Cure kinetics of an epoxidized hemp oil based bioresin system
Nathan W. Manthey, Francisco Cardona, Thiru Aravinthan, Tyson Cooney
Abstract
Nathan W. Manthey, Francisco Cardona, Thiru Aravinthan, Tyson Cooney
Abstract
Abstract A novel epoxidized hemp oil (EHO) based bioresin was synthesized by epoxidation in situ with peroxyacetic acid. In this research the cure kinetics of an EHO based bioresin system cured with triethylenetetramine (TETA) was studied by differential scanning calorimetry using both isothermal and nonisothermal data. The results show that the curing behavior can be modeled with a modified Kamal autocatalytic model that accounts for a shift to a diffusion‐controlled reaction postvitrification. The total order of the reaction was found to decrease with an increase in temperature from ∼ 5.2 at 110°C to ∼ 2.4 at 120°C. Dynamic activation energies were determined from the Kissinger (51.8 kJ/mol) and Ozawa‐Flynn‐Wall (56.3 kJ/mol) methods. Activation energies determined from the autocatalytic method were 139.5 kJ/mol and −80.5 kJ/mol. The observed negative activation energy is thought to be due to an unidentified competitive reaction that gives rise to the appearance of k2 decreasing with increasing temperature. The agreement of fit of the model predictions with experimental values was satisfactory for all temperatures. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011
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Abstract A novel epoxidized hemp oil (EHO) based bioresin was synthesized by epoxidation in situ with peroxyacetic acid. In this research the cure kinetics of an EHO based bioresin system cured with triethylenetetramine (TETA) was studied by differential scanning calorimetry using both isothermal and nonisothermal data. The results show that the curing behavior can be modeled with a modified Kamal autocatalytic model that accounts for a shift to a diffusion‐controlled reaction postvitrification. The total order of the reaction was found to decrease with an increase in temperature from ∼ 5.2 at 110°C to ∼ 2.4 at 120°C. Dynamic activation energies were determined from the Kissinger (51.8 kJ/mol) and Ozawa‐Flynn‐Wall (56.3 kJ/mol) methods. Activation energies determined from the autocatalytic method were 139.5 kJ/mol and −80.5 kJ/mol. The observed negative activation energy is thought to be due to an unidentified competitive reaction that gives rise to the appearance of k2 decreasing with increasing temperature. The agreement of fit of the model predictions with experimental values was satisfactory for all temperatures. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011
Key concepts: Autocatalysis, Activation energy, Triethylenetetramine, Kinetics, Differential scanning calorimetry, Curing (chemistry), Isothermal process, Materials science