Analyzing the discrepancies in the activation energies of the backbiting and β-scission reactions in the radical polymerization of n-butyl acrylate

2016 ◽  
Vol 7 (11) ◽  
pp. 2069-2077 ◽  
Author(s):  
S. Hamzehlou ◽  
N. Ballard ◽  
Y. Reyes ◽  
A. Aguirre ◽  
J. M. Asua ◽  
...  

Activaton energies for backbiting and β-scission reactions for the polymerization of n-BA were determined by fitting experimental data to a mathematical model. The activation energy for backbiting was higher and that for β-scission lower than those accepted in the literature.


Polymers ◽  
2020 ◽  
Vol 12 (5) ◽  
pp. 1070 ◽  
Author(s):  
Sergey Vyazovkin

The objective of this review paper is to survey the phase transition kinetics with a focus on the temperature dependence of the rates of crystallization and melting, as well as on the activation energies of these processes obtained via the Arrhenius kinetic treatment, including the treatment by isoconversional methods. The literature is analyzed to track the development of the basic models and their underlying concepts. The review presents both theoretical and practical considerations regarding the kinetic analysis of crystallization and melting. Both processes are demonstrated to be kinetically complex, and this is revealed in the form of nonlinear Arrhenius plots and/or the variation of the activation energy with temperature. Principles which aid one to understand and interpret such results are discussed. An emphasis is also put on identifying proper computational methods and experimental data that can lead to meaningful kinetic interpretation.



Computation ◽  
2020 ◽  
Vol 8 (4) ◽  
pp. 89
Author(s):  
Ratmir Dashkin ◽  
Georgii Kolesnikov ◽  
Pavel Tsygankov ◽  
Igor Lebedev ◽  
Artem Lebedev ◽  
...  

The presented work is devoted to isocyanate synthesis by the thermal decomposition of carbamates model. The work describes the existing isocyanate-obtaining processes and the main problems in the study of isocyanate synthesis by the thermal decomposition of carbamates, which can be solved using mathematical and computer models. Experiments with carbamates of various structures were carried out. After processing the experimental data, the activation energy and the pre-exponential factor for isocyanate synthesis by the thermal decomposition of carbamates were determined. Then, a mathematical model of the reactor for the thermal decomposition of carbamates using the COMSOL Multiphysics software was developed. For this model, computational experiments under different conditions were carried out. It was shown that the calculation results correspond to the experimental ones, so the suggested model can be used in the design of the equipment for isocyanate synthesis by the thermal decomposition of carbamates.





2018 ◽  
Vol 15 (1) ◽  
pp. 169-181
Author(s):  
M. I. Sidorov ◽  
М. Е. Stavrovsky ◽  
V. V. Irogov ◽  
E. S. Yurtsev

Using the example of van der Pol developed a mathematical model of frictional self-oscillations in topochemically kinetics. Marked qualitative correspondence of the results of calculation performed using the experimental data of researchers.



1982 ◽  
Vol 47 (7) ◽  
pp. 1780-1786 ◽  
Author(s):  
Rostislav Kudláček ◽  
Jan Lokoč

The effect of gamma pre-irradiation of the mixed nickel-magnesium oxide catalyst on the kinetics of hydrogenation of maleic acid in the liquid phase has been studied. The changes of the hydrogenation rate are compared with the changes of the adsorbed amount of the acid and with the changes of the solution composition, activation energy, and absorbed dose of the ionizing radiation. From this comparison and from the interpretation of the experimental data it can be deduced that two types of centers can be distinguished on the surface of the catalyst under study, namely the sorption centres for the acid and hydrogen and the reaction centres.



Metals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 581
Author(s):  
Abdulhakim A. Almajid

This study is focused on the deformation mechanism and behavior of naturally aged 7010 aluminum alloy at elevated temperatures. The specimens were naturally aged for 60 days to reach a saturated hardness state. High-temperature tensile tests for the naturally aged sample were conducted at different temperatures of 573, 623, 673, and 723 K at various strain rates ranging from 5 × 10−5 to 10−2 s−1. The dependency of stress on the strain rate showed a stress exponent, n, of ~6.5 for the low two temperatures and ~4.5 for the high two temperatures. The apparent activation energies of 290 and 165 kJ/mol are observed at the low, and high-temperature range, respectively. These values of activation energies are greater than those of solute/solvent self-diffusion. The stress exponents, n, and activation energy observed are rather high and this indicates the presence of threshold stress. This behavior occurred as a result of the dislocation interaction with the second phase particles that are existed in the alloy at the testing temperatures. The threshold stress decreases in an exponential manner as temperature increases. The true activation energy was computed by incorporating the threshold stress in the power-law relation between the stress and the strain. The magnitude of the true activation energy, Qt dropped to 234 and 102 kJ/mol at the low and high-temperature range, respectively. These values are close to that of diffusion of Zinc in Aluminum and diffusion of Magnesium in Aluminum, respectively. The Zener–Hollomon parameter for the alloy was developed as a function of effective stress. The data in each region (low and high-temperature region) coalescence in a segment line in each region.



Energies ◽  
2021 ◽  
Vol 14 (6) ◽  
pp. 1592
Author(s):  
Dominik Gryboś ◽  
Jacek S. Leszczyński ◽  
Dorota Czopek ◽  
Jerzy Wiciak

In this paper, we demonstrate how to reduce the noise level of expanded air from pneumatic tools. Instead of a muffler, we propose the expanded collecting system, where the air expands through the pneumatic tube and expansion collector. We have elaborated a mathematical model which illustrates the dynamics of the air flow, as well as the acoustic pressure at the end of the tube. The computational results were compared with experimental data to check the air dynamics and sound pressure. Moreover, the study presents the methodology of noise measurement generated in a pneumatic screwdriver in a quiet back room and on a window-fitting stand in a production hall. In addition, we have performed noise measurements for the pneumatic screwdriver and the pneumatic screwdriver on an industrial scale. These measurements prove the noise reduction of the pneumatic tools when the expanded collecting system is used. When the expanded collecting system was applied to the screwdriver, the measured Sound Pressure Level (SPL) decreased from 87 to 80 dB(A).



2021 ◽  
Vol 10 (1) ◽  
pp. 011-020
Author(s):  
Luyao Kou ◽  
Junjing Tang ◽  
Tu Hu ◽  
Baocheng Zhou ◽  
Li Yang

Abstract Generally, adding a certain amount of an additive to pulverized coal can promote its combustion performance. In this paper, the effect of CaO on the combustion characteristics and kinetic behavior of semi-coke was studied by thermogravimetric (TG) analysis. The results show that adding proper amount of CaO can reduce the ignition temperature of semi-coke and increase the combustion rate of semi-coke; with the increase in CaO content, the combustion rate of semi-coke increases first and then decreases, and the results of TG analysis showed that optimal addition amount of CaO is 2 wt%. The apparent activation energy of CaO with different addition amounts of CaO was calculated by Coats–Redfern integration method. The apparent activation energy of semi-coke in the combustion reaction increases first and then decreases with the increase in CaO addition. The apparent activation energies of different samples at different conversion rates were calculated by Flynn–Wall–Ozawa integral method. It was found that the apparent activation energies of semi-coke during combustion reaction decreased with the increase in conversion.



2020 ◽  
Vol 0 (0) ◽  
Author(s):  
Mykhaylo Tkach ◽  
Serhii Morhun ◽  
Yuri Zolotoy ◽  
Irina Zhuk

AbstractNatural frequencies and vibration modes of axial compressor blades are investigated. A refined mathematical model based on the usage of an eight-nodal curvilinear isoparametric finite element was applied. The verification of the model is carried out by finding the frequencies and vibration modes of a smooth cylindrical shell and comparing them with experimental data. A high-precision experimental setup based on an advanced method of time-dependent electronic interferometry was developed for this aim. Thus, the objective of the study is to verify the adequacy of the refined mathematical model by means of the advanced time-dependent electronic interferometry experimental method. The divergence of the results of frequency measurements between numerical calculations and experimental data does not exceed 5 % that indicates the adequacy and high reliability of the developed mathematical model. The developed mathematical model and experimental setup can be used later in the study of blades with more complex geometric and strength characteristics or in cases when the real boundary conditions or mechanical characteristics of material are uncertain.



2020 ◽  
Vol 2020 ◽  
pp. 1-12
Author(s):  
Xiaoguo Wang ◽  
Jian Qin ◽  
Hiromi Nagaumi ◽  
Ruirui Wu ◽  
Qiushu Li

The hot deformation behaviors of homogenized direct-chill (DC) casting 6061 aluminum alloys and Mn/Cr-containing aluminum alloys denoted as WQ1 were studied systematically by uniaxial compression tests at various deformation temperatures and strain rates. Hot deformation behavior of WQ1 alloy was remarkably changed compared to that of 6061 alloy with the presence of α-Al(MnCr)Si dispersoids. The hyperbolic-sine constitutive equation was employed to determine the materials constants and activation energies of both studied alloys. The evolution of the activation energies of two alloys was investigated on a revised Sellars’ constitutive equation. The processing maps and activation energy maps of both alloys were also constructed to reveal deformation stable domains and optimize deformation parameters, respectively. Under the influence of α dispersoids, WQ1 alloy presented a higher activation energy, around 40 kJ/mol greater than 6061 alloy’s at the same deformation conditions. Dynamic recrystallization (DRX) is main dynamic softening mechanism in safe processing domain of 6061 alloy, while dynamic recovery (DRV) was main dynamic softening mechanism in WQ1 alloy due to pinning effect of α-Al(MnCr)Si dispersoids. α dispersoids can not only resist DRX but also increase power required for deformation of WQ1 alloy. The microstructure analysis revealed that the flow instability was attributed to the void formation and intermetallic cracking during hot deformation of both alloys.



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