scholarly journals Rheological and thermal degradation properties of hyperbranched polyisoprene prepared by anionic polymerization

2019 ◽  
Vol 6 (11) ◽  
pp. 190869 ◽  
Author(s):  
Shehu Habibu ◽  
Norazilawati Muhamad Sarih ◽  
Nor Asrina Sairi ◽  
Muzafar Zulkifli

Hyperbranched polyisoprene was prepared by anionic copolymerization under high vacuum condition. Size exclusion chromatography was used to characterize the molecular weight and branching nature of these polymers. The characterization by differential scanning calorimetry and melt rheology indicated lower T g and complex viscosity in the branched polymers as compared with the linear polymer. Degradation kinetics of these polymers was explored using thermogravimetric analysis via non-isothermal techniques. The polymers were heated under nitrogen from ambient temperature to 600°C using heating rates from 2 to 15°C min −1 . Three kinetics methods namely Friedman, Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose were used to evaluate the dependence of activation energy ( E a ) on conversion ( α ). The hyperbranched polyisoprene decomposed via multistep mechanism as manifested by the nonlinear relationship between α and E a while the linear polymer exhibited a decline in E a at higher conversions. The average E a values range from 258 to 330 kJ mol −1 for the linear, and from 260 to 320 kJ mol −1 for the branched polymers. The thermal degradation of the polymers studied involved one-dimensional diffusion mechanism as determined by Coats–Redfern method. This study may help in understanding the effect of branching on the rheological and decomposition kinetics of polyisoprene.

2019 ◽  
Vol 38 (1) ◽  
pp. 95
Author(s):  
Mirjana Jovicic ◽  
Oskar Bera ◽  
Katalin Meszaros Szecsenyi ◽  
Predrag Kojic ◽  
Jaroslava Budinski-Simendic ◽  
...  

PMMA (poly(methyl methacrylate)) nanocomposites differing in their nature, size, and surface area were prepared containing one volume percent of silica, alumina or titania. These samples and pure PMMA were prepared in order to analyze how the presence of nanooxides affects the thermal stability and degradation kinetics of the materials. A detailed study of thermal degradation and thermal changes was performed by Simultaneous Thermogravimetry and Differential Scanning Calorimetry (SDT). The proposed mathematical model, including all three heating rates in one minimizing function, well fitted all TGA data obtained with a very high coefficient of correlation. This enabled an assessment of four decomposition steps of the PMMA samples and a calculation of their activation energies and individual contributions to total mass loss. The addition of the largest nanoparticles (titania) caused the highest activation energy for each DTG stage of the PMMA/nanooxide systems. The enhancement of head-to-head H–H bonding strength was achieved by addition of alumina and titania. The influence of the size and nature of nanoparticles on the glass transition temperature of prepared PMMA systems was also determined.


2010 ◽  
Vol 123-125 ◽  
pp. 667-670 ◽  
Author(s):  
Jae Young Lee ◽  
Bum Choul Choi ◽  
Hong Ki Lee

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.


2017 ◽  
Vol 30 (7) ◽  
pp. 787-793 ◽  
Author(s):  
Xu Su ◽  
Yong Xu ◽  
Linshuang Li ◽  
Chaoran Song

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.


Materials ◽  
2019 ◽  
Vol 12 (5) ◽  
pp. 699 ◽  
Author(s):  
Ying Liu ◽  
Liutao Yang ◽  
Chunping Ma ◽  
Yingzhe Zhang

In this study, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) methods were used to study the structure, the thermal degradation kinetics, and the thermogram of sweet potato starch, respectively. The thermal decomposition kinetics of sweet potato starch was examined within different heating rates in a nitrogen atmosphere. Different models of kinetic analysis were used to calculate the activation energies using the thermogravimetric data of the thermal degradation process. The activation energies got from Kissinger, Flynn–Wall–Ozawa, and Šatava–Šesták models were 173.85, 174.87, and 174.34 kJ·mol−1, respectively. Thermogravimetry–Fourier transform infrared spectroscopy (TG-FTIR) analysis showed that the main pyrolysis products included water, carbon dioxide, and methane.


2012 ◽  
Vol 486 ◽  
pp. 27-33 ◽  
Author(s):  
Jae Young Lee ◽  
Sung Wan Hong ◽  
Kyeong Sik Han ◽  
Taeck Hong Lee ◽  
Hong Ki Lee

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.


2018 ◽  
Vol 39 (1) ◽  
pp. 58-67 ◽  
Author(s):  
Dev K. Mandal ◽  
Haripada Bhunia ◽  
Pramod K. Bajpai

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.


2018 ◽  
Vol 32 (12) ◽  
pp. 1714-1730 ◽  
Author(s):  
Dev K Mandal ◽  
Haripada Bhunia ◽  
Pramod K Bajpai

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.


Coatings ◽  
2020 ◽  
Vol 10 (9) ◽  
pp. 871
Author(s):  
Maryam Jouyandeh ◽  
Behzad Shirkavand Hadavand ◽  
Farimah Tikhani ◽  
Reza Khalili ◽  
Babak Bagheri ◽  
...  

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.


Molecules ◽  
2021 ◽  
Vol 26 (6) ◽  
pp. 1597
Author(s):  
Iman Jafari ◽  
Mohamadreza Shakiba ◽  
Fatemeh Khosravi ◽  
Seeram Ramakrishna ◽  
Ehsan Abasi ◽  
...  

The incorporation of nanofillers such as graphene into polymers has shown significant improvements in mechanical characteristics, thermal stability, and conductivity of resulting polymeric nanocomposites. To this aim, the influence of incorporation of graphene nanosheets into ultra-high molecular weight polyethylene (UHMWPE) on the thermal behavior and degradation kinetics of UHMWPE/graphene nanocomposites was investigated. Scanning electron microscopy (SEM) analysis revealed that graphene nanosheets were uniformly spread throughout the UHMWPE’s molecular chains. X-Ray Diffraction (XRD) data posited that the morphology of dispersed graphene sheets in UHMWPE was exfoliated. Non-isothermal differential scanning calorimetry (DSC) studies identified a more pronounced increase in melting temperatures and latent heat of fusions in nanocomposites compared to UHMWPE at lower concentrations of graphene. Thermogravimetric analysis (TGA) and derivative thermogravimetric (DTG) revealed that UHMWPE’s thermal stability has been improved via incorporating graphene nanosheets. Further, degradation kinetics of neat polymer and nanocomposites have been modeled using equations such as Friedman, Ozawa–Flynn–Wall (OFW), Kissinger, and Augis and Bennett’s. The "Model-Fitting Method” showed that the auto-catalytic nth-order mechanism provided a highly consistent and appropriate fit to describe the degradation mechanism of UHMWPE and its graphene nanocomposites. In addition, the calculated activation energy (Ea) of thermal degradation was enhanced by an increase in graphene concentration up to 2.1 wt.%, followed by a decrease in higher graphene content.


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