scholarly journals Nonisothermal Cure Kinetics of Epoxy/Polyvinylpyrrolidone Functionalized Superparamagnetic Nano-Fe3O4 Composites: Effect of Zn and Mn Doping

2020 ◽  
Vol 4 (2) ◽  
pp. 55 ◽  
Author(s):  
Maryam Jouyandeh ◽  
Mohammad Reza Ganjali ◽  
Farzad Seidi ◽  
Huining Xiao ◽  
Mohammad Reza Saeb

The effects of the bulk and surface modification of nanoparticles on the cure kinetics of low-filled epoxy nanocomposites containing electrochemically synthesized polyvinylpyrrolidone (PVP) functionalized superparamagnetic iron oxide (PVP-SPIO), Zn-doped PVP-SPIO (Zn-PVP-SPIO), and Mn-doped PVP-SPIO (Mn-PVP-SPIO) were studied using differential scanning calorimetry (DSC) and cure kinetics analyses. Integral and differential isoconversional methods were used to calculate the activation energies (Eα) and consequently propose the appropriate reaction model for the curing reaction under nonisothermal conditions. According to the alteration of Eα versus the fractional extent of conversion, the Eα trend was changed through the partial replacement of Fe2+ sites by the Zn2+ and Mn2+ cations in the general formula of MxFe3-xO4, due to smaller amounts of energy being required for curing by the incorporation of Zn-PVP-SPIO and Mn-PVP-SPIO nanoparticles into the epoxy resin. A good agreement was observed between the theoretical calculation and the observed calorimetric data for the model validation.

2020 ◽  
Vol 4 (3) ◽  
pp. 111
Author(s):  
Zohre Karami ◽  
Seyed Mohammad Reza Paran ◽  
Poornima Vijayan P. ◽  
Mohammad Reza Ganjali ◽  
Maryam Jouyandeh ◽  
...  

Layered double hydroxide (LDH) minerals are promising candidates for developing polymer nanocomposites and the exchange of intercalating anions and metal ions in the LDH structure considerably affects their ultimate properties. Despite the fact that the synthesis of various kinds of LDHs has been the subject of numerous studies, the cure kinetics of LDH-based thermoset polymer composites has rarely been investigated. Herein, binary and ternary structures, including [Mg0.75 Al0.25 (OH)2]0.25+ [(CO32−)0.25/2∙m H2O]0.25−, [Mg0.75 Al0.25 (OH)2]0.25+ [(NO3−)0.25∙m H2O]0.25− and [Mg0.64 Zn0.11 Al0.25 (OH)2]0.25+ [(CO32−)0.25/2∙m H2O]0.25−, have been incorporated into epoxy to study the cure kinetics of the resulting nanocomposites by differential scanning calorimetry (DSC). Both integral and differential isoconversional methods serve to study the non-isothermal curing reactions of epoxy nanocomposites. The effects of carbonate and nitrate ions as intercalating agents on the cure kinetics are also discussed. The activation energy of cure (Eα) was calculated based on the Friedman and Kissinger–Akahira–Sunose (KAS) methods for epoxy/LDH nanocomposites. The order of autocatalytic reaction (m) for the epoxy/Mg-Al-NO3 (0.30 and 0.254 calculated by the Friedman and KAS methods, respectively) was smaller than that of the neat epoxy, which suggested a shift of the curing mechanism from an autocatalytic to noncatalytic reaction. Moreover, a higher frequency factor for the aforementioned nanocomposite suggests that the incorporation of Mg-Al-NO3 in the epoxy composite improved the curability of the epoxy. The results elucidate that the intercalating anions and the metal constituent of LDH significantly govern the cure kinetics of epoxy by the participation of nitrate anions in the epoxide ring-opening reaction.


e-Polymers ◽  
2007 ◽  
Vol 7 (1) ◽  
Author(s):  
Marcelo Hernandez ◽  
Jérôme Dupuy ◽  
Jannick Duchet ◽  
Henry Sautereau

Abstract The effect of thermoplastic PMMA and clay Cloisite 30B addition on the cure kinetics of an epoxy/amine thermosetting system was investigated using differential scanning calorimetry (DSC) and modelled using a single kinetic model. For obtaining a good agreement between the experimental results and theoretical modeling, it was necessary to separate the ternary system in two formulations: matrix/PMMA and matrix/clay systems. It appeared that the addition of PMMA delays the reaction up to the phase separation phenomenon due to a dilution effect of the reactive species. In opposition, the presence of clays accelerates the reaction (probably due to a catalytic effect of some metals ions introduced with the clay) but it has no sensitive effect on the cloud point conversion in the presence of PMMA. The modeling results are in good agreement with those experimentally obtained.


2020 ◽  
Vol 4 (3) ◽  
pp. 102
Author(s):  
Maryam Jouyandeh ◽  
Zohre Karami ◽  
Seyed Mohammad Reza Paran ◽  
Amin Hamed Mashhadzadeh ◽  
Mohammad Reza Ganjali ◽  
...  

This short communication aims to evaluate the cure kinetics of epoxy/NixFe3−xO4 nanocomposites. Differential scanning calorimetry (DSC) provided support for cure kinetics analysis based on the variation of activation energy (Eα) as a function of the extent of crosslinking reaction, α. The average values of Eα calculated based on Kissinger and Friedman methods were 59.22 and 57.35 kJ/mol for the neat epoxy, 43.37 and 48.74 kJ/mol for the epoxy/Fe3O4, and eventually 50.48 and 49.19 kJ/mol for the epoxy/NixFe3−xO4 nanocomposites. The partial replacement of Fe2+ ion sites in the Fe3O4 crystal lattice by the Ni2+ ions changed to some content the cure kinetic profile because of the fact that a lower level of energy was needed for curing by incorporation of NixFe3−xO4 into the epoxy matrix. The rate of reaction calculated theoretically adequately fitted with experimental profiles obtained in DSC experiments.


2021 ◽  
pp. 002199832110015
Author(s):  
Alexander Vedernikov ◽  
Yaroslav Nasonov ◽  
Roman Korotkov ◽  
Sergey Gusev ◽  
Iskander Akhatov ◽  
...  

Pultrusion is a highly efficient composite manufacturing process. To accurately describe pultrusion, an appropriate model of resin cure kinetics is required. In this study, we investigated cure kinetics modeling of a vinyl ester pultrusion resin (Atlac 430) in the presence of aluminum hydroxide (Al(OH)3) and zinc stearate (Zn(C18H35O2)2) as processing additives. Herein, four different resin compositions were studied: neat resin composition, composition with Al(OH)3, composition comprising Zn(C18H35O2)2, and composition containing both Al(OH)3 and Zn(C18H35O2)2. To analyze each composition, we performed differential scanning calorimetry at the heating rates of 5, 7.5, and 10 K/min. To characterize the cure kinetics of Atlac 430, 16 kinetic models were tested, and their performances were compared. The model based on the [Formula: see text]th-order autocatalytic reaction demonstrated the best results, with a 4.5% mean squared error (MSE) between the experimental and predicted data. This study proposes a method to reduce the MSE resulting from the simultaneous melting of Zn(C18H35O2)2. We were able to reduce the MSE by approximately 34%. Numerical simulations conducted at different temperatures and pulling speeds demonstrated a significant influence of resin composition on the pultrusion of a flat laminate profile. Simulation results obtained for the 600 mm long die block at different die temperatures (115, 120, 125, and 130 °C) showed that for a resin with a final degree of cure exceeding 95% at the die exit, the maximum difference between the predicted values of pulling speed for a specified set of compositions may exceed 1.7 times.


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Ali Kuliaei ◽  
Iraj Amiri Amraei ◽  
Seyed Rasoul Mousavi

Abstract The purpose behind this research was to determine the optimum formulation and investigate the cure kinetics of a diglycidyl ether of bisphenol-A (DGEBA)-based epoxy resin cured by dicyandiamide and diuron for use in prepregs. First, all formulations were examined by the tensile test, and then, the specimens with higher mechanical properties were further investigated by viscometry and tack tests. The cure kinetics of the best formulation (based on tack test) in nonisothermal mode was investigated using differential scanning calorimetry at different heating rates. Kissinger and Ozawa method was used for determining the kinetic parameters of the curing process. The activation energy obtained by this method was 71.43 kJ/mol. The heating rate had no significant effect on the reaction order and the total reaction order was approximately constant ( m + n ≅ 2.1 $m+n\cong 2.1$ ). By comparing the experimental data and the theoretical data obtained by Kissinger and Ozawa method, a good agreement was seen between them. By increasing the degree of conversion, the viscosity decreased; as the degree of conversion increased, so did the slope of viscosity. The results of the tack test also indicated that the highest tack could be obtained with 25% progress of curing.


2018 ◽  
Vol 7 (1) ◽  
pp. 21-30 ◽  
Author(s):  
Norbert Halmen ◽  
Christoph Kugler ◽  
Eduard Kraus ◽  
Benjamin Baudrit ◽  
Thomas Hochrein ◽  
...  

Abstract. The degree of cross-linking and curing is one of the most important values concerning the quality of cross-linked polyethylene (PE-X) and the functionality of adhesives and resin-based components. Up to now, the measurement of this property has mostly been time-consuming and usually destructive. Within the shown work the feasibility of single-sided nuclear magnetic resonance (NMR) for the non-destructive determination of the degree of cross-linking and curing as process monitoring was investigated. First results indicate the possibility of distinguishing between PE-X samples with different degrees of cross-linking. The homogeneity of the samples and the curing kinetics of adhesives can also be monitored. The measurements show good agreement with reference tests (wet chemical analysis, differential scanning calorimetry, dielectric analysis). Furthermore, the influence of sample temperature on the characteristic relaxation times can be observed.


2020 ◽  
Vol 4 (3) ◽  
pp. 107
Author(s):  
Maryam Jouyandeh ◽  
Mohammad Reza Ganjali ◽  
Zohre Karami ◽  
Morteza Rezapour ◽  
Babak Bagheri ◽  
...  

This work reports on the thermal analysis of epoxy containing polyvinyl chloride (PVC) surface-functionalized magnetic nanoparticles (PVC–S/MNP) and its bulk-modified nickel-doped counterpart (PVC–S/MNP/Bi–B). Nanoparticles were synthesized through the cathodic electro-deposition method. The morphology of particles was imaged on a field-emission scanning electron microscope (FE-SEM), while X-ray diffraction analysis and Fourier-transform infrared spectroscopy (FTIR) were used to detect changes in the structure of nanoparticles. The magnetic behavior of particles was also studied by vibrating sample magnetometry (VSM). In particular, we focused on the effect of the bulk (Ni-doping) and surface (PVC-capping) modifications of MNPs on the thermal crosslinking of epoxy using nonisothermal differential scanning calorimetry (DSC) varying the heating rate. The cure labels of the prepared nanocomposites were assigned to them, as quantified by the cure index. The good cure state was assigned to the system containing PVC–S/MNP/Bi–B as a result of excessive ring opening of epoxy. Cure kinetics parameters of PVC–S/MNP/Bi–B incorporated epoxy was obtained by the use of isoconversional methodology. The activation energy of epoxy was decreased upon addition of 0.1 wt% of PVC–S/MNP/Bi–B due to the reaction of Cl− of PVC by the functional groups of resin.


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