Nonisothermal crystallization kinetics: poly(ethylene terephthalate)-poly(ethylene oxide) segmented copolymer and poly(ethylene oxide) homopolymer

The nonisothermal crystallization behavior of polyethylene oxide (PEO) in poly(ethylene terephthalate)poly(ethylene oxide) (PETPEO) segmented copolymer and PEO homopolymer has been studied by means of differential scanning calorimetry, as well as transmission electron microscope. The kinetics of PEO in copolymer and PEO homopolymer under nonisothermal crystallization condition has been analyzed by Ozawa equation. The results show that Ozawa equation only describes the crystallization behavior of PEO-6000 homopolymer successfully, but fails to describe the whole crystallization process of PEO in copolymer because the secondary crystallization in the later stage could not be neglected. Due to the constraint of PET segments imposed on the PEO segments, a distinct two stage of crystallization of PEO in copolymer has been investigated by using Avrami equation modified by Jeziorny to deal with the nonisothermal crystallization data. In the case of PEO-6000 homopolymer, good linear relation for the whole crystallization process is obtained owing to the secondary crystallization does not occur under our experimental condition. (C) 2001 Elsevier Science Ltd. All rights reserved.

Nonisothermal crystallization kinetics of PEO in ethylene terephthalate-ethylene oxide segmented copolymers

The nonisothermal crystallization behavior of Ethylene Terephthalate-Ethylene Oxide (ET-EO) segmented copolymers has been studied with the use of differential scanning calorimetry (DSC). The kinetics of PEO in ET-EO segmented copolymer under nonisothermal crystallization conditions has been analyzed with the Ozawa equation. The results show that there is no agreement with Ozawa's theoretical predictions in the whole crystallization process owing to the constraint of ET segments imposed on the EO segments. A distinct two-crystallization process has been investigated by using the Avrami equation modified by Jeziorny to deal with the nonisothermal crystallization data. The value of the Avrami exponent n is independent of the length of soft segments. However, the crystallization rate is sensitive to the length of soft segments. The longer the soft segments, the faster the crystallization will be.

Diffusion-limited kinetics modeling of one-step polyimide formation

A diffusion-limited kinetic model was developed to describe the imidization of one-step polythioetherimide formation based on an endgroup diffusion model. The changes of conversion and viscosity during the imidization were monitored with thermogravimetric analysis and dynamic stress rheometry, respectively. It was observed that the imidization rate began to decelerate after a fast early stage, whereas the viscosity in the system increased dramatically after a period of low value. Amic acid and imide formations concurrently take place in the one-step polyimide formation, but the formation of amic acid is much slower than that of imide and is the rate-limiting step of imidization. When a second-order kinetic model was used to describe the imidization, the effect of viscosity on the diffusion resistance of reactive groups needed to be included. In order to predict the change of viscosity during the imidization, the Lipshitz-Macosko model was modified and introduced into the diffusion-limited kinetic model by the Stokes-Einstein equation. The comparison of the modeled results with experimental data indicated that the diffusion-limited kinetic model and the modified Lipshitz-Macosko model were able to efficiently predict the changes of conversion and viscosity with temperature and time during the one-step polythioetherimide formation. (C) 2001 John Wiley & Sons, Inc.

Non-isothermal crystallization kinetics of the poly(3-alkylthiophenes)

According to the data obtained from Differential Scanning Calorimetry (DSC),the method of Jeziorny, BOPOXOBCKHH and a new approach proposed by our laboratry are applied to study the nonisothermal crystallization behavior of poly( 3-dodecylthiophene) (P3DDT) and poly(3-octadecylthiophene) (P3ODT),and Kissinger method is used to get the value of the crystallization activation energy. The effect of the different alkyl substitution on crystallization is also investigated. In comparison to the methods of Jeziorny and BOPOXOBCKHH in which it can be found that the deviation from the line occurs in the later stage of crystallization, the new approach appears applicable due to the better linear relation. The values of the crystallization activation energy of P3DDT and P3ODT are estimated as 184.78kJ/mol and 246.93kJ/mol, respectivley, which implies that it is easiser to crystallize P3DDT than P3ODT.

EQCM characterization of self-assembled kinetics of 4-pyridyl hydroquinone at Pt surface and its ion transfer in electrochemical redox

The adsorbed kinetics, proton transportation in electrochemical redox process of 4-pyridyl hydroquinone (4PHQ) self-assembled monolayer (SAM) modified Pt electrode were studied by electrochemical quartz crystal microbalance (EQCM) in situ. It proved that the electrode was modified by a monolayer and underwent a rapid electron transfer. It was a slow adsorbed kinetic process. The ion transfer in the electrochemical redox at the SAM-modified electrode surface mainly involved into the hydrate hydrogen ion.

Isothermal and non-isothermal crystallization kinetics of syndiotactic polypropelene

Isothermal and non-isothermal crystallization kinetics of a syndiotactic polypropylene(sPP) sample synthesized by new metallocene catalyst at different annealing temperatures and different cooling rates have been investigated by using differential scanning calorimetry(DSC) and density analysis. The equilibrium melting temperature( T-m(0)) is 158 degrees C by Hoffman-Weeks method. The equilibrium heat of fusion(Delta H-m(0)) is 88J/g in terms of the density analysis and DSC methods. The lateral and end surface free energies derived from the Lauritzen-Hoffman spherulitic growth rate equation are sigma = 5.2erg/cm(2) and sigma(e) = 69erg/cm(2), respectively. The work of chain folding is determined to be q = 33.75kJ/mol. Modified Avrami equation and Ozawa equation can be used to describe the non-isothermal crystallization behavior. And a new and convenient approach by combining the Avrami equation and Ozawa equation in a same crystallinity is used to describe the non-isothermal behavior as well. The crystallization activation energies are evaluated to be 73.7kJ/mol and 73.1kJ/mol for isothermal crystallization and non-isothermal crystallization, respectively. The Avrami exponent n is 1.5 similar to 1.6 for isothermal crystallization procedure, while the Avrami exponent n,is 2.5 similar to 3.5 for non-isothermal crystallization procedure. This indicated the difference of nucleation and growth between the two procedures.

Ultrasonic relaxation kinetics on fast deuteron transfer reaction

Propylamine has been selected to investigate the isotope effect of a fast deuteron transfer reaction by ultrasonic relaxation method. Ultrasonic absorption coefficients of propylamine in heavy water (D2O) at 25 degrees C in the concentration range from 0.0107 to 0.6300 mol dm(-3) have been measured by pulse and resonance methods over the frequency range from 0.8 to 220 MHz. A Debye-type single relaxation absorption has been observed in the solution. From the dependence of the ultrasonic relaxation parameters on the concentration and solution pH, the source of the observed relaxation has been attributed to a perturbation of the chemical equilibrium associated with the deuteron transfer reaction. The rate and equilibrium constants have been determined by the measurement of the deuteroxyl ion concentration dependence of the relaxation frequency. Also the standard volume change of the reaction has been determined from the concentration dependence of the maximum absorption per wavelength and the adiabatic compressibility has been calculated from the density and the sound velocity in the solution. These results have then been compared with those obtained for propylamine in light water (H2O). The forward rate constant is greater and the reverse rate constant is smaller in DO than in H2O. The standard volume change for deuteron transfer is greater than that for proton transfer reaction, and the adiabatic compressibility shows a similar trend. These data support an argument that there exists a stronger hydrogen bond in D2O than in H2O. The difference of the stability in the intermediate states, R-ND3+... OD- and R-NH3+... OH-, has also been considered from the results of the isotope effects.

A study of dimethylferrocene diffusion and electrode kinetics using microelectrode voltammetry in poly(ethylene glycol) solvent

The heterogeneous electron transfer rate constant (k(s)) of dimethylferrocene (DMFc) was estimated using cyclic voltammetric peak potential separations taken typically in a mixed diffusion geometry regime in a polyelectrolyte, and the diffusion coefficient (D) of DMFc was obtained using a steady-state voltammogram. The heterogeneous electron transfer rate constant and diffusion coefficient are both smaller by about 100-fold in the polymeric solvent than in the monomeric solvent. The results are in agreement with the difference of longitudinal dielectric relaxation time (tau(L)) in the two kinds of solvents, poly(ethylene glycol) (PEG) and CH3CN, indicating that k(s) varies inversely with tau(L); k(s), is proportional to D of DMFc. Both D and k(s) of DMFc in PEG containing different supporting electrolytes and at different temperatures have been estimated. These results show that D and k(s) of DMFc increase with increasing temperature in the polyelectrolyte, whereas they vary only slightly with changing the supporting electrolyte.

Isothermal crystallization kinetics and melting behavior of poly(beta-hydroxybutyrate)/poly(vinyl acetate) blends

The overall isothermal crystallization kinetics and melting behavior of poly(beta-hydroxybutyrate) (PHB)/poly(vinyl acetate) (PVAc) blends were studied by using differential scanning calorimetry(DSC). The Avrami analysis indicates that the addition of PVAc into PHB results in the decrease in the overall crystallization rate of the PHB phase, but does not affect PHB's nucleation mechanism and geometry of crystal growth. The activation energy of the overall process of crystallization increases with the increasing PVAc content in the blends. The phenomenon of multiple melting endotherms is observed, which is caused by melting and recrystallization during the DSC heating run. (C) 1998 Elsevier Science Ltd. All rights reserved.

Crystallization kinetics of poly(ether ether ketone) (PEEK) from its metastable melt

After isothermal crystallization of the amorphous poly(ether ether ketone), double endothermic behaviour can be found through differential scanning calorimetry experiments. During the heating scan of semicrystalline PEEK, a metastable melt, which comes from the melt of the thinner lamellar crystal populations, can be obtained between these two endotherms. The metastable melt can recrystallize immediately just above the lower melting temperature and form slightly thicker lamellae than the original ones. The thickness and the perfection depend upon the crystallization time and the crystallization temperature. By comparing the TEM morphological observations of the samples before and after partial melting, it can be shown that lamellar crystals, having different thermodynamic stability, form during isothermal crystallization. After partial melting, only the type of lamellar crystal exhibiting the higher thermodynamic stability remains. Wide angle X-ray diffraction measurements shows a slightly change in the crystallinity of the samples before and after the partial melting. Small angle X-ray scattering results exhibit a change in the long period of the lamellar crystals before and after the partial melting process. The crystallization kinetics of the metastable melt can be determined by means of differential scanning calorimetry. The kinetic analysis showed that the isothermal crystallization of the metastable PEEK melt proceeds with an Avrami exponent of n = 1.0 similar to 1.4, reflecting that probably one-dimensional or an irregular line growth of the crystal occurred between the existing main lamellae with heterogeneous nucleation. (C) 1998 Elsevier Science Ltd. All rights reserved.

Isothermal and nonisothermal crystallization kinetics of nylon-11

Analysis of the isothermal, and nonisothermal crystallization kinetics of Nylon-11 is carried out using differential scanning calorimetry. The Avrami equation and that modified by Jeziorny can describe the primary stage of isothermal and nonisothermal crystallization of Nylon-11. In the isothermal crystallization process, the mechanism of spherulitic nucleation and growth are discussed; the lateral and folding surface free energies determined from the Lauritzen-Hoffman equation are sigma = 10.68 erg/cm(2) and sigma(e) = 110.62 erg/cm(2); and the work of chain folding q = 7.61 Kcal/mol. In the nonisothermal crystallization process, Ozawa analysis failed to describe the crystallization behavior of Nylon-ii. Combining the Avrami and Ozawa equations, we obtain a new and convenient method to analyze the nonisothermal crystallization kinetics of Nylon-11; in the meantime, the activation energies are determined to be -394.56 and 328.37 KJ/mol in isothermal and nonisothermal crystallization process from the Arrhonius form and the Kissinger method. (C) 1998 John Wiley & Sons, Inc.

The kinetics study in liquid-liquid systems with constant interfacial area cell with Laminar flow

A novel constant interfacial cell with laminar flow is proposed as an approach to obtain extraction kinetics data in liquid-liquid systems. Applications and theoretical fundamentals of the apparatus have been elaborated.. The equation which can express the mass transfer of liquid-liquid system run in the constant interfacial cell with laminar flow is deduced. Simulations from the equations indicate that diffusivity is a suitable factor to represent the characteristics of extraction kinetics rather than the extraction rate in the diffusion controlling step. The dependence of the aqueous phase concentration on time is recommended to determine the extraction regime. The diffusivities of the EuCl3-HDEHP extraction system obtained by different methods are compared to certify the hydrodynamic theory of the cell. The diffusivities of the ErCl3-HEH/EHP extraction system are determined, which show that this technique is a convenient method to obtain the diffusivities in the liquid-liquid system and to determine the extraction regime. (C) 1998 Elsevier Science Ltd. All rights reserved.

Nonisothermal crystallization kinetics of poly(beta-hydroxybutyrate)

Kinetics of nonisothermal crystallization of poly( beta-hydroxybutyrate) from melt and glassy states were performed by differential scanning calorimetry under various heating and cooling rates. Several different analysis methods were used to describe the process of nonisothermal crystallization. The results showed that both Avrami treatment and a new method developed by combining the Avrami equation and Ozawa equation could describe this system very well. However, Ozawa analysis failed. By using an evaluation method, proposed by Kissinger, activation energies have been evaluated to be 92.6 kJ/mol and 64.6 kJ/mol for crystallization from the glassy and melt state, respectively. (C) 1998 John Wiley & Sons, Inc.

Studies of ferrocene derivative diffusion and heterogeneous kinetics in polymer electrolyte by using microelectrode voltammetry

The heterogeneous electron transfer rate constants (k(s)) of seven ferrocene derivatives were estimated using cyclic voltammograms under mixed spherical/semi-infinite linear diffusion and steady-state voltammetry at a microdisk electrode in polymer electrolyte. The k(s) and diffusion coefficient (D) are both 100 to 1000-fold smaller in polymer solvent than in monomeric solvents, and the D and k(s) decrease with increasing polymer chain length. The results conform to the difference of viscosity (eta) or relaxation time (tau(L)) for these different solvents. The k(s) and D increase with increasing temperature, and the activation barriers of the electrode reaction are obtained. The influences of the substituting group in the ferrocene ring on k(s) and D are discussed. The k(s) are proportional to the D of the ferrocene derivatives, which indicates that solvent dynamics control the electrode reaction. (C) 1998 Elsevier Science S.A.

Isothermal melt and cold crystallization kinetics of poly(aryl ether ether ketone ketone) (PEEKK)

Isothermal melt and cold crystallization kinetics of PEEKK have been investigated by differential scanning calorimetry in two temperature regions. During the primary crystallization process, the relative crystallinity develops with a time dependence described by the Avrami equation, with exponent n = 2 for both melt and cold crystallization. The activation energies are -544.5 and 466.7 kJ/mol for crystallization from the melt and amorphous glassy state, respectively. The equilibrium melting point T-m(o) is estimated to be 371 degrees C by using the Hoffman-Weeks approach. The lateral and end surface free energies derived from the Lauritzen-Hoffman spherulitic growth rate equation are sigma=10 erg/cm(2) and sigma(e) = 60 erg/cm(2), respectively. The work of chain folding q is determined as 3.98 kcal/mol. These observed crystallization kinetic characteristics of PEEKK are compared with those of PEEK. (C) 1997 Elsevier Science Ltd.