scholarly journals ISOTHERMAL CURING KINETICS OF POLYMETHACRYLIMIDE/NANO-SiO2 COMPOSITES BASED ON A DYNAMIC THERMOMECHANICAL ANALYSIS

2021 ◽  
Vol 55 (2) ◽  
pp. 293-304
Author(s):  
Jing Zhang ◽  
Yi-min Wu ◽  
Xu Ma ◽  
Bao-Yu Huang ◽  
Song Lv ◽  
...  

The isothermal curing kinetics of polymethacrylimide/nano-SiO2 composites were investigated using a dynamic thermomechanical analysis. The relative conversion was defined with the storage modulus. The Avrami model-fitting method, Friedman method and integral method were applied to analyze the curing kinetics. The storage modulus and loss modulus increased appreciably, spanning three orders of magnitude throughout the curing. The frequency correlation of the relative conversion was noticeable at 180 °C because the glass transition took place when the curing degree was not high enough. The Avrami model-fitting analysis gave good fits for the experimental data. The activation energy calculated with the Avrami equation changed from 65.46 kJ/mol to 25.28 kJ/mol at 180–190 °C, while at 190–200 °C, the activation energy changed from 107.14 kJ/mol to 63.82 kJ/mol. The model-free analysis revealed the dependence of the activation energy on the relative conversion. The activation energy increased from 104.3 kJ/mol to 130.6 kJ/mol with the use of the Friedman method when the relative conversion ranged between 0.4–0.8. Similarly, the activation energy calculated with the integral method increased from 71.5 kJ/mol to 103.4 kJ/mol. When the relative conversion exceeded 0.8, the activation energy decreased gradually. The mobility of the reactive groups was hindered and the crosslinking density of the composite was much higher. The curing kinetics became diffusion controlled. The activation energy of the PMI/SiO2 composite was greater than that of PMI, which could be attributed to the hindrance effect caused by nano-SiO2.

2020 ◽  
Vol 15 (1) ◽  
pp. 253-263
Author(s):  
Sharmeela Matali ◽  
Norazah Abd Rahman ◽  
Siti Shawalliah Idris ◽  
Nurhafizah Yaacob

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 


2014 ◽  
Vol 988 ◽  
pp. 31-35
Author(s):  
Jia Le Song ◽  
Chan Chan Li ◽  
Zhi Mi Zhou ◽  
Chao Qiang Ye ◽  
Wei Guang Li

Curing kinetics of MEP-15/593 system and MEP-15/593/660 system is studied by means of differential scanning calorimetry (DSC). Curing kinetic parameters are evaluated and the relationship between diluent 660 and the curing properties is investigated. The results show that the diluent 660 can not only reduce viscosity and activation energy, but also improve the degree of cure and conversion ratio.


2011 ◽  
Vol 525 (1-2) ◽  
pp. 31-39 ◽  
Author(s):  
Jintao Wan ◽  
Zhi-Yang Bu ◽  
Cun-Jin Xu ◽  
Hong Fan ◽  
Bo-Geng Li

2011 ◽  
Vol 688 ◽  
pp. 180-185
Author(s):  
Yu Zhang ◽  
Wei Lu ◽  
Biao Yan ◽  
Yu Xin Wang ◽  
Ying Yang

The nanocrystallization kinetics of the Fe81Si3.5B13.5C2amorphous alloy was investigated by differential scanning calorimetry (DSC). The apparent activation energy Ea, as well as the nucleation and growth kinetic parameters has been calculated by Kissinger and Ozawa methods. The changeable activation energy Eawith crystalline fraction α was obtained by the expended Friedman method without assuming the kinetic model function, and the average value of Eawas 364±20 kJ/mol. It was shown that the crystallization mechanism of initial stage (0<α<0.7) of the transformation was bulk crystallization with two and three dimensional nucleation graining growth which was controlled by diffusion. For the middle stage (0.7<α<0.9), the crystallization mechanism is surface crystallization with one dimensional nucleation graining growth at a near-zero nucleation rate. In the final stage(α>0.9),the local Avrami exponents rose anomalously from 1.4 to about 2.0.


2021 ◽  
Vol 65 (1) ◽  
pp. 33-39
Author(s):  
Z. Nait Abdellah ◽  
M. Keddam ◽  
P. Jurči

Abstract In this study, two different mathematical models have been proposed for estimating the diffusivities of boron in the Fe2B layer on ASTM A36 steel in the range of 1173 to 1273 K with exposure times of 2 to 8 h. The boride incubation period required for the formation of such a layer was constant regardless of the boriding conditions. In both approaches, the boron diffusivity in the iron phase was considered in an unsaturated matrix. The first approach was derived from the mass balance equation at the (Fe2B/substrate) interface while the second approach employed the integral diffusion model. The calculated values of boron activation energies for ASTM A36 steel were found to be very comparable for the two approaches (161.65 and 160.96 and kJ mol-1). Afterwards, these values of activation energy were confronted with the results from the literature. Experimental validation of these two approaches has been done by comparing the experimental value of Fe2B layer thickness measured at 1123 K for 2.5 h with the simulated values. Finally, the predicted values of Fe2B layer thickness were in line with the experimental measurement.


RSC Advances ◽  
2015 ◽  
Vol 5 (110) ◽  
pp. 90437-90450 ◽  
Author(s):  
L. Vertuccio ◽  
S. Russo ◽  
M. Raimondo ◽  
K. Lafdi ◽  
L. Guadagno

Variation of the activation energy with conversion obtained by “advanced isoconversional method”.


2018 ◽  
Vol 5 (10) ◽  
pp. 181282 ◽  
Author(s):  
Liming He ◽  
Wei He ◽  
Zhongliang Ma

We have conducted a novel study of the influence of energy components (RDX, AP and CL-20) on curing kinetics of glycidyl azide polymer (GAP) spherical propellant based on rheological method. The autocatalytic model was used to describe curing kinetics and the parameters were determined by the model-fitting method. It was found that the incorporation of components hinders the cross-linking reaction of GAP spherical propellant. Integral isoconversional method was used on rheological kinetics to investigate the changes of the activation energy and we confirmed that the incorporation of components increased the activation energy. It was also found that such components had no effect on the trend of activation energy curves but shrank the peak value at a = 0.2. Dynamic mechanical analysis (DMA) showed the differences between pure curing system and its components. These findings are potentially helpful to control the curing effectively and optimize the processing schedules. The addition of components decreased α translation temperature which means the reduction in cross-links. The differences in the values of loss factor tan δ and β translation showed that pure curing system has lower resistance for side chain to motion.


e-Polymers ◽  
2016 ◽  
Vol 16 (3) ◽  
pp. 199-206 ◽  
Author(s):  
Aleš Ručigaj ◽  
Špela Gradišar ◽  
Matjaž Krajnc

AbstractCuring kinetics of guaiacol based benzoxazine synthesized from guaiacol, furfurylamine and formaldehyde forming bio-based polybenzoxazine was investigated. The curing process showed complex polymerization behavior, as the exothermal signal consisted of several overlapped peaks. Differentiation and fitting of overlapped peaks was performed by Pearson VII distribution obtaining two separate exothermal signals further associated to stage 1 and stage 2. The apparent activation energies of both stages were determined to be 113.8 kJ mol-1 and 117.5 kJ mol-1, respectively, according to Kissinger. The first could be explained by benzoxazine ring-opening and electrophilic substitution, whereas the second stage corresponds to the rearrangement and diffusion-controlled step. Kinetics of each stage was studied separately. As a result, the first stage was described by Šesták-Berggren autocatalytic model, whereas the second stage appeared to follow nth order kinetics proved by the Friedman method. Application of both kinetic models demonstrated that the predicted curves fit well with the non-isothermal DSC thermograms and as such sufficiently describes the complex curing behavior of guaiacol based benzoxazine.


2019 ◽  
Vol 8 (3) ◽  
pp. 649-653

Copper perchlorate complex with 4-aminopyridine and water has been prepared with molecular formula [Hg2(C5H6N2)3(ClO4)4].2H2O. It has been characterised by elemental analysis, thermogravimetry, and IR spectroscopic data. Thermal behaviours have been studied by thermogravimetry (TG) in static air and simultaneous thermogravimetry-derivative thermogravimetry analysis (TG-DTG) in flowing nitrogen atmosphere. Complex decomposes in four steps (less resolved). Difference in decomposition under air and inert atmosphere has been also discussed. Kinetics of thermal decomposition has been investigated using isothermal TG data recorded at five different temperatures applying model-fitting as well as isoconversional method on these data. Model-fitting methods have yielded a single value of activation energy whereas isoconversional method has given different values of activation energy for each extent of conversion, α. Response of synthesized complex towards rapid heating has been investigated by recording explosion delay time (DE) at five different temperatures and using these data kinetics of explosion has been analysed. Activation energy for explosion has been also calculated.


2013 ◽  
Vol 798-799 ◽  
pp. 17-24
Author(s):  
Shou Yuan Fan ◽  
Jian Kui Chen ◽  
Zhou Ping Yin

The study of the epoxy-based anisotropic conductive adhesive in electronic packaging interconnects applications (chip-on-glass, chip-on-flex, etc. especially in RFID applications) has received particular attention. This is due to its potential advantages of finer pitch printing, reducing environmental contamination. The thermal curing process is critical to develop the ultimate electrical and mechanical properties of the ACA devices. In this article, the curing kinetics of ACA was studied with a differential scanning calorimeter (DSC) under constant heating rates conditions in the range of 520 °C/min. The model free method was used to describe the curing reaction. The degree-of-cure and the activation energy through the whole conversion range were mathematically determined and used to predict the progress of the curing process. Experimental results show that the activation energy of the ACA varies significantly with degree-of-cure during the curing process. The peculiar phenomenon indicates that the ACA underwent a complex series of reactions. The kinetics of curing reaction changes when large conversion values are reached at low heating rates. The change in the reaction kinetics is due to vitrification of the ACA during heating. In addition, the degree-of-cure of the ACA as a function of bonding times during isothermal ACA bonding process was theoretically predicted.


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