Cyclo dehydration reaction of polyhydrazides. II. Kinetic parameters obtained from isothermal thermogravimetry

The kinetics of the thermal conversion reaction of poly-(1,3-phenyl-1,4-phenyl)-hydrazide into poly-(1,3-phenyl-1,4-phenyl)-1,3,4-oxadiazole have been studied with isothermal thermogravimetry in continuation of a study with nonisothermal thermogravimetry described in a previous paper. Although the isothermal measurements are much more time-consuming, they provide some new information and insight about the cyclo dehydration reaction of the polyhydrazide. The physical state of the sample, rubbery or glassy, seems to influence the kinetics considerably. The kinetic parameters determined with the isothermal method for the polymer in its glassy state agree well with the parameters derived from the previously reported nonisothermal measurements, while the kinetic parameters for the expected rubbery state differ considerably. The morphological state or the history of the polymer has also a considerable influence on the kinetics of the isothermal conversion process. The powder form of the polymer has a much lower isothermal conversion rate than the film form

Gas separation properties of a thermally stable and chemically resistant polytriazole membrane

The polymer poly (1,3-phenyl-1,4-phenyl)-4-phenyl-1,3,4-triazole has been investigated for its gas separation properties. This thermally stable and chemically resistant polymer can be processed into membranes by the phase-inversion technique because of its unexpectedly good solubility in formic acid. Homogeneous membranes have been tested with respect to their permeability for several gases, and the influence of time and temperature upon permeation has been investigated. The polymer shows reasonable permeabilities for several gases and excellent selectivities. After a conditioning time of several days in which the permeability of the faster-moving gases increases by a factor of about 2, the permeation properties of the polymer remain constant for at least two months. A thermal treatment at 295°C, just above the glass transition temperature, can reduce the conditioning time and can prevent the film from shrinkage at high permeation temperatures without affecting the permeation properties

Thermal behavior of polytriazole films: a thermal analysis study

The thermal behavior of poly(1,3-phenyl-1,4-phenyl)-4-phenyl-1,2,4-triazole has been investigated using different scanning calorimetry (DSC) and thermogravimetry (TG). Processes are studied for this thermally stable polymer that take place between 200 and 500°C. While the polycondensation reaction product in powder from appeared to be partially crystalline, films prepared by casting from a formic acid solution appeared to be completely amorphous. A thermal treatment between Tg(~ 270°C) and Tm(~430°C) can introduce crystallinity in the films because of the polymer's ability to cold crystallize. The cold crystallization temperature Tc seems to be dependent on the preparation history of the solid polymer phase. Thermal annealing of the films just below Tg does not introduce crystallinity but inhibits subsequent cold crystallization at higher temperatures. Crystallization upon cooling from the crystalline melt has not been observed either. At temperatures just above the crystalline melting point the polymer starts to decompose in an exothermic reaction

Cyclo dehydration reaction of polyhydrazides. I. Kinetic parameters obtained with nonisothermal thermogravimetry

The thermal conversion reaction of poly-(1,3-phenyl-1,4-phenyl)-hydrazide into poly-(1,3-phenyl-1,4-phenyl)-1,3,4-oxadiazole has been studied using thermogravimetry (TG). For the evaluation of the energie of activation and other kinetic parameters of this cyclo dehydration reaction a method developed by Ozawa was used, where polymer samples are heated with different constant heating rates. With this method the energy of activation can be determined accurately as a function of the degree of conversion. In this way a parallel reaction could be observed starting at the end of the nonisothermal conversion process. The polymer was used in two different morphological states, a powder and a film. A slightly higher energy of activation and a considerably higher pre-exponential factor were observed for the film indicating a dependency of the kinetics on the morphological state or on the history of the polymer sample

Reactions with 1.3 propane sultone for the synthesis of cation-exchange membranes

For several reasons it is interesting for membrane technology to introduce strongly anionic groups in membranes. Therefore the possibilities of 1.3 propane sultone were studied to modify cellulose, cellulose acetate and polyacrylonitrile.\ud \ud The results showed that cellulose and cellulose acetate could be modified by a direct reaction of 1.3 propane sultone with the available hydroxyl groups. The nitrile groups in polyacrylonitrile had to be reacted first with hydrogen sulphide to give reactive thioamide groups, able to react with the sultone. These results give evidence for 1.3 propane sultone being a useful chemical for modification of polymers, its carcinogenic properties will however prevent application

Cyclodehydration reaction of polyhydrazides. III. Influence of the sample history

The influence of preparation history upon the thermal cyclodehydration reaction of polyhydrazide samples has been investigated. Solid polyhydrazide samples were prepared from DMSO solutions using the phase-inversion technique. Significant differences in conversion rates were observed between samples prepared by nonsolvent immersion precipitation and by evaporation of solvent. It appeared that contact with the nonsolvent water during the sample preparation process has considerable influence on the conversion rate. Not only does the immersion in and washing with water lead to a better removal of the solvent also the pH of the water determines the rate of conversion. A distinct change in the conversion rate is found for washing water at a pH of 7. Basic washing solutions showing lower conversion rates than acid ones. A mechanism explaining these phenomena is proposed

Analysis of the polarization properties of dual polarized inverted vee dipole antennas over a ground plane

This paper presents the derivation of an explicit closed-form expression of dual-polarized inverted-vee dipole antenna behavior based upon electromagnetic theory and physical explanations. The expression is used to determine the intrinsic cross-polarization ratio (IXR) as function of the droop angle, position of the sky-vector, the height above a ground plane and frequency. The expression is verified using full-wave simulations with a Method-of-Moments solver, and shows excellent agreement with simulations. It explains the increase observed in IXR if an infinite perfect electric conductor ground plane is deployed

3D-to-2D Transition of Anion Vacancy Mobility in CsPbBr₃under Hydrostatic Pressure

We study the effects of hydrostatic pressure in the range 0.0--2.0 GPa on anion mobility in the orthorhombic $Pnma$ phase of CsPbBr$_{3}$. Using density functional theory and the climbing nudged elastic band method, we calculate the transition states and activation energies for anions to migrate both within and between neighbouring PbBr$_{3}$ octahedra. The results of those calculations are used as input to a kinetic model for anion migration, which we solve in the steady state to determine the anion mobility tensor as a function of applied pressure. We find that the response of the mobility tensor to increasing pressure is highly anisotropic, being strongly enhanced in the $(010)$ lattice plane and strongly reduced in the direction normal to it at elevated pressure. These results demonstrate the potentially significant influence of pressure and strain on the magnitude and direction of anion migration in lead--halide perovskites.Comment: 25 pages, 3 figure