritzen-Hoffman spherulitic growth rate equation are sigma = 8.45 erg/cm(2) and sigma(e) = 45.17 erg/cm(2), respectively. The work of chain folding q is determined as 3.06 kcal/mol. These observed crystallization characteristics of PEDEKmK are compared with those of the other members of poly(aryl ether ketone) family. (C) 1997 John Wiley & Sons, Inc.

EQUATION OF STATE FOR POLYMER SOLIDS

A new equation of state for polymer solids is given by P = B0/4 98[(V0/V)7.14 - (V0/V)2.16 + T/T0] comparison of the equation of state with experimental data is made for six kinds of polymers at different temperatures and pressures. The results obtained shown that the equation is suitable to describe the compression behavior of solid polymers in the region without transition.

A NEW ISOTHERMAL EQUATION OF STATE FOR POLYMERS

A new isothermal equation of state for polymers in the solid and the liquid is given by P = B(T, 0)/(n - m){[V(T, 0)/V(T, P)]n + 1 - [V(T, 0)/V(T, P)]m + 1} where n = 6.14 and m = 1.16 are general constant's for polymer systems. Comparison of the equation with experimental data is made for six polymers at different temperatures and pressures. The results predict that the equation of state describes the isothermal compression behaviour of polymers in the glass and the melt states, except at the transition temperature.

DETERMINATION OF THE MARK-HOUWINK EQUATION FOR CHITOSANS WITH DIFFERENT DEGREES OF DEACETYLATION

The values of k and alpha in the Mark-Houwink equation have been determined for chitosans with different degrees of deacetylation (DD) (69, 84, 91 and 100% respectively), in 0.2 M CH3COOH/0.1 M CH3COONa aqueous solution at 30-degrees-C by the light scattering method. It was shown that the values of alpha-decreased from 1.12 to 0.81 and the values of k increased from 0.104 x 10(-3) to 16.80 x 10(-3) ml/g, when the DD varied from 69 to 100%. This is due to a reduction of rigidity of the molecular chain and an increase of the electrostatic repulsion force of the ionic groups along the polyelectrolyte chain in chitosan solution, when the DD of chitosan increases gradually.

EQUATION OF STATE FOR POLYMERS

In the theoretical study on equation of state for polymers, much attention has been paid to the polymer in liquid state, but less to that in solid state. Therefore, some empirical and semi-empirical equations of state have been used to describe its pressure-volume-temperature (P-V-T) relations.

A comparative study of thermolysis characteristics and kinetics of seaweeds and fir wood

Thermal analysis and thermolysis kinetics of three kinds of seaweeds and fir wood (M. glyptostriboides Huet Cheng), a kind of typical land plant, had been conducted. The results showed that thermal stability follows the order of Grateloupia filicina < Ulva lactuca < Dictyopteris divaricata < fir wood. A notable difference on heat flow between seaweeds and fir wood during thermolysis was that the former were mainly connected with exothermic processes at relatively lower temperature regimes. while the latter was connected with an apparent endotherm at a relatively higher temperature regime followed by a maximum exothermic peak. This suggested that the heat coupling might be realized if co-thermolysis of seaweeds and fir wood were carried out. The main devolatilization phase of each seaweed could be described by Avrami-Erofeev equation, which indicated that thermolysis of seaweeds follows the mechanism of random nucleation and nuclei growth, whereas that of fir wood by Z-L-T equation and its thermolysis mechanism was three-dimensional diffusion. The activation energies calculated for both seaweeds and fir wood increase as conversion increases. However, those for the former have wider distribution. (c) 2006 Elsevier Ltd. All rights reserved.

Modification to the Hardisty equation, regarding the relationship between sediment transport rate and particle size

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.

The nonlinear evolution equation on the shallow water wave

Based on the variation principle, the nonlinear evolution model for the shallow water waves is established. The research shows the Duffing equation can be introduced to the evolution model of water wave with time.