Application of Monte‐Carlo simulation to estimate the kinetic parameters for pyrolysis—Part I

A mathematical model was developed to represent pyrolysis. The components of primary and secondary pyrolysis reactions were simply lump into different groups and were represented through a set of pseudo‐first‐order reactions. This study presents an algorithm to estimate the kinetic parameters using Monte‐Carlo (MC) simulation. The combination of an analytical reaction model and the MC simulation technique rapidly generates a large number of numerical values. Results show that MC‐simulated data and experimental data are in fair agreement. Though the technique developed in this study proved to have potential, more experimental data are needed to check the robustness of the model. © 2011 Canadian Society for Chemical Engineering     

Pyrolysis and thermo‐oxidative degradation of polycyclopentadiene

Thermal degradation of polycyclopentadiene polymer (PCPD) was investigated by pyrolysis gas chromatography (PGC) in the temperature range of 500–950°C. The nature and composition of the pyrolyzates at various temperatures are presented, and the mechanism of degradation is explained. The activation energy of decomposition (E_a) was obtained from an Arrhenius‐type plot using the concentration of the product ethylene (C₂) at different pyrolysis temperatures and the value was found to be 138 kJ mol⁻¹. Thermo‐oxidative degradation of PCPD in the presence of ammonium perchlorate (AP), the most commonly used oxidizer for polymeric fuel binders, was studied at a pyrolysis temperature of 700°C. The compositions of the products with varying amounts of AP are given, and the exothermicity of oxidative decomposition reactions is evaluated. The energetics of the degradation processes are compared with those of polybutadiene type polymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 635–641, 2000     

Thermal degradation of flax: The determination of kinetic parameters with thermogravimetric analysis

The thermal degradation of flax was investigated with thermogravimetric analysis. The flax used for these experiments underwent different stages of retting or, in one case, boiling. The most retted type of flax was also chemically treated to obtain elementary fibers. These samples were all tested in dynamic and isothermal runs after careful sample preparation. The resulting thermograms were analyzed and later used to calculate the kinetic parameters of cellulose degradation. These kinetic parameters included reaction constants and activation energies. A clear difference in the various tested types of flax was observed through a comparison of these values, and an explanation for these differences was suggested. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2634–2643, 2002     

Thermal degradation mechanism of poly(ether imide) by stepwise Py–GC/MS

The thermal degradation of poly(ether imide) (PEI) was studied through a combination of thermogravimetric analysis and stepwise pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) techniques with consecutive heating of the samples at fixed temperature intervals to achieve narrow temperature pyrolysis conditions. The individual mass chromatograms of various pyrolysates were correlated with pyrolysis temperatures to determine the pyrolysis mechanism. The major mechanisms were two‐stage pyrolysis, involving main‐chain random scission, and carbonization. In the first stage, the scission of hydrolyzed imide groups, ether groups, and isopropylidene groups produced CO+CO₂ and phenol as the major products and was accompanied by chain transfer of carbonization to form partially carbonized solid residue. In the second pyrolysis stage, the decomposition of the partially carbonized solid residue and remaining imide groups formed CO+CO₂ as the major product along with benzene and a small amount of benzonitrile. The yield of CO+CO₂ was the largest fraction in the total ion chromatogram of the evolved gas mixtures. Hence, the thermal stability of the imide group was identical to the maximum thermogravimetry loss rates in the two‐stage pyrolysis regions. Afterward, carbonization dominated the decomposition of the solid residue at high temperatures. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1151–1161, 2001     

Thermal degradation and combustion of polymeric blends

The thermal stability of polymer blends was investigated by means of gas chromatography–mass spectroscopy (GC/MS) and thermal analysis. Evaluated changes in thermal stability can be attributed to blending. On the other hand, we were interested in whether blending may provide a method to control thermal stability and combustibility of polymeric materials. A new scheme of thermal degradation for polystyrene‐polydimethylsiloxane (PDMS) blend was suggested. In the case of polystyrene (PS) as a part of the blend, the products of degradation of PS diffuse through the phase boundary, which cause interaction with PDMS polymers. Apparently, PDMS acts as an inert component, slowing down the termination reaction by dilution of macroradicals formed in random scission degradation process of the PS component. On the other hand, it stabilizes the PS by means of interpolymer recombination, which leads to cross products of thermal degradation. Two of the degradation products: 2‐phenyl‐4(1′,3′,3′,5′,5′‐pentamethylcyclotrisiloxane)‐butane and 2‐phenyl‐4(1′,3′,3′,5′,5′,7′,7′‐heptamethylcyclotrisiloxane)‐butane were assigned to the products of cross‐interpolymer recombination which can accelerate the process of PDMS depolymerization by means of radical initiation of PS* fragments. The connection between a polymer thermal oxidative degradation and its combustion under diffusion flames condition was shown by using composition of polypropylene‐polypropylene‐co‐polyethylene (PP/PP‐co‐PE). In general, the solid‐phase polymer reaction can play a very important role in the reduction of polymer combustibility. It was shown that the composition of PP/PP‐co‐PE (62 : 38) has the highest induction period of autooxidation, which correlates with its combustibility. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3300–3311, 2002     

Flammability of polyacrylonitrile and its copolymers II. Thermal behaviour and mechanism of degradation

Homopolymeric polyacrylonitrile and fibre-forming copolymers containing either vinyl acetate or methyl acrylate comonomer have been studied by thermal analysis (DSC, TGA and DTG) at various heating rates (10–100 K min^?1) and under air and nitrogen. Three well-defined pyrolysis stages have been observed which occur over the temperature ranges 250–350°C, 350–550°C and above 550°C. Each stage involves a competition between volatilisation and cyclisation or char-forming reactions which depends on heating rate and the presence or absence of oxygen. The well-established dominance of cyclisation in the 250–350°C temperature range obtained during carbon fibre production from acrylic precursors occurs only at low heating rates. At high heating rates, volatilisation dominates and this explains why acrylic polymers have high flammabilities when heating rapidly. The full pyrolysis mechanism has been semi-quantitatively analysed and the role that comonomers play discussed. This has enabled a fuller understanding of the potential burning behaviour of these polymers to be developed.     

Two‐step consecutive reaction model and kinetic parameters relevant to the decomposition of Chinese forest fuels

Decomposition of some Chinese forest fuels has been studied by means of nonisothermal thermogravimetric analysis in oxidative and inert atmosphere at low heating rates. A comparison between thermogravimetric curves obtained in air and nitrogen shows that the existence of oxygen enhances the decomposition rate and changes the mechanisms of thermal degradation. After the water evaporation, two well‐defined decomposition stages have been observed in thermogravimetric curves obtained in air, which correspond to oxidative degradation of main components and oxidation of char formed. A kinetic model named “two‐step consecutive reaction model” is developed to describe the thermal degradation process of these materials in air, and there is a good agreement between the experimental and calculated thermogravimetric and derivative thermogravimetric curves. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 571–576, 2006     

Thermal degradation of new copolymers from pyromellitic anhydride

A series of new copolyimides has been synthesized from pyromellitic anhydride. Copoly(imide esters) and copoly(imide amides) were synthesized from bis(N-methylcarboxychloride)pyromellitimide with diols and amines, respectively. One copoly(imide amine) was obtained from bis(N-allyl)pyromellitimide and piperazine via the Michael reaction. The thermal degradation of the copolymides obtained was studied by direct pyrolysis mass spectrometry. Our results show that a selective β-CH hydrogen transfer reaction occurs in copoly(imide esters) containing 1,3-propyl and 1,6-hexane diols, while an intramolecular ester exchange process takes place in copoly(imide ester) with a neopentylglycol moiety. Copoly(imide amide) containing 1,6-hexane diamine decomposes by an N-H hydrogen transfer process, although extensive crosslinking is observed, while that containing piperazine decomposes by an -CH hydrogen transfer. In contrast, copoly(imide amine) undergoes a very selective depolymerization process, yielding bis(N-allyl)pyromellitimide and piperazine.     

Thermal degradation of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) as studied by TG,TG–FTIR,and Py–GC/MS

The thermal degradation kinetics of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [poly(HB–HV)] under nitrogen was studied by thermogravimetry (TG). The results show that the thermal degradation temperatures (T_o, T_p, and T_f) increased with an increasing heating rate (B). Poly(HB–HV) was thermally more stable than PHB because its thermal degradation temperatures, T_o(0), T_p(0), and T_f(0)—determined by extrapolation to B = 0°C/min—increased by 13°C–15°C over those of PHB. The thermal degradation mechanism of PHB and poly(HB–HV) under nitrogen were investigated with TG–FTIR and Py–GC/MS. The results show that the degradation products of PHB are mainly propene, 2‐butenoic acid, propenyl‐2‐butenoate and butyric‐2‐butenoate; whereas, those of poly(HB–HV) are mainly propene, 2‐butenoic acid, 2‐pentenoic acid, propenyl‐2‐butenoate, propenyl‐2‐pentenoate, butyric‐2‐butenoate, pentanoic‐2‐pentenoate, and CO₂. The degradation is probably initiated from the chain scission of the ester linkage. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1530–1536, 2003     

Thermal and fire degradation of recycled and polluted polypropylene‐based materials

In this study, the effect of processing cycles and two pollutants (engine oil (HM) and ethylene glycol (EG)) on the thermal and rheological properties of polypropylene‐based materials (108MF97 and 7510) has been studied. It was investigated if polymers coming from bumper face bar could keep their properties and can be reused after recycling. The different results demonstrate that the two polymers that were polluted and recycled do not show any decrease of their intrinsic properties. Moreover, for one of the two polymers (108MF97), the presence of engine oil enables to increase the thermal stability and reaction to fire. Finally, it appears that the reuse of such polymers is possible. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Multi-scale simulations of the thermal degradation of thin wooden plates: Evaluation of two kinetic mechanisms

This study evaluates two kinetic mechanisms to predict, on matter-level and material-level scales, the thermal degradation of thin plates of oak and eucalyptus as representing vegetative fuel involved in wildfires. The lumped mechanism considers four successive steps, whereas the simplified one includes two steps. The kinetic parameters of these mechanisms were identified with thermogravimetric analysis in air for heating rates between 2 and 30 °C min^?1. On the matter-level scale, kinetic mechanisms were tested for heating rates inside and outside the parameters optimization range. The simulations of the mass loss were close to the experimental data. The lumped mechanism gave better results than the simplified one. On the material-level scale, the mass loss and temperature recorded during thermal degradation of thin wooden plates, with a heating cone, were compared to simulations performed with GPYRO. When only the gasification stage occurred, both mechanisms predicted results close to the experimental data. When char oxidation occurred, the beginning of the gasification stage was well predicted, whereas some differences appeared during the transition between the gasification and char oxidation stages. The performance of both mechanisms indicates that a two-step mechanism is capable of modeling the thermal degradation of thin wooden plates on a material scale.     

Some remarks on the use of isothermal thermogravimetric data for the evaluation of kinetic parameters. Applications for degradation of polymeric materials

A critical analysis of the isoconversional methods for evaluating kinetic parameters of decomposition of solids from isothermal thermogravimetric data is presented. An isoconversional integral method to evaluate the activation energy is suggested. This method allows removing the errors due the correction of the degradation time by subtracting the induction period to onset of the main reaction (also including the time required to heat the sample to the temperature at which the isotherm is recorded). This procedure was used to study the degradation of two series of polymeric materials, (a) poly(vinyl chloride)/acrilonitrile–butadiene–styrene (PVC/ABS) blends and (b) poly(vinyl chloride)/chlorinated poly(ethylene) (PVC/CPE) blends. The values obtained for the activation energy are in fairly good agreement with those obtained from the Prout–Tompkins model in case (a) and from nonisothermal data in case (b). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 355–360, 2003     

Synthesis,characterization, and kinetic of thermal degradation of oligo‐2‐[(4‐bromophenylimino)methyl]phenol and oligomer‐metal complexes

Oligo‐2‐[(4‐bromophenylimino)methyl]phenol (OBPIMP) was synthesized from the oxidative polycondensation reaction of 2‐[(4‐bromophenylimino)methyl]phenol (BPIMP) with air and NaOCl oxidants in an aqueous alkaline medium between 50 and 90°C. The yield of OBPIMP was found to be 67 and 88% for air and NaOCl oxidants, respectively. Their structures were confirmed by elemental and spectral such as IR, ultraviolet–visible spectrophotometer (UV–vis), ¹H‐NMR, and ¹³C‐NMR analyses. The characterization was made by TG‐DTA, size exclusion chromatography, and solubility tests. The resulting complexes were characterized by electronic and IR spectral measurements, elemental analysis, AAS, and thermal studies. According to TG analyses, the weight losses of OBPIMP, and oligomer‐metal complexes with Co⁺², Ni⁺², and Cu⁺² ions were found to be 93.04%, 59.80%, 74.23%, and 59.30%, respectively, at 1000°C. Kinetic and thermodynamic parameters of these compounds investigated by Coats‐Redfern, MacCallum‐Tanner, and van Krevelen methods. The values of the apparent activation energies of thermal decomposition (E_a), the reaction order (n), preexponential factor (A), the entropy change (ΔS*), enthalpy change (ΔH*), and free energy change (ΔG*) obtained by earlier‐mentioned methods were all good in agreement with each other. It was found that the thermal stabilities of the complexes follow the order Cu(II) > Co(II) > Ni(II). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal degradation of ethylene–carbon monoxide alternating copolymer under inert atmosphere

This work aims to understand the mechanism of the thermal degradation of the ethylene–carbon monoxide (E-CO) alternating copolymer under mild conditions. The copolymer was subjected to accelerated ageing in an oven at different temperatures below the copolymer melting point, under argon atmosphere, and in the absence of light. The properties of the aged samples were compared with the properties of the untreated copolymer. Untreated and aged samples were analysed by mass spectroscopy (MS) with the direct introduction probe (DIP) and pyrolysis (Py) techniques. The accelerated ageing experiments showed that the thermal degradation of the E-CO alternating copolymer under inert atmosphere is characterized by chain cross-linking, loss of water, and changes in the UV absorption spectrum. The IR spectrum shows modifications only for highly degraded samples in which O−H and C=C groups are present. The experiments performed with the DIP-MS technique have confirmed that the E-CO alternating copolymer loses water during its thermal ageing. The pyrolysis products of the copolymer are linear molecules with 1,4-diketonic structure, 2-cyclopentenone derivatives, alkyl furans, and aromatic compounds. These results suggest that during the thermal degradation of the E-CO alternating copolymer under inert atmosphere, and at low temperatures, aldol condensations and/or dehydration to furan rings probably occur. © 1998 SCI.     

Kinetic investigation of thermooxidative degradation of poly(vinyl chloride)/acrylonitrile–butadiene–styrene blends by isothermal thermogravimetric analysis

The thermal degradation of poly(vinyl chloride)/acrylonitrile–butadiene–styrene (PVC/ABS) blends of different compositions was investigated by means of isothermal thermogravimetric analysis at temperatures of 210°–240°C in flowing atmosphere of air. The Flynn equation, the method of stationary point, and kinetic equation using the Prout–Tompkins model proved to be satisfactory in describing the thermooxidative degradation in the range of 5–30% conversions. The apparent activation energy E and preexponential factor Z were calculated for all compositions of PVC/ABS blends. The ratios E/ln Z are constant for pure and modified PVC and point to the unique mechanism of degradation process. Upon increasing the ratio of ABS in the PVC/ABS blend up to 50%, only the rate of the process is changed; the mechanism remains unchanged. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 833–839, 1999     

Pyrolysis of polyurethane foam: optimized search for kinetic properties via simultaneous K–K method,genetic algorithm and elemental analysis

This study focuses on the determination of kinetic properties for non‐fire retardant (NFR) and fire retardant (FR) polyurethane foams. Based on the experimental thermogravimetric (TG) curves, this paper describes the application of an in‐depth mathematical analysis and genetic algorithm (GA) to produce the kinetic properties. A recent developed technique, K–K method, is used for calculating kinetic properties and determining the search regions of these properties for GA. Elemental analysis is also used to study the pyrolysis mechanism. Three decomposition models were investigated for comparison, and the results show that the decomposition model with three sub‐reactions achieves the closest representation with experimental results. In the model, two sub‐reactions capture the foam and melt decompositions, and another sub‐reaction with relatively lower activation energy captures the early onset of foam decomposition. The kinetic properties of melt decomposition are found similar because of the similarity of melt chemical formulas and decomposition of NFR and FR foams. The kinetic properties of foam decomposition between NFR and FR foams are different because of the mechanism of FR additives. Validation of the successive and parallel reaction schemes shows no noticeable difference between the two schemes in the modelling decomposition. Copyright © 2015 John Wiley & Sons, Ltd.     

Thermal stability and degradation mechanism of C60 fullerene-based polymers

In this paper, the thermal stability and degradation mechanisms of C₆₀ fullerene-based polymers, obtained by click polymerization between dialkyne-substituted C₆₀ derivative monomers and 1,3,5-tris(dodecyloxy)benzene-based diazide comonomers, were evaluated. The activation energy of the fullerene polymer C₆₀P2 with an ethylene spacer, determined under peak degradation rate conditions, was lower than that of the counter polymer C₆₀P1 with a methylene spacer, suggesting lower thermal stability of C₆₀P2. The combined technique of thermogravimetric analysis—mass spectroscopy and Fourier transform infrared spectroscopy revealed that the thermal decomposition onset of the analyzed samples is accompanied by C C cleavage of the dodecyloxyside chain groups, followed by the decomposition of the 1,2,3-triazole, dicarboxylate and benzoate moieties. It was found that no thermal decomposition of the fullerene carbon cage occurs up to 670°C. Molecular modeling with Hyperchem software version 7.5 confirmed that C₆₀P1 is more thermally stable than C₆₀P2.     

Polymer pyrolysis: A resolution of anomalies in kinetic schemes for the rate of evolution of volatile products

Kinetic schemes proposed by three groups of workers for polymer pyrolysis have been critically examined, in order to resolve apparent anomalies, especially in the way in which the overall first-order rate constant for volatile evolution by depropagation mechanisms, involving different modes of initiation and termination, have been interpreted. In one scheme, the treatment of rate was found to be inappropriate for changing-volume systems, and the resulting rate expressions therefore cannot be recommended. When choice of units, conventions, and symbols was taken into account, the other schemes were found to be totally compatible. These schemes lead to identical expressions for the initial rate of evolution of a volatile product, provided the symbols are defined specifically according to the conventions chosen. These expressions are to be recommended for studies of this kind.     

Thermal degradation of Kevlar fiber by high‐resolution thermogravimetry

A novel high‐resolution thermogravimetry (TG) technique in a variable heating rate mode that maximizes resolution and minimizes the time required for TG experiments has been performed for evaluating the thermal degradation and its kinetics of Kevlar fiber in the temperature range ∼ 25–900°C. The degradation of Kevlar in nitrogen or air occurs in one step. The decomposition rate and char yield at 900°C are higher in air than in nitrogen, but the degradation temperature is higher in nitrogen than in air. The initial degradation temperature and maximal degradation rate for Kevlar are 520°C and 8.2%/min in air and 530°C and 3.5%/min in nitrogen. The different techniques for calculating the kinetic parameters are compared. The respective activation energy, order, and natural logarithm of preexponential factor of the degradation of Kevlar are achieved at average values of 133 kJ/mol (or 154 kJ/mol), 0.7 (or 1.1), and 16 min⁻¹ (or 20 min⁻¹) in air (or nitrogen). The technique based on the principle that the maximum weight loss rate is observed at the minimum heating rate gives thermal degradation results that were in excellent agreement with values determined by traditional TG experiments. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 565–571, 1999     

New method for kinetic analysis of decomposition of biomass materials—Based on critical analysis of Moll method

Moll method used in extracting the kinetic parameters of thermal decomposition of biomass materials is theoretically analyzed and the limitation of the method is critically examined. It is demonstrated that Moll method can only be used under strict conditions within narrow temperature intervals. In light of the idea of Moll method and also in view of the limitations of Moll method, a two‐point data set method is developed for the kinetic analysis of the decomposition of biomass materials in air, using single heating rate mass‐loss curve. The method is justified by comparing the resulted kinetic parameters with those by integral and differential methods. Compared with Moll method, the new method is applicable to the mass‐loss data within wide temperature intervals, whereby the kinetic parameters (especially the activation energy) can be evaluated without any prior knowledge of reaction order, with fairly high reliability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009