The kinetics of the thermal decomposition of poly(3-hydroxybutyrate) and maleated poly(3-hydroxybutyrate)

The thermal decomposition mechanism of maleated poly(3-hydroxybutyrate) (PHB) was investigated by FTIR and H-1 NMR. The results of experiments showed that the random chain scission of maleated PHB obeyed the six-membered ring ester decomposition process. The thermal decomposition behavior of PHB and maleated PHB with different graft degree were studied by thermogravimetry (TGA) using various heating-up rates. The thermal stability of maleated PHB was evidently better than that of PHB. With increase in graft degree, the thermal decomposition temperature of maleated PHB gradually increased and then declined. Activation energy E. as a kinetic parameter of thermal decomposition was estimated by the Flynn-Wall-Ozawa and Kissinger methods, respectively. It could be seen that approximately equal values of activation energy were obtained by both methods.

Isothermal crystallization kinetics and melting behavior of poly (beta-hydroxybutyrate) and maleated poly (beta-hydroxybutyrate)

The overall isothermal crystallization kinetics and melting behavior of poly(beta-hydroxybutyrate) (PHB) and maleated PHB with different graft degree were studied by using differential scanning calorimetry (DSC). The Avrami analysis indicates that the introduction of maleic anhydride results in the decrease in the overall crystallization rate of PHB, but does not affect its nucleation mechanism and geometry of crystal growth. The activation energy of the overall crystallization process increases with the increase in graft degree. The phenomenon of multiple melting endotherms is observed, which results from melting and recrystallization during the DSC heating run.

Isothermal and nonisothermal melt-crystallization kinetics of syndiotactic polystyrene

Analyses of the isothermal and nonisothermal melt kinetics for syndiotactic polystyrene have been performed with differential scanning calorimetry, and several kinetic analyses have been used to describe the crystallization process. The regime II-->III transition, at a crystallization temperature of 239degrees, is found. The values of the nucleation parameter K-g for regimes II and III are estimated. The lateral-surface free energy, sigma = 3.24 erg cm(-2), the fold-surface free energy, sigma(e) = 52.3 +/- 4.2 erg cm(-2), and the average work of chain folding, q = 4.49 +/- 0.38 kcal/mol, are determined with the (040) plane assumed to be the growth plane. The observed crystallization characteristics of syndiotactic polystyrene are compared with those of isotactic polystyrene. The activation energies of isothermal and nonisothermal melt crystallization are determined to be DeltaE = -830.7 kJ/mol and DeltaE = -315.9 kJ/mol, respectively.

Study on the kinetics of ferrocene derivatives in polymer electrolyte/electrode interface at microelectrode

Heterogeneous electron transfer rate constants (k(s)) and diffusion coefficients (D) of the ferrocene and its derivatives. in a new synthetic comb polymer solvent, poly(dimethylsiloxane-g-monomethylether polyethylene glycol) (SCP), and several other polymer solvents were estimated by using microelectrodes. Also, the influence of various supporting electrolytes on k(s) and D of ferrocene was studied. It was shown that k(s) and D of ferrocene decreased with increasing anionic size of the supporting electrolyte, but k(s) tended to increase with increasing radius of the solvated cation. Also, the cationic size of the supporting electrolytes had little effects on D. The values of k(s) and D for the ferrocene derivatives in the polymer solvents were in sharp contrast to those in monomeric solvents. Thus. the k(s) values were proportional to D in the polymer solvents. which indicates that solvent dynamics control of the electrode reaction. The values of k(s) and D of ferrocene in SCP were larger than those in other polymer solvents indicating that SCP is a good polymer solvent. (C) 2000 Elsevier Science B.V. All rights reserved.

Crystallization kinetics of narrow molecular weight distribution metallocene short-chain-branched polyethylene

Isothermal and non-isothermal crystallization kinetics of three metallocene-catalysed short-chain-branched polyethylene (SCBPE) fractions with different degree of branching were investigated by using differential scanning calorimetry (DSC). Narrow molecular weight fractions (M-w = 20,000 and M-w/M-n < 1.15) are used and the degree of branching (CH3 per 1000C) are 1.6, 10.4, 40 respectively. The regime I - II transition temperature are 119.8C, 115.9 degreesC, 113.3 degreesC with the decreasing of degree of branching. Increasing the branch content decreases the rate of secondary nucleation, i,relative to the rate of surface spreading and so increases the range of supercooling over which regime I exists. The rate of bulk crystallization for both isothermal and non-isothermal crystallization decreases with the increasing of degree of branching. Both Ozawa Equation and Kissinger Equation are invalid for non-isothermal crystallization kinetics of SCBPE fractions,that means the effects of the branched chain on crystallization process are more complex than expected.

Kinetics separation of copper and palladium by sodium hydroxide precipitation and its analytical application

The method of the kinetics separation of copper and palladium by sodium hydroxide precipitation was described. The reaction orders, apparent rate constants, apparent activation energy of the reactions between sodium hydroxide and copper, and palladium were determined, and the introduced error for the determination of palladium with separating copper and-palladium by sodium hydroxide precipitation was calculated, The proposed method has been applied to determine palladium in the aldehyde catalyst with good result.

Isothermal crystallization kinetics of PEO in poly(ethylene terephthalate)-poly(ethylene oxide) segmented copolymers. I. Effect of the sofi-block length

The isothermal crystallization kinetics of poly(ethylene oxide) (PEO) block in two poly(ethylene terephthalate) (PET)-PEO segmented copolymers was studied with differential scanning calorimetry. The Avrami equation failed to describe the overall crystallization process, but a modified Avrami equation, the Q equation, did. The crystallizability of the PET block and the different lengths of the PEO block exerted strong influences on the crystallization process, the crystallinity, and time final morphology of the PEO block. The mechanism of nucleation and the growth dimension of the PEG block were different because of the crystallizability of time PET block and the compositional heterogeneity. The crystallization of the PEO block was physically constrained by the microstructure of time PET crystalline phase, which resulted in a lower crystallization rate. However, this influence became weak with the increase in the soft-block length. (C) 2000 John Wiley & Sons, Inc.

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

The isothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone) are investigated by differential scanning calorimetry over two temperature regions. The Avrami equation describes the primary stage of isothermal crystallization kinetics with the exponent n approximate to 2 for both melt and cold crystallization. With the Hoffman-Weeks method, the equilibrium melting point is estimated to be 406 degrees C. From the spherulitic growth equation proposed by Hoffman and Lauritzen, the nucleation parameter (K-g) of the isothermal melt and cold crystallization is estimated. In addition, the K-g value of the isothermal melt crystallization is compared to those of the other poly(aryl ether ketone)s. (C) 2000 John Wiley & Sons, Inc.

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

Nonisothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone) (PEKEKK) were investigated by differential scanning calorimetry (DSC). The Avrami equation modified by Jeziorny could only describe the primary stage of nonisothermal crystallization kinetics of PEKEKK. Also, the Ozawa equation could not describe its nonisothermal crystallization behavior. A convenient and reasonable kinetic approach was used to describe the nonisothermal crystallization behavior. The crystallization activation energy were estimated to be -264 and 370 KJ/mol for nonisothermal melt and cold crystallization by the Kissinger method. (C) 2000 John Wiley & Sons, Inc.

Miscibility, crystallization kinetics, and morphology of poly(beta-hydroxybutyrate) and poly(methyl acrylate) blends

The miscibility, spherulite growth kinetics, and morphology of binary blends of poly(beta-hydroxybutyrate) (PHB) and poly(methyl acrylate) (PMA) were studied with differential scanning calorimetry, optical microscopy, and small-angle X-ray scattering (SAXS). As the PMA content increases in the blends, the glass-transition temperature and cold-crystallization temperature increase, but the melting point decreases. The interaction parameter between PHB and PMA, obtained from an analysis of the equilibrium-melting-point depression, is -0.074. The presence of an amorphous PMA component results in a reduction in the rate of spherulite growth of PRE. The radial growth rates of spherulites were analyzed with the Lauritzen-Hoffman model. The spherulites of PHB were volume-filled, indicating the inclusion of PMA within the spherulites. The long period obtained from SAXS increases with increased PMA content, implying that the amorphous PMA is entrapped in the interlamellar region of PHB during the crystallization process of PHB. All the results presented show that PHB and PMA are miscible in the melt. (C) 2000 John Wiley & Sons, Inc.

Investigation into self-assembled monolayers of a polyether dendron thiol: Chemisorption, kinetics, and patterned surface

Different sizes of Frechet-type dendrons with a thiol group at the focal point were synthesized, well characterized, and used as building blocks for the preparation of self-assembled monolayers (SAMs) on metal surfaces. From the studies of the kinetic process of dendron thiol self-assembling on gold, it is shown that the dendron thiol assembling proceeds with different adsorption rates depending on the assembly time. In contrast to normal alkanethiols forming highly molecular structures on metal surfaces, the SAMs of polyether dendron form patterned surfaces with nanometer-sized features and in long-range order. It is found that the patterned stripes are closely related to the size of the dendron, and the patterned stripes can be improved by thermal annealing.

Nonisothermal crystallization kinetics of ethylene terephthalate-ethylene oxide segmented copolymers with two crystallizing segments

The nonisothermal crystallization behavior of ethylene terephthalate-ethylene oxide segmented copolymers has been studied by means of differential scanning calorimetry (DSC). The kinetics of ET-EO segmented copolymer under nonisothermal crystallization conditions has been analyzed by the Ozawa equation. During the crystallization of the high-T-m segments (PET), the low-T-m segments (PEO) act as a noncrystalline diluent, the crystallization behavior of PET obeys the Ozawa theory. When the PEO segments begin to crystallize, the PET phase is always partially solidified and the presence of the spherulitic microstructure of PET profoundly influences the crystallization behavior, which results in that the overall crystallization process does not obey the Ozawa equation. (C) 2000 Elsevier Science Ltd. All rights reserved.

A heterogeneous catalytic kinetics for enzymatic biodegradation of poly(epsilon-caprolactone) nanoparticles in aqueous solution

Water insoluble poly(epsilon-caprolactone) (PCL) was micronized into narrowly distributed stable nanoparticles. The biodegradation of such PCL nanoparticles in the presence of the enzyme, Lipase PS, was monitored by using laser light scattering because the scattering intensity is directly related to the particle concentration. The PCL and enzyme concentration dependence of the biodegradation rate supports a heterogeneous catalytic kinetics in which we have introduced an additional equilibrium between the inactive and active enzyme/substrate complexes. The initial rate equation derived on the basis of this mechanism was used to successfully explain the influence of surfactant, pH and temperature on the enzymatic biodegradation. Our results confirmed that both the adsorption and the enzymatic catalysis were important for the biodegradation of the PCL nanoparticles. (C) 2000 Elsevier Science Ltd. All rights reserved.

Phase transition and transition kinetics of a thermotropic poly(amide-imide) derived from 70% pyromellitic dianhydride, 30% terephthaloyl chloride, and 1,3-bis[4-(4 '-aminophenoxy)cumyl]benzene

The phase transition and transition kinetics of a liquid crystalline copoly(amide-imide) (PAI37), which was synthesized from 70 mol% pyromellitic dianhydride, 30 mol% terephthaloyl chloride, and 1,3-bis[4-(4'-aminophenoxy)cumyl]benzene, was characterized by differential scanning calorimetry, polarized light microscopy, X-ray diffraction, and rheology. PAI37 exhibits a glass transition temperature at 182 degreesC followed by multiple phase transitions. The crystalline phase starts to melt at similar to 220 degreesC and forms smectic C (S-C) phase. The Sc phase transforms into smectic A (S-A) phase when the temperature is above 237 degreesC. The S-C to S-A transition spans a broad temperature range in which the S-A phase vanishes and forms isotropic melt. The WARD fiber pattern of PAI37 pulled from the anisotropic melt revealed an anomalous chain orientation, which was characterized by its layer normal perpendicular to the fiber direction. The transition kinetics for the mesophase and crystalline phase formation was also studied.