Thermal degradation kinetics and lifetime of HDPE/PLLA/pro-oxidant blends

2016 ◽  
Vol 36 (9) ◽  
pp. 917-931 ◽  
Author(s):  
Gaurav Madhu ◽  
Dev K. Mandal ◽  
Haripada Bhunia ◽  
Pramod K. Bajpai
Keyword(s):  
Activation Energy ◽  
Thermal Degradation ◽  
Degradation Kinetics ◽  
Model Fitting ◽  
Frequency Factor ◽  
Thermal Degradation Kinetics ◽  
Heating Rates ◽  
Model Free ◽  
Calculation Technique ◽  
Thermal Degradation Behavior

Abstract The effect of adding poly(L-lactic acid) (PLLA) with and without a pro-oxidant additive cobalt stearate (CoSt) and compatibilizer maleic anhydride grafted polyethylene (MA-g-PE) on the thermal degradation and stability of high-density polyethylene (HDPE) films was analyzed using thermogravimetric analysis (TGA). The kinetic parameters [i.e. activation energy (Ea), order of reaction (n), and frequency factor ln(A)] of the samples were studied over a temperature range of 25°C–600°C at four heating rates (i.e. 5, 10, 15, and 20°C/min) through model-free techniques (e.g. Friedman, second Kissinger, and Flynn-Wall-Ozawa) and model-fitting techniques (e.g. Freeman-Carroll and Kim-Park). The value of Ea for neat HDPE was found to be much higher than PLLA; for the HDPE/PLLA blend, it was nearer to that of HDPE. An increase in the activation energy of 80/20 (HDPE/PLLA) blend was noticed by the addition of MA-g-PE. The TGA data and degradation kinetics were also used to predict the lifetime of the film samples. The lifetime of HDPE was found to decrease with the increase in the concentration of CoSt, thereby revealing its pro-oxidative ability. Minimum lifetime was noted for the HDPE/PLLA (80/20) sample blended with CoSt, which increased slightly in the presence of MA-g-PE. Studies indicated that the thermal degradation behavior and lifetime of the investigated film samples depends not only on the fractions of their constituents but also on the heating rates and calculation technique.

Thermal degradation kinetics of PP/PLA nanocomposite blends

2018 ◽  
Vol 32 (12) ◽  
pp. 1714-1730 ◽  
Author(s):  
Dev K Mandal ◽  
Haripada Bhunia ◽  
Pramod K Bajpai
Keyword(s):  
Thermal Degradation ◽  
Degradation Kinetics ◽  
Frequency Factor ◽  
Nitrogen Atmosphere ◽  
Thermal Degradation Kinetics ◽  
Heating Rates ◽  
Degradation Kinetic ◽  
Thermal Degradation Behavior ◽  
Kinetics Of ◽  
Thermal Stability Of

In this article, the effect of adding polylactide (PLA) and nanoclay on the thermal stability of polypropylene (PP) films was analyzed using thermogravimetric analysis. The thermal degradation kinetic parameters such as activation energy ( Ea), order of reaction ( n), and frequency factor (ln ( Z)) of the samples were studied over a temperature range of 30–550°C. Analyses were performed under nitrogen atmosphere with four different heating rates (i.e. 5, 10, 15, and 20°C min−1). The Ea was calculated by Kissinger, Kim–Park, and Flynn–Wall methods. The Ea value of PP was much higher than PLA, whereas the addition of PLA and nanoclay in PP decreased the Ea. The addition of compatibilizer increased the compatibility and Ea of blended films upto some extent. The lifetime of PP was found to be decreased with the addition of PLA and nanoclay. Studies indicated that the thermal degradation behavior and lifetime of the investigated samples depend on the fractions of constituents and heating rates.

Thermal degradation kinetics and lifetime of high-density polyethylene/poly (l-lactic acid) blends

2015 ◽  
Vol 30 (6) ◽  
pp. 773-793 ◽  
Author(s):  
Gaurav Madhu ◽  
Dev K Mandal ◽  
Haripada Bhunia ◽  
Pramod K Bajpai
Keyword(s):  
Lactic Acid ◽  
Thermal Degradation ◽  
High Density Polyethylene ◽  
Degradation Kinetics ◽  
Estimation Method ◽  
Frequency Factor ◽  
High Density ◽  
Thermal Degradation Kinetics ◽  
Heating Rates ◽  
Model Free

In this work, a kinetic study on the thermal degradation of films prepared from high-density polyethylene (HDPE), poly(l-lactic acid) (PLLA) and their blends is presented. Activation energy ( Ea), order of reaction ( n) and frequency factor (ln ( A)) were studied through thermogravimetric analysis (TGA) over a temperature range of 25–600°C at four heating rates, that is, 5, 10, 15, and 20°C min−1. The TGA data were used to predict the thermal stability of the film samples, comparing the kinetic parameters obtained by three model-free isoconversional techniques and estimating the lifetime of the films. The value of Ea for neat HDPE was found to be much higher than that for PLLA, but for HDPE/PLLA blends, it was nearer to that of HDPE. An increase in Ea of 80/20 (HDPE/PLLA) blends was noticed with the addition of compatibilizer, maleic anhydride-grafted HDPE. Overall, the thermal kinetics of the polymer samples depends on fractions of their constituents, heating rates and calculation technique used. It was proved, through lifetime estimation method, that the lifetime of neat HDPE decreases by addition of PLLA. With increase in temperature, the lifetime of all samples decreased exponentially. Scanning electron microscopy studies verified that HDPE and PLLA interfaces became fairly compatible by adding the compatibilizer.

Effect of Pd Nanoparticle on the Thermal Degradation Kinetics of Nylon 6/Pd Nanocomposite Prepared by a Dry Process

2012 ◽  
Vol 486 ◽  
pp. 27-33 ◽  
Author(s):  
Jae Young Lee ◽  
Sung Wan Hong ◽  
Kyeong Sik Han ◽  
Taeck Hong Lee ◽  
Hong Ki Lee
Keyword(s):  
Activation Energy ◽  
Thermal Degradation ◽  
Degradation Kinetics ◽  
Pd Nanoparticles ◽  
Nylon 6 ◽  
Thermal Degradation Kinetics ◽  
Heating Rates ◽  
Dry Process ◽  
Effect Of Pd ◽  
Kinetics Of

Palladium (Pd) nanoparticles were incorporated into a nylon 6 film via a dry process which consisted of simultaneous vaporization, penetration and reduction processes of palladium (II) bis (acetylacetonate, Pd (acac)2) at 180°C for various exposure time. The even dispersion of the generated Pd nanoparticles were observed by transmission electron microscope (TEM) and the Pd loading weight of about 15~43 wt% was measured by thermogravimetric analysis (TGA). In order to study the catalytic effect of Pd nanoparticles on the thermal degradation kinetics of nylon 6, TGA data at various heating rates were introduced to Flynn & Wall equation. The thermal degradation activation energy for neat nylon 6 was ca. 162~178 kJ/mol over the thermal degradation fraction of 0.05~0.40 while that of the nylon 6/Pd (26.5 wt%) nanocomposite was ca. 110~169 kJ/mol over the same fraction range. It meant the Pd nanoparticles were acted as a catalyst on the depolymerization of amide group in nylon 6. It was also found that the activation energy decreased slightly with the increasing Pd loading weight.

Thermal degradation kinetics of oxo-degradable PP/PLA blends

2018 ◽  
Vol 39 (1) ◽  
pp. 58-67 ◽  
Author(s):  
Dev K. Mandal ◽  
Haripada Bhunia ◽  
Pramod K. Bajpai
Keyword(s):  
Activation Energy ◽  
Thermal Stability ◽  
Thermogravimetric Analysis ◽  
Thermal Degradation ◽  
Kinetic Parameters ◽  
Degradation Kinetics ◽  
Nitrogen Atmosphere ◽  
Thermal Degradation Kinetics ◽  
Heating Rates ◽  
Kinetics Of

AbstractIn this article, the influence of polylactide and pro-oxidant on the thermal stability, degradation kinetics, and lifetime of polypropylene has been investigated using thermogravimetric analysis under nitrogen atmosphere at four different heating rates (i.e. 5, 10, 15, and 20°C/min). The kinetic parameters of degradation were studied over a temperature range of 30–550°C. The derivative thermogravimetric curves have indicated single stage and two stage degradation processes. The activation energy was evaluated by using the Kissinger, Kim-Park, and Flynn-Wall methods under the nitrogen atmosphere. The activation energy value of polypropylene was much higher than that of polylactide. Addition of polylactide and pro-oxidant in polypropylene decreased the activation energy. The lifetime of polypropylene has also decreased with the addition of polylactide and pro-oxidant.

Estimation of Cure and Thermal Degradation Kinetics of Epoxy/Organoclay Nanocomposite

2010 ◽  
Vol 123-125 ◽  
pp. 667-670 ◽  
Author(s):  
Jae Young Lee ◽  
Bum Choul Choi ◽  
Hong Ki Lee
Keyword(s):  
Activation Energy ◽  
Thermal Degradation ◽  
Epoxy Matrix ◽  
Degradation Kinetics ◽  
Cure Kinetics ◽  
Diglycidyl Ether ◽  
Thermal Degradation Kinetics ◽  
Heating Rates ◽  
Scanning Calorimetry ◽  
Kinetics Of

Polymer nanocomposite was synthesized through the intercalation and exfoliation of organoclay in an epoxy matrix. The epoxy matrix was composed of diglycidyl ether of bisphenol A (DGEBA, epoxy base resin), 4,4'-methylene dianiline (MDA, curing agent) and malononitrile (MN, chain extender) and organoclay was prepared by treating the montmorillonite with octadecyltrimethylammonium bromide (ODTMA). The intercalation of the organoclay was estimated by wide angle X-ray diffraction (WAXD) and transmission electron microscope (TEM) analyses. In order to measure the cure rate of DGEBA/MDA (30 phr)/MN (5 phr)/Organoclay (5 phr), differential scanning calorimetry (DSC) analysis were performed at the heating rates of 5, 10, 15 and 20 oC/min, and the data was interpreted by Kissinger equation. Thermal degradation kinetics of the epoxy nanocomposite was also studied by thermogravimetric analysis (TGA). The epoxy sample was decomposed in the TGA furnace at the heating rates of 5, 10, 15 and 20 oC/min with nitrogen atmosphere of 50 ml/min. The TGA data was introduced to the Ozawa equation and the degradation activation energy was calculated according to the degradation ratio. The activation energy for cure kinetics was 43.3 kJ/mol and that for thermal degradation was 171.5 kJ/mol.

scholarly journals Thermal-Resistant Polyurethane/Nanoclay Powder Coatings: Degradation Kinetics Study

Coatings ◽  
2020 ◽  
Vol 10 (9) ◽  
pp. 871
Author(s):  
Maryam Jouyandeh ◽  
Behzad Shirkavand Hadavand ◽  
Farimah Tikhani ◽  
Reza Khalili ◽  
Babak Bagheri ◽  
...  
Keyword(s):  
Activation Energy ◽  
Thermal Degradation ◽  
Degradation Kinetics ◽  
Decomposition Reaction ◽  
Thermal Degradation Kinetics ◽  
Powder Coatings ◽  
Heating Rates ◽  
Uniform Dispersion ◽  
Nano Clay ◽  
Kinetics Of

In the present study, thermal degradation kinetics of polyurethane (PU) powder coatings reinforced with organo-modified montmorillonite (OMMT) was investigated. PU nanocomposites were prepared in different concentrations of 1, 3, and 5 wt.% of OMMT via the extrusion method. The microstructure of the nanocomposites was observed by scanning electron microscope (SEM) illustrating uniform dispersion of OMMT nano-clay platelets in the PU matrix except for the sample containing 5 wt.% nano-palates. Thermal degradation kinetics of the PU nanocomposite was investigated using thermogravimetric analysis (TGA) at different heating rates of 5, 10, and 20 °C/min. The results showed that the initial decomposition temperatures were shifted toward higher values (more than 40 °C for T5% and up to 20 °C for T10%) by introducing the nano-clay to the PU matrix. Friedman, Kissinger–Akahira–Sunose (KAS), Flynn–Wall–Ozawa (FWO), and modified Coats-Redfern iso-conversional methods were applied to model the decomposition reaction and the activation energy of the nanocomposite powder coatings. Overall, the presence of nano-clay increased the activation energy of the PU degradation up to 45 kJ/mol, when compared to the blank PU, which suggests very high thermal stability of nanocomposites. The Sestak-Berggren approach proposed a good approximation for the reaction model, especially at low temperatures. Thus, PU decomposition was detected as an autocatalytic reaction, which was suppressed by the barrier effect of OMMT nano-palates intercalated with polymer chains.

Thermal degradation kinetics of a lignin particle-reinforced phenolic foam

2020 ◽  
pp. 0021955X2093288
Author(s):  
Juan Carlos Domínguez ◽  
Belén Del Saz-Orozco ◽  
Mercedes Oliet ◽  
M Virginia Alonso ◽  
Francisco Rodriguez
Keyword(s):  
Activation Energy ◽  
Thermal Degradation ◽  
Kinetic Parameters ◽  
Degradation Kinetics ◽  
Degradation Process ◽  
Activation Energies ◽  
Thermal Degradation Kinetics ◽  
Model Free ◽  
Predicted Values ◽  
Kinetics Of

In the present work, the thermal degradation kinetics of a phenolic (PF) and lignin particle-reinforced phenolic (LRPF) foam and the lignin used as the reinforcement (LR) were studied. The activation energies of the degradation processes were obtained using a discrete distributed activation energy model (discrete DAEM) and the Vyazovkin model-free kinetic (MFK) method. The discrete DAEM was validated by comparing the predicted values with the data obtained at 8 °C min−1. Heating ramps of 6 and 12 °C min−1 were used to calculate the kinetic parameters through the model. The effect of the reinforcement on the kinetics of the LRPF was studied by comparison with the results obtained for the PF. For reactions with non-zero mass fractions, the activation energies of the PF were in the range between 79.9 and 177.6 kJ mol−1, and the activation energy for the LRPF ranged from 91 to 187 kJ mol−1. For the LR, the activation energy values were in a narrower range than for the foams: 150–187 kJ mol−1. The degradation process of the LRPF was modified due to the use of LR: the range of activation energy for LRPF was between the ranges for the PF and LR. The activation energy dependence on conversion was also calculated using the Vyazovkin method and compared with the DAEM results; no compensation effect for the kinetic parameters was found.

Thermal degradation kinetics of Opuntia Ficus Indica flour and talc-filled poly (lactic acid) hybrid biocomposites by TGA analysis

2021 ◽  
pp. 002199832110082
Author(s):  
Azzeddine Gharsallah ◽  
Abdelheq Layachi ◽  
Ali Louaer ◽  
Hamid Satha
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Thermal Degradation ◽  
Degradation Kinetics ◽  
Degradation Mechanism ◽  
Melt Processing ◽  
Thermal Degradation Kinetics ◽  
Poly Lactic Acid ◽  
Opuntia Ficus Indica ◽  
Model Free

This paper reports the effect of lignocellulosic flour and talc powder on the thermal degradation behavior of poly (lactic acid) (PLA) by thermogravimetric analysis (TGA). Lignocellulosic flour was obtained by grinding Opuntia Ficus Indica cladodes. PLA/talc/ Opuntia Ficus Indica flour (OFI-F) biocomposites were prepared by melt processing and characterized using Wide-angle X-ray scattering (WAXS) and Scanning Electron Microscope (SEM). The thermal degradation of neat PLA and its biocomposites can be identified quantitatively by solid-state kinetics models. Thermal degradation results on biocomposites compared to neat PLA show that talc particles at 10 wt % into the PLA matrix have a minor impact on the thermal stability of biocomposites. Loading OFI-F and Talc/OFI-F mixture into the PLA matrix results in a decrease in the maximum degradation temperature, which means that the biocomposites have lower thermal stability. The activation energies (Ea) calculated by the Flynn Wall Ozawa (FWO) and Kissinger Akahira Sunose (KAS) model-free approaches and by model-fitting (Kissinger method and Coats-Redfern method) are in good agreement with one another. In addition, in this work, the degradation mechanism of biocomposites is proposed using Coats-Redfern and Criado methods.

Thermo-catalytic decomposition of polystyrene waste: Comparative analysis using different kinetic models

2019 ◽  
Vol 38 (2) ◽  
pp. 202-212 ◽  
Author(s):  
Ghulam Ali ◽  
Jan Nisar ◽  
Munawar Iqbal ◽  
Afzal Shah ◽  
Mazhar Abbas ◽  
...  
Keyword(s):  
Activation Energy ◽  
Copper Oxide ◽  
Solid Waste ◽  
Thermodynamic Parameters ◽  
Model Fitting ◽  
Catalytic Decomposition ◽  
Decomposition Reaction ◽  
Inert Atmosphere ◽  
Heating Rates ◽  
Model Free

Due to a huge increase in polymer production, a tremendous increase in municipal solid waste is observed. Every year the existing landfills for disposal of waste polymers decrease and the effective recycling techniques for waste polymers are getting more and more important. In this work pyrolysis of waste polystyrene was performed in the presence of a laboratory synthesized copper oxide. The samples were pyrolyzed at different heating rates that is, 5°Cmin−1, 10°Cmin−1, 15°Cmin−1 and 20°Cmin−1 in a thermogravimetric analyzer in inert atmosphere using nitrogen. Thermogravimetric data were interpreted using various model fitting (Coats–Redfern) and model free methods (Ozawa–Flynn–Wall, Kissinger–Akahira–Sunose and Friedman). Thermodynamic parameters for the reaction were also determined. The activation energy calculated applying Coats–Redfern, Ozawa–Flynn–Wall, Kissinger–Akahira–Sunose and Friedman models were found in the ranges 105–148.48 kJmol−1, 99.41–140.52 kJmol−1, 103.67–149.15 kJmol−1 and 99.93–141.25 kJmol−1, respectively. The lowest activation energy for polystyrene degradation in the presence of copper oxide indicates the suitability of catalyst for the decomposition reaction to take place at lower temperature. Moreover, the obtained kinetics and thermodynamic parameters would be very helpful in determining the reaction mechanism of the solid waste in a real system.

Characterization and thermal degradation kinetics of thermoplastic polyimide based on BAPP

2017 ◽  
Vol 30 (7) ◽  
pp. 787-793 ◽  
Author(s):  
Xu Su ◽  
Yong Xu ◽  
Linshuang Li ◽  
Chaoran Song
Keyword(s):  
Thermogravimetric Analysis ◽  
Thermal Degradation ◽  
Degradation Kinetics ◽  
Degradation Process ◽  
Thermal Degradation Kinetics ◽  
Heating Rates ◽  
Step Method ◽  
Nitrogen Derivative ◽  
Degradation Reaction ◽  
Kinetics Of

Two kinds of thermoplastic polyimides (PIs) were synthesized via a two-step method with 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4′-oxydianiline (ODA) diamine, and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), and their thermal degradation kinetics was studied by thermogravimetric analysis at different heating rates under nitrogen. Derivative thermogravimetric analysis curves indicated a simple, single-stage degradation process in PI BTDA-BAPP and a two-stage degradation process in PI BTDA-ODA-BAPP. The activation energies ( Eas) of the thermal degradation reaction were determined by the Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose methods without a knowledge of the kinetic reaction mechanism. By comparing the values of Ea and weight loss temperatures, it was demonstrated that the thermal stability of PI BTDA-ODA-BAPP was superior to that of PI BTDA-BAPP.

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