Isoconversional kinetic analysis of novolac-type lignophenolic resins cure

Several phenomenological models (including simple models by Ozawa and Kissinger and the Kissinger–Akahira–Sunose isoconversional method) have been used to compare the cure kinetics of two lignin-based novolac-type phenolic resins with those from a commercial novolac system. When 45 wt% phenol is substituted by a sulfonated kraft lignin, an important reduction in the activation energy is obtained. This behaviour has been attributed to the incorporation of an extra amount of hydroxymethyl groups in the formulation, as they are present in important quantities in the original lignin structure. KAS isoconversional model shows that the rise in viscosity derived from lignin introduction leads to a moderate change in the limiting stage from a kinetic to a diffusion regime, while condensation reactions, which are favoured by the abundance of lignin hydroxymethyl groups, acquire high relevance in LPF-45 system cure. Finally, competition with other mechanisms initiated at high temperature is reported at high conversion grades for all cases.     

“Model-free” kinetic analysis?

All kinetic analyses aim to determine a sufficient number of kinetic parameters, usually at least an apparent Arrhenius activation energy and pre-exponential factor, and a conversion function or kinetic model (making up a ‘kinetic triplet’), so that accurate extrapolations of kinetic behaviour can be made. “Model-free” methods of kinetic analysis postpone the problem of identifying a suitable kinetic model until an estimate of the activation energy has been made. A major reason for doing this is that misidentification of the kinetic model has a marked effect on the values obtained for the Arrhenius parameters in both isothermal and non-isothermal kinetic analyses. Some aspects of this problem are discussed.

The non-parametric kinetics (NPK) method [1 and 2] is a “model-free” method of kinetic analysis that does not seem to have received the attention that it deserves. This is probably because of its mathematical sophistication and the fact that the matrix and non-linear regression calculations involved are not readily automated. The principle of the method appears to be that of “forcing” a set of non-isothermal data into the set which should have been obtained if the experiments had been carried out isothermally. The method deserves wider testing and also raises some interesting aspects of the philosophy behind non-isothermal kinetic analysis.     

Polymer blends based on an epoxy-amine thermoset and a thermoplastic

The effect of thermoplastic modification of an epoxy-amine system on the cure reaction, miscibility and thermal stability of the system was investigated. The cure kinetics showed an autocatalytic behavior. Modifier did not affect either the total reaction heat or the achieved maximum conversion but delayed the kinetics. The model of Horie-Kamal corrected by diffusion factor was used to adjust kinetics in the whole range of conversions. The modified systems showed two glass transitions indicating two separated phases, whose compositions were estimated using the Fox and Couchman equations. Modifier did not affect the thermal and thermooxidative stability of the system.     

Kinetics study of imidazole-cured epoxy-phenol resins

The reaction kinetics of diglycidyl ether of bisphenol A (DGEBA) cured with different concentrations of imidazole and bisphenol A (BPA) were investigated by using differential scanning calorimetry. Both dynamic and isothermal DSC were studied. Two initiation mechanisms were found to play roles in the curing reactions. One was based on adduct formation of epoxy groups with pyridine-type nitrogen and the other was based on ionic complexes of imidazole and BPA. The subsequent propagation was composed of three main reactions, viz. the epoxide/phenol reaction, the acid/base reaction, and the epoxide/R-O⁻ reaction. A generalized kinetics model was developed and used to predict the conversion of epoxide groups using a wide range of imidazole and BPA concentrations, and cure temperature. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3233–3242, 1999     

Isoconversional kinetic study of alachlor and metolachlor vaporization by thermal analysis

The vaporization kinetics of two acetamide pesticides, namely alachlor and metolachlor, was studied by thermogravimetric analysis under nonisothermal conditions (using heating rates between 1.0 and 10 K min^?1). A model‐free isoconversional method of kinetic analysis was proposed, and activation energy dependences on the extent of conversion α for nonisothermal experiments were given. An increase in activation energy is shown for alachlor from 50 to 60 kJ mol^?1, while E values do not significantly vary in the range α > 0.1: 63 kJ mol^?1 for metolachlor while 60 kJ mol^?1 for alachlor. At the end of vaporization (0.9 < α < 1.0), the activation energies are in close agreement with the enthalpies of vaporization calculated from DSC measurements. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 37: 74–80, 2005     

Comparison between 3-point bending and torsion methods for determining the viscoelastic properties of fiber-reinforced epoxy

Dynamic mechanical analysis is a technique used to determine the viscoelastic properties of polymers and their composites. The storage modulus, loss modulus and loss factor in correlation with the glass transition temperature can be detected by several means. In this study, these properties are determined using a dynamic mechanical analyzer in 3-point bending mode, as well as a rheometer in torsion mode. The materials under consideration are a unidirectional glass fiber-reinforced epoxy, a quasi-isotropic carbon fiber-reinforced epoxy and a quasi-isotropic glass fiber-reinforced epoxy. The results of each method and material are presented and the advantages and limitations of each method are discussed. 3-point bending proved to be more suitable to detect the effect of fiber orientation for unidirectional fiber-reinforced epoxy but requires careful control of sample dimensions for accuracy. Torsion, on the other hand, gave consistent measurements for samples of varying lengths, proving to be a suitable method if materials are scarce and limited.     

Kinetic analysis of isothermal decomposition of 2,4-dinitrophenylhydrazine using differential scanning calorimetry

Differential scanning calorimetry was used to study the thermal decomposition of 2,4-dinitrophenylhydrazine (DNPH) in isothermal regime. The DSC curves were carried out at several constant temperatures lower than the melting temperature. The standard isoconversional analysis of the obtained curves suggests an autocatalytic decomposition mechanism. This mechanism is also supported by the temperature dependence of the observed induction periods.     

Isoconversional method to explore the cure reaction mechanisms and curing kinetics of DGEBA/EMI‐2,4/nano‐SiC system

The curing kinetics of the diglycidyl ether of bisphenol‐A (DGEBA)/2‐ethyl‐4‐methylimidazole (EMI‐2,4)/nano‐sized carborundum (nano‐SiC) system was studied by means of nonisothermal differential scanning calorimetry (DSC). An isoconversional method of kinetic analysis yields a dependence of the effective activation energy E on the extent of conversion that decreases initially, and then increases as the cure reaction proceeds. The variations of E were used to study the cure reaction mechanisms, and the Shrinking Core Model was used to study the resin–particle reaction. The results show that the presence of nano‐SiC particles prevents the occurrence of vitrification, as well as inhibits the cure reaction. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 371–379, 2006     

Rheological and dielectric changes during isothermal epoxy-amine cure

Dynamic viscosity and ionic conductivity were measured simultaneously during the cure of a digylcidyl ether of bisphenol-A (DGEBA) epoxy resin with diamino-diphenyl sulfone (DDS) by mounting a microdielectric sensor into the plates of a rheometer. Two different cure temperatures were examined. Periodically, throughout the cure, samples were removed from the plates of the rheometer, quenched, and analyzed for the glass transition temperature and epoxide conversion. The relationship between conductivity and viscosity appeared to be independent of cure temperature. A linear relation with a slope of ?1 was observed between the natural logarithms of conductivity and viscosity during the cure up to approximately 85% cure conversion. It was hypothesized that the reaction rate was hindered by diffusion at this stage in the polymerization. A free volume relationship was used to successfully correlate conductivity with viscosity up to the diffusion limited region. ©1995 John Wiley & Sons, Inc.     

Application of isoconversional and multivariate non-linear regression methods for evaluation of the degradation mechanism and kinetic parameters of an epoxy resin

The thermo-oxidative degradation of an epoxy resin obtained by curing of an industrially produced DGEBA mixture with 4,4′-methylene-dianiline (MDA) and used as electric insulator has been investigated by TG + DTG + DSC simultaneous analyses performed in static air atmosphere, at five heating rates. TG, DTG and DSC curves showed that, in the temperature range 25-900 °C, a glass transition followed by three thermo-oxidative processes occur. The processing of the non-isothermal data corresponding to the first process of thermo-oxidation was performed by using Netzsch Thermokinetics - A Software Module for Kinetic Analysis. The dependence of the activation energy, evaluated by isoconversional methods, on the conversion degree and the relative high standard deviations of this quantity show that the investigated process is a complex one. The mechanism and the corresponding kinetic parameters were determined by multivariate non-linear regression program and checked for quasi-isothermal data. It was pointed out that the first process of thermo-oxidation of the investigated resin consists in four steps, each step having a specific kinetic triplet. The obtained results were used for prediction of the thermal lifetime of the material corresponding to some temperatures of use and the end point criterion 5% and 10% mass loss.     

The basic processes of polymerization and its real kinetic analysis

The method of computer experiments can be successfully applied to radical polymerization with the inclusion of initiation, propagation and termination. The convenient PC-program TAkin for non-linear estimation of the parameters of calorimetric and thermoanalytical experiments was applied for determination of the activation parameters of chain propagation and termination. The overall evaluation of three or more data sets was preferred. The determination of the kinetic parameters proceeds satisfactorily of the measured curves are strongly different, e.g. with a changed start temperature of modified application of batch and semi-batch technique, including acceptable experimental errors. Eight recommendations for laboratory experts are given.The autors thank Prof. H. A. Schneider (UniversitÄt Freiburg, FMF, Meierstr. 21, D79104 Freiburg) for helpful discussions concerning the rational application of modern kinetic methods.     

The basic processes of depolymerization and its real kinetic analysis

The method of computer-experiments can be applied successfully on the radical depolymerization under inclusion of initiation, depropagation and termination. The comfortable PC-program TA-kin for the non-linear estimation of parameters for TG- or DSC-experiments was applied to the determination of activation parameters of depropagation and termination. Therefore the overall-evaluation of three or more data sets is a prerequisite. The determination of kinetic parameters runs satisfactory if the measured curves are strongly different, e.g. by varying the heating rate, including acceptable experimental errors. Several recommendations for laboratory experts are given. A great support for a very sufficient estimation is the inclusion of simultaneous analysis of the radical concentration.     

Copolyesteramides: synthesis and kinetic analysis

The synthesis of copolyesteramides using para-acetamido benzoic acid (PABA) and polyethylene terephthalate (PET) by melt polymerization has been studied in detail. The performance of three transesterification catalysts are assessed for three different initial compositions, PABA 60 mol%/PET 40%, PABA 50 mol%/PET 50% and PABA 40 mol%/PET 60%. The polycondensations are found to obey second order kinetics, irrespective of whether the reaction was catalysed or not. The mechanism of initial stage polymerization kinetics of the copolymers has been fully explained.It is suggested that acetic acid is evolved only by the homopolymerization of PABA and that the insertion of a monomer of homopolymer of PABA into PET does not yield any acetic acid. A set of differential equations containing three different rate constants, k₁ for homopolymerization of PABA, k₂ for PET reaction with dimer of PABA and k₃ for PABA reaction with copolymer of PABA and PET has been developed and numerically solved, to study the initial stage kinetics. The computed values of acetic acid are compared with the experimentally collected amount and the three rate constants are optimized using a differential algebraic optimization technique. The present model represents the data with an acceptable accuracy with an average % error of less than 5% between experimental and computed values for the entire experimental range. The correlation coefficient values range between 0.988 and 0.999.Differential scanning analysis of the copolyestermides indicates that 40 mol% PABA and 60% PET had the highest enthalpy values of the order of 18 kJ/mol. It is found that within the copolyesteramide series the degree of crystallinity increased with the increase of PET contents in the feed mixture to the batch reactor.     

Isoconversional kinetic analysis of thermal decomposition of 1-butyl-3-methylimidazolium hexafluorophosphate under inert nitrogen and oxidative air atmospheres

Journal of Thermal Analysis and Calorimetry - Non-isothermal decomposition of 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF6) in inert nitrogen and air atmospheres was investigated by...     

The effect of zeolite on the curing of epoxy resin by polyaniline: a kinetic study

Polyaniline sulfate‐zeolite composite was prepared by emulsion polymerization. Epoxy resin was cured using polyaniline‐sulfate salt and various amounts of polyaniline sulfate‐zeolite composite. The kinetics of the cure reaction for an epoxy resin based on the diglycidyl ether of bisphenol A (DGEBA) with polyaniline‐sulfate and polyaniline sulfate‐zeolite composite have been studied using differential scanning calorimetry (DSC) under isothermal and dynamic conditions. Isothermal kinetics analysis was performed using the phenomenological model of Kamal. Dynamic kinetic analysis was performed using Kissinger's method. Copyright © 2002 John Wiley & Sons, Ltd.     

Thermal analysis and kinetic study of decomposition processes of some pesticides

The thermal analysis of some pesticides using simultaneous TG-DSC measurements and kinetic calculations by the dynamic TG technique have been carried out.With this technique it was attempted to group compounds with similar structures according to the shape and number of peaks of their thermoanalytical curves and to characterize their features by means of thermodynamic and kinetic quantities.Small variations in the structure of the components of a class make larger variations in the thermodynamic and kinetic values being in close agreement with the observed differences in their biological behaviour.

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Zusammenfassung Mittels simultanen TG-DSC-Messungen und kinetischen Berechnungen bei der DTG-Technik wurde eine thermische Analyse einiger Pestizide durchgeführt.Mit dieser Methode wurde versucht, Verbindungen mit ähnlichen Strukturen anhand der Form und Anzahl von Peaks ihrer thermoanalytischen Kurven zu gruppieren und ihre Eigenschaften mittels thermodynamischen und kinetischen Mengen zu charakterisieren.Geringe Änderungen in der Struktur der Komponenten einer Klasse verursachen größere Veränderungen der thermodynamischen und kinetischen Größen, was in enger Übereinstimmung mit den beobachteten Unterschieden ihrer biologischen Aktivität steht.

     

Non-isothermal kinetic analysis and feasibilty study of medium grade crude oil field

In this research, non-isothermal kinetics and feasibility study of medium grade crude oil is studied in the presence of a limestone matrix. Experiments were performed at a heating rate of 10°C min⁻¹, whereas the air flow rate was kept constant at 50 mL min⁻¹ in the temperature range of 20 to 600°C (DSC) and 20 to 900°C (TG). In combustion with air, three distinct reaction regions were identified in all crude oil/limestone mixtures, known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO). The activation energy values were in the order of 5–9 kJ mol⁻¹ in LTO region and 189–229 kJ mol⁻¹ in HTO region. It was concluded that the medium grade crude oil field was not feasible for a self-sustained combustion process.     

Application of complex reaction kinetic models in thermal analysis

The complexity of the phenomena which arise during the heating of the various substances seldom can be described by a single reaction kinetic equation. As a consequence, sophisticated models with several unknown parameters have to be developed. The determination of the unknown parameters and the validation of the models requires the simultaneous evaluation of whole series of experiments. We can accept a model and its parameters if, and only if we get a reasonable fit to several experiments carried out at different experimental conditions. In the field of the thermal analysis the method of least squares alone seldom can select abest model or abest set of parameter values. Nevertheless, the careful evaluation of the experiments may help in the discerning between various chemical or physical assumptions by the quality of the corresponding fit between the experimental and the simulated date. The problem is illustrated by the thermal de-composition of cellulose under various experimental conditions.This research program was funded by the National Science Foundation (grant INT 8914934), the US Hungarian Science and Technology Joint Fund (grants 90b-22 and 93b-375), the Hungarian National Research Fund (OTKA, grant 3077/91) and the Coral Industries Endowment.     

Nonisothermal crystallization kinetics of amorphous Te51.3As45.7Cu3

The structure and kinetics of the crystallization reaction of amorphous Te_51.3As_45.7Cu₃ were studied under nonisothermal conditions using scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). Two exothermic changes were reported. Five isoconversional methods, of Kissinger–Akahira–Sunose (KAS), Flynn–Wall–Ozawa (FWO), Tang, Starink, and Vyazovkin, were used to determine the variation of the activation energy for crystallization with temperature, E(T). The results show that the activation energy for crystallization associated with the first peak first decreases with increasing temperature and then increases. Different behaviour was observed for the second peak, where an increase of E with temperature followed by a decrease. The effect of heating rate on the reaction model, g(), was also different for the two crystallization peaks.