scholarly journals Kinetic Analysis of the Thermal Degradation of Recycled Acrylonitrile-Butadiene-Styrene by non-Isothermal Thermogravimetry

Polymers ◽  
2019 ◽  
Vol 11 (2) ◽  
pp. 281 ◽  
Author(s):  
Rafael Balart ◽  
David Garcia-Sanoguera ◽  
Luis Quiles-Carrillo ◽  
Nestor Montanes ◽  
Sergio Torres-Giner
Keyword(s):  
Thermal Degradation ◽  
Kinetic Analysis ◽  
Acrylonitrile Butadiene Styrene ◽  
Isoconversional Methods ◽  
Reaction Model ◽  
Integral Model ◽  
Heating Rates ◽  
Exponential Factor ◽  
Model Free ◽  
Butadiene Styrene

This work presents an in-depth kinetic study of the thermal degradation of recycled acrylonitrile-butadiene-styrene (ABS) polymer. Non-isothermal thermogravimetric analysis (TGA) data in nitrogen atmosphere at different heating rates comprised between 2 and 30 K min−1 were used to obtain the apparent activation energy (Ea) of the thermal degradation process of ABS by isoconversional (differential and integral) model-free methods. Among others, the differential Friedman method was used. Regarding integral methods, several methods with different approximations of the temperature integral were used, which gave different accuracies in Ea. In particular, the Flynn-Wall-Ozawa (FWO), the Kissinger-Akahira-Sunose (KAS), and the Starink methods were used. The results obtained by these methods were compared to the Kissinger method based on peak temperature (Tm) measurements at the maximum degradation rate. Combined Kinetic Analysis (CKA) was also carried out by using a modified expression derived from the general Sestak-Berggren equation with excellent results compared with the previous methods. Isoconversional methods revealed negligible variation of Ea with the conversion. Furthermore, the reaction model was assessed by calculating the characteristic and functions and comparing them with some master plots, resulting in a nth order reaction model with n = 1.4950, which allowed calculating the pre-exponential factor (A) of the Arrhenius constant. The results showed that Ea of the thermal degradation of ABS was 163.3 kJ mol−1, while ln A was 27.5410 (A in min−1). The predicted values obtained by integration of the general kinetic expression with the calculated kinetic triplet were in full agreement with the experimental data, thus giving evidence of the accuracy of the obtained kinetic parameters.

Kinetic Studies on the Thermal Synthesis of Fluorapatite: Model Free and Model-Fitting Methods

2018 ◽  
Vol 28 ◽  
pp. 75-89
Author(s):  
Hamid Reza Javadinejad ◽  
Sayed Ahmad Hosseini ◽  
Mohsen Saboktakin Rizi ◽  
Eiman Aghababaei ◽  
Hossein Naseri
Keyword(s):  
Activation Energy ◽  
Model Fitting ◽  
Kinetic Studies ◽  
Isoconversional Methods ◽  
Reaction Model ◽  
Heating Rates ◽  
Thermal Synthesis ◽  
Exponential Factor ◽  
Model Free ◽  
Master Plots

The kinetic study for the synthesis of Fluorapatite has been done using the thermogravimetric technique under non-isothermal conditions and at four heating rates of 5, 10, 15 and 20 °C. Both model free and model-fitting methods were used to investigate kinetic parameters. Calcium oxide, phosphorus pentoxide and calcium fluoride were used as the precursor materials. The activation energy values were calculated through model-fitting and isoconversional methods and were used to predict the reaction model and pre-exponential factor. In this case several techniques were considered such as master plots and compensation effects. The results indicated that the reaction mechanism was chemically controlled with second and third order reaction models in the whole range of conversion which the activation energy varied from 25 to 43 kJ/mol.

scholarly journals Kinetic Analysis of Pyrolysis and Thermo-Oxidative Decomposition of Tennis String Nylon Wastes

Materials ◽  
2021 ◽  
Vol 14 (24) ◽  
pp. 7564
Author(s):  
Haibo Wan ◽  
Zhen Huang
Keyword(s):  
Thermal Degradation ◽  
Kinetic Analysis ◽  
Model Fitting ◽  
Degradation Process ◽  
Nylon 6 ◽  
Reaction Model ◽  
Heating Rates ◽  
Model Free ◽  
Order Chemical Reaction ◽  
First Order Chemical Reaction

Thermal degradation of nylon-6 tennis string nylon wastes in inert nitrogen and air atmospheres was investigated by means of multiple heating-rate thermogravimetric analyses. The results obtained under the heating rates of 5–20 K/min are compared in terms of degradation feature and specific temperature for two atmospheres. Using nonisothermal data, kinetic analysis was thoroughly conducted using various isoconversional model-free methods, including Starink, Madhusudanan–Krishnan–Ninan, Tang, Coats–Redfern, and Flynn–Wall–Ozawa methods. With these kinetic analysis methods, the activation energy over the entire degradation process was successfully calculated. By means of the model-fitting master-plots method, the first-order chemical reaction model was determined to be the most appropriate mechanism function for describing pyrolysis and oxidative thermal degradation of nylon-6 waste. Using kinetic parameters, satisfactory matching against experimental data resulted using the Coats–Redfern method for both cases. Furthermore, thermodynamic parameters such as changes in entropy, enthalpy, and Gibbs free energy during thermal degradation processes were evaluated.

scholarly journals Study of thermal degradation behavior and kinetics of ABS/PC blend

2020 ◽  
Vol 22 (3) ◽  
pp. 64-69
Author(s):  
Saira Bano ◽  
Naveed Ramzan ◽  
Tanveer Iqbal ◽  
Hamayoun Mahmood ◽  
Farhan Saeed
Keyword(s):  
Thermal Degradation ◽  
Mass Loss ◽  
Acrylonitrile Butadiene Styrene ◽  
Entropy Change ◽  
Heating Rates ◽  
Exponential Factor ◽  
Model Free ◽  
Thermogravimetric Curve ◽  
Thermal Degradation Behavior ◽  
Kinetics Of

AbstractThis work investigated kinetics and thermal degradation of acrylonitrile butadiene styrene and polycarbonate (ABS/PC) blend using thermogravimetric analysis in the range of 25 to 520°C. For thermal degradation of blend, activation energy (Ea) and pre-exponential factor (A) were calculated under various heating rates as 5, 10, 15 and 20°C/min using iso-conversional model-free methods (Kissinger, Flynn-Wall- Ozawa and Friedman). Mass loss of the blend as a function of temperature was plotted as thermogravimetric curve (TG) while derivative values of mass loss were drawn as derivative thermogravimetric (DTG) curve. Using Kissinger method, Ea was 51.4 kJ/mol, while values calculated from FWO and Friedman method were 86–161 and 30–251 kJ/mol respectively. Results showed increasing trend of Ea with higher conversion values indicating different degradation mechanisms at the initial and final stages of the experiment. Thermodynamic parameters such as enthalpy change (ΔH), Gibbs free energy (ΔG) and entropy change (ΔS) were also calculated.

scholarly journals Eriobotrya japonica Lindl. Kernels: Kinetics of Thermal Degradation under Inert Atmosphere Using Model-Free and Fitting Methods

2020 ◽  
Vol 11 (4) ◽  
pp. 11357-11379
Keyword(s):  
Activation Energy ◽  
Thermal Degradation ◽  
Mass Loss ◽  
Kinetic Parameters ◽  
Inert Atmosphere ◽  
Eriobotrya Japonica ◽  
Heating Rates ◽  
Noticeable Effect ◽  
Exponential Factor ◽  
Model Free

A kinetic study of the pyrolysis process of raw Eriobotrya japonica Lindl. Kernels (RLK) was investigated using a thermogravimetric analyzer. The weight loss was measured in a nitrogen atmosphere. The samples were heated over a range of temperature from 298 K to 873 K with four different heating rates of 5, 10, 15, 20 K min-1. Mass loss (TGA) and derivative mass loss (DTG) measurements indicate that the increase in heating rate has no noticeable effect on the thermal degradation of the RLK. The results obtained from the thermal decomposition process indicate that there are three main stages such as dehydration, active, and passive pyrolysis. TGA curves indicate that active pyrolysis of RLK is between 160 and 450 °C. In this interval, a shoulder followed by a peak exists on the DTG plots. The shoulder corresponds to the decomposition of hemicelluloses, the first peak to that of cellulose. Lignin decomposes through all temperature range. The kinetic parameters such as activation energy and pre-exponential factor were obtained for two degradation steps by isoconversional model-free methods proposed by FWO, KAS, Kissinger, Tang, MKN, and FR, with degradation mode being: f(α)=(1-α)n with n = 1 for FR and g(α)=-Ln(1- α) for the other methods. The activation energy and pre-exponential factor obtained by the Kissinger method are 173 kJ/mol and 1.9×1016 min-1. While for free model methods, the average kinetic parameters calculated are 172-248 kJ.mol-1 and 5,30×1020 for integral methods (FWO, KAS, Tang and MKN) and 190-271 kJ.mol-1 and 1.77×1022 min-1 for differential Fr method. The activation energy decreases in the final stages of the process. The energy required for hemicellulose degradation is lower than that of cellulose. The most probable reaction functions have thus been determined for these two stages by Coats-Redfern and Criado method, leading to greatly improved calculation performance over the entire conversion range. The reaction, second-order F2, describes the pyrolysis reaction models of RLK. With the Arrhenius parameters obtained from the fitting model of CR, we attempt to reconstruct the temperature-dependent mass conversion curves and have resulted in generally acceptable results. Based on the Arrhenius parameter values obtained by Kissinger equation, the changes in entropy, enthalpy and Gibbs free energy, and lifetime predictions have been estimated concerning the thermal degradation processes of RLK.

Kinetic Analysis of Thermal Decomposition of Unirradiated and γ-Irradiated Tris(ACEtylacetonato)-Ruthenium(III) [Ru(acac)3]

2007 ◽  
Vol 32 (1) ◽  
pp. 1-27 ◽  
Author(s):  
R. M. Mahfouz ◽  
M. R. H. Siddiqui ◽  
Sh. A. Al-Ahmari ◽  
W. Z. Alkayali
Keyword(s):  
Model Fitting ◽  
Isoconversional Methods ◽  
Short Review ◽  
Reaction Model ◽  
Major Step ◽  
Exponential Factor ◽  
Temperature Range ◽  
Model Free ◽  
Kinetic Triplet ◽  
Isothermal Measurements

The thermal decompositions of unirradiated and γ-irradiated Ru(acac)3 were studied in air. The results show that decomposition proceeds in one major step in the temperature range of 150-250°C with the formation of RuO2 as a final solid residue for unirradiated Ru(acac)3. For γ-irradiated Ru(acac)3, with a total γ-ray dose of 102kGy, the decomposition goes eventually to completion with almost 100% decomposition and proceeds in one major step which contains four overlapping decomposition stages in the temperature range of 200 −320°C. The kinetics were followed isothermally and non-isothermally using both model-fitting and model-free approaches. IR spectroscopy and X-ray powder diffraction techniques were employed to follow the chemical composition of the solid residues obtained at different temperatures. In a model-fitting approach, the kinetic triplet, i.e. the apparent activation energy Ea, the pre-exponential factor, ln A, and the reaction model f (α), were analyzed and calculated using straight line plots, and reduced time plots by isothermal measurements. For non-isothermal measurements we have applied the Coats and Redfern, and Kennedy and Clark methods. In the model-free approach, the non-thermal data for both unirradiated and γ-irradiated Ru(acac)3 samples were analyzed using the Flynn-Wall-Ozawa (FWO), Tang (T), and Vyazovkin (Vyz) isoconversional methods. The results of application of model-free and model-fitting approaches to the thermal decompositions of both unirradiated and γ-irradiated Ru(acac)3 were compared and evaluated to deduce the most probable kinetic triplet that describes correctly the thermal behavior of Ru(acac)3. Discussion of the results is preceded by a short review of the models relevant to this study.

scholarly journals Dynamic Model-Free and Model-Fitting Kinetic Analysis during Torrefaction of Oil Palm Frond Pellets

2020 ◽  
Vol 15 (1) ◽  
pp. 253-263
Author(s):  
Sharmeela Matali ◽  
Norazah Abd Rahman ◽  
Siti Shawalliah Idris ◽  
Nurhafizah Yaacob
Keyword(s):  
Activation Energy ◽  
Thermal Degradation ◽  
Oil Palm ◽  
Model Fitting ◽  
Integral Model ◽  
Model Free ◽  
Solid Biofuel ◽  
Oil Palm Frond ◽  
Kinetics Of ◽  
Palm Frond

Torrefaction is a thermal conversion method extensively used for improving the properties of biomass. Usually this process is conducted within a temperature range of 200-300 °C under an inert atmosphere with residence time up to 60 minutes. This work aimed to study the kinetic of thermal degradation of oil palm frond pellet (OPFP) as solid biofuel for bioenergy production. The kinetics of OPFP during torrefaction was studied using frequently used iso-conversional model fitting (Coats-Redfern (CR)) and integral model-free (Kissinger-Akahira-Sunose (KAS)) methods in order to provide effective apparent activation energy as a function of conversion. The thermal degradation experiments were conducted at four heating rates of 5, 10, 15, and 20 °C/min in a thermogravimetric analyzer (TGA) under non-oxidative atmosphere. The results revealed that thermal decomposition kinetics of OPFP during torrefaction is significantly influenced by the severity of torrefaction temperature. Via Coats-Redfern method, torrefaction degradation reaction mechanism follows that of reaction order with n = 1. The activation energy values were 239.03 kJ/mol and 109.28 kJ/mol based on KAS and CR models, respectively. Copyright © 2020 BCREC Group. All rights reserved 

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