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

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.


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.


2010 ◽  
Vol 123-125 ◽  
pp. 651-654
Author(s):  
Jae Young Lee ◽  
Bum Choul Choi ◽  
Ji Jung Lee ◽  
Sung Won Yang ◽  
Hong Ki Lee

Palladium (Pd) nanoparticles were incorporated into free-standing polymer films, where isotactic polypropylene (iPP) was used, by a one-step dry process involving simultaneous vaporization, absorption and reduction schemes of palladium(II) bis(acetylacetonate), Pd(acac)2 at 180oC, used as a precursor. iPP film was exposed to the sublimed Pd(acac)2 vapor in a glass vessel with nitrogen atmosphere heated at 180oC. The exposing time was 30 min and the Pd nanoparticle contents in polymer films were estimated from ash contents in a sample of about 5 mg by pyrolysis of the films at 800 oC for 1 h in an electric furnace of the TGA apparatus under dry argon atmosphere. The sensitivity of the TGA apparatus was 0.2 mg, and thus the minimum content to be measured was 0.004 wt% of a 5 mg sample. The reduced Pd nanoparticles were observed by transmission electron microscope (TEM), and it was found that metal nanoparticles were selectively loaded into the amorphous regions between the lamellae of crystalline polymers having higher melting temperatures than the processing temperature (180 oC). In order to measure the thermal degradation rate, TGA data measured by the heating rates of 5, 10, 15 and 20 oC /min at the nitrogen atmosphere of 200 ml/min. The TGA data was introduced to the Ozawa equation and the degradation activation energy was calculated according to the degradation ratio.


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.


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.


e-Polymers ◽  
2017 ◽  
Vol 17 (5) ◽  
pp. 373-381 ◽  
Author(s):  
Xinxin Cao ◽  
Mengqi Wu ◽  
Aiguo Zhou ◽  
You Wang ◽  
Xiaofang He ◽  
...  

AbstractA novel two-dimensional material MXene was used to synthesize nanocomposites with linear low-density polyethylene (LLDPE). The influence of MXene on crystallization and thermal degradation kinetics of LLDPE was investigated. Non-isothermal crystallization kinetics was investigated by using differential scanning calorimetry (DSC). The experimental data was analyzed by Jeziorny theory and the Mo method. It is found that MXene acted as a nucleating agent during the non-isothermal crystallization process, and 2 wt% MXene incorporated in the nanocomposites could accelerate the crystallization rate. Findings from activation energy calculation for non-isothermal crystallization came to the same conclusion. Thermal gravity (TG) analysis of MXene/LLDPE nanocomposites was conducted at different heating rates, and the TG thermograms suggested the nanocomposites showed an improvement in thermal stability. Apparent activation energy (Ea) of thermal degradation was calculated by the Kissinger method, and Ea values of nanocomposites were higher than that of pure LLDPE. The existence of MXene seems to lead to better thermal stability in composites.


Materials ◽  
2018 ◽  
Vol 12 (1) ◽  
pp. 63 ◽  
Author(s):  
Claudia Barile ◽  
Caterina Casavola ◽  
Paramsamy Vimalathithan ◽  
Marco Pugliese ◽  
Vincenzo Maiorano

The present work describes the mechanical characterization combined with the thermal degradation kinetics of Carbon Fiber Reinforced Polymers (CFRP). The thermal degradation kinetics of CFRP have never been studied in the past. In that regard, the present work focuses on studying the thermal degradation kinetics of CFRP tested mechanically at different environmental conditions. Tensile tests were performed on the specimens with different lay-ups at room temperature, elevated temperature (71 °C), and cryogenic conditions (−54 °C), and the same specimens were used for thermal degradation kinetic studies. Mechanical tests show different responses respect to the different environmental conditions and different fibers orientation. On the other hand, the thermogravimetric results, mass loss, and derivative mass loss, show no significant difference in the degradation of CFRP tested at different temperatures. However, the thermal degradation kinetics shows more insight into the degradation pattern of the materials. The activation energy of degradation shows that the degradation of materials subjected to elevated conditions increases rapidly in the later stages of degradation, suggesting the formation of high char yield. The varying activation energy has been related to different degradation mechanisms. Lastly, the morphology of the materials was studied under SEM to understand the structural change in the material after tested in different weather conditions.


2010 ◽  
Vol 96 ◽  
pp. 245-249 ◽  
Author(s):  
Bin Han ◽  
Yu Long Wu ◽  
Guo Rui ◽  
Wei Feng ◽  
Zhen Chen ◽  
...  

The thermal degradation of PVC resin was examined by the thermogravimetric analysis (TGA). The pyrolysis volatile products were analyzed by Fourier transform infrared spectrometer synchronized with TG test (TG-FTIR). Based on the TG results, the kinetics of thermal degradation was studied by Friedman method. The pyrolysis mechanism was discussed also. The results indicate that the pyrolysis process of PVC can be divided into two main stages: 220°C - 380°C and 380°C - 560°C. By the calculation of mass conservation and TG-FTIR results, it can be supposed that not only HCl, but also some unsubstituted aromatics such as benzene were released during the first stage. The comparison of activation energy shows that the second stage exhibited higher activation energy than the first stage. Two activation energy values in the first stage confirm that there arose two reactions in the first stage.


2016 ◽  
Vol 36 (9) ◽  
pp. 917-931 ◽  
Author(s):  
Gaurav Madhu ◽  
Dev K. Mandal ◽  
Haripada Bhunia ◽  
Pramod K. Bajpai

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.


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