Open Access Open Access  Restricted Access Subscription Access

Effects of Stoichiometry on Properties of DGEBF/DETDA Epoxy Using Molecular Dynamics



This article details the molecular modeling of full and off-stoichiometry models of the DGEBF/DETDA epoxy system using Molecular Dynamics to predict the mechanical properties as a function of the crosslinking density. The Reactive Interface Force Field (IFF-R) is implemented in this work to simulate mechanical deformation. The “fix bond/react” command in LAMMPS is used to simulate crosslinking between epoxy monomers. The results show that the predicted mass density, volumetric shrinkage, and bulk modulus have a strong dependence on the stoichiometry of the epoxy.


Full Text:



Skourlis, T.P. and R.L. McCullough, An experimental investigation of the effect of prepolymer

molecular weight and stoichiometry on thermal and tensile properties of epoxy resins. Journal

of Applied Polymer Science, 1996. 62(3): p. 481-490.

Meyer, F., et al., The effect of stoichiometry and thermal history during cure on structure and

properties of epoxy networks. Polymer, 1995. 36(7): p. 1407-1414.

Gude, M.R., S.G. Prolongo, and A. Ureña, Effect of the epoxy/amine stoichiometry on the

properties of carbon nanotube/epoxy composites. Journal of Thermal Analysis and

Calorimetry, 2012. 108(2): p. 717-723.

Minty, R.F., L. Yang, and J.L. Thomason, The influence of hardener-to-epoxy ratio on the

interfacial strength in glass fibre reinforced epoxy composites. Composites Part A: Applied

Science and Manufacturing, 2018. 112: p. 64-70.

Morgan, R.J., F.-M. Kong, and C.M. Walkup, Structure-property relations of

polyethertriamine-cured bisphenol-A-diglycidyl ether epoxies. Polymer, 1984. 25(3): p. 375-

Calventus, Y., S. Montserrat, and J.M. Hutchinson, Enthalpy relaxation of non-stoichiometric

epoxy-amine resins. Polymer, 2001. 42(16): p. 7081-7093.

Gupta, V.B. and C. Brahatheeswaran, Molecular packing and free volume in crosslinked epoxy

networks. Polymer, 1991. 32(10): p. 1875-1884.

Fernandez-Nograro, F., et al., Dynamic and mechanical properties of DGEBA/poly(propylene

oxide) amine based epoxy resins as a function of stoichiometry. European Polymer Journal,

32(2): p. 257-266.

Cheng, X., et al., Morphologies and mechanical properties of polyethersulfone modified epoxy

blends through multifunctional epoxy composition. Journal of Applied Polymer Science, 2017.


Olaya, M.N., G.M. Odegard, and M. Maiaru, A Novel Approach to Characterization of

Composite Polymer Matrix Materials for Integrated Computational Materials Engineering

Approaches, in AIAA Scitech 2021 Forum.

Chinkanjanarot, S., et al., Multiscale thermal modeling of cured cycloaliphatic epoxy/carbon

fiber composites. Journal of Applied Polymer Science, 2018. 135(25).

Bandyopadhyay, A. and G.M. Odegard, Molecular modeling of crosslink distribution in epoxy

polymers. Modelling and Simulation in Materials Science and Engineering, 2012. 20(4).

Li, C. and A. Strachan, Molecular simulations of crosslinking process of thermosetting

polymers. Polymer, 2010. 51(25): p. 6058-6070.

Radue, M.S., et al., Comparing the Mechanical Response of Di-, Tri-, and Tetra-functional

Resin Epoxies with Reactive Molecular Dynamics. J Polym Sci B Polym Phys, 2018. 56(3): p.


Patil, S.U., et al., Interfacial characteristics between flattened CNT stacks and polyimides: A

molecular dynamics study. Computational Materials Science, 2020. 185: p. 109970.

Odegard, G.M., et al., Predicting mechanical response of crosslinked epoxy using ReaxFF.

Chemical Physics Letters, 2014. 591: p. 175-178.

Pisani, W.A., et al., Interfacial modeling of flattened CNT composites with cyanate ester and

PEEK polymers. Composites Part B: Engineering, 2021. 211: p. 108672.

Odagiri, N., et al., Amine/epoxy stoichiometric ratio dependence of crosslinked structure and

ductility in amine-cured epoxy thermosetting resins. Journal of Applied Polymer Science,

138(23): p. 50542.

Okabe, T., et al., Curing reaction of epoxy resin composed of mixed base resin and curing

agent: Experiments and molecular simulation. Polymer, 2013. 54(17): p. 4660-4668.

Alhabill, F.N., et al., Influence of filler/matrix interactions on resin/hardener stoichiometry,

molecular dynamics, and particle dispersion of silicon nitride/epoxy nanocomposites. Journal

of Materials Science, 2018. 53(6): p. 4144-4158.

Sagar Patil, S.S., Prathamesh Deshpande, Khatereh Kashmari, Michael Olaya, Gregory

Odegard, Marianna Maiarù. Multi-scale Approach to Predict Cure-Induced Residual Stresses

in an Epoxy System. in Proceedings of the American Society for Composites—Thirty-fifth

Technical Conference. 2020. Virtual.

P. P. Deshpande, S.S., S. Patil, K. Kashmari, Michael Olaya, G. M. Odegard, M. Maiarù.

Multiscale Modelling of the Cure Process in Thermoset Polymers using ICME. in Proceedings

of the American Society for Composites—Thirty-fifth Technical Conference. 2020. Virtual.

Sagar Patil, S.S., Prathamesh Deshpande, Khatereh Kashmari, Gregory Odegard, Marianna

Maiarù. Prediction Of Residual Stress Build-Up In Polymer Matrix Composite During Cure

Using A Two-Scale Approach. in Proceedings of the American Society for Composites—

Thirty-fourth Technical Conference. 2019.

P.P. Deshpande, S.S., S. Patil, K. Kashmari, G.M. Odegard, M. Maiaru. A Multi-Scale

Approach For Modelling The Cure Of Thermoset Polymers Within ICME. in Proceedings of

the American Society for Composites—Thirty-fourth Technical Conference. 2019.

Heinz, H., et al., Thermodynamically consistent force fields for the assembly of inorganic,

organic, and biological nanostructures: the INTERFACE force field. Langmuir, 2013. 29(6): p.


Pramanik, C., et al., Carbon Nanotube Dispersion in Solvents and Polymer Solutions:

Mechanisms, Assembly, and Preferences. ACS Nano, 2017. 11(12): p. 12805-12816.

Plimpton, S., Fast Parallel Algorithms for Short-Range Molecular Dynamics. Journal of

Computational Physics, 1995. 117(1): p. 1-19.

Gissinger, J.R., B.D. Jensen, and K.E. Wise, Modeling chemical reactions in classical

molecular dynamics simulations. Polymer, 2017. 128: p. 211-217.

Tack, J.L. and D.M. Ford, Thermodynamic and mechanical properties of epoxy resin DGEBF

crosslinked with DETDA by molecular dynamics. Journal of Molecular Graphics and

Modelling, 2008. 26(8): p. 1269-1275.

Al Mahmud, H., et al., Multiscale modeling of carbon fiber- graphene nanoplatelet-epoxy

hybrid composites using a reactive force field. Composites Part B: Engineering, 2019. 172: p.


Varshney, V., et al., A Molecular Dynamics Study of Epoxy-Based Networks: Cross-Linking

Procedure and Prediction of Molecular and Material Properties. Macromolecules, 2008.

(18): p. 6837-6842.

Nouri, N. and S. Ziaei-Rad, A Molecular Dynamics Investigation on Mechanical Properties of

Cross-Linked Polymer Networks. Macromolecules, 2011. 44(13): p. 5481-5489.

Estridge, C.E., The effects of competitive primary and secondary amine reactivity on the

structural evolution and properties of an epoxy thermoset resin during cure: A molecular

dynamics study. Polymer, 2018. 141: p. 12-20.

Dixon, S., et al., The Development of Shear and Compression Elastic Moduli in Curing Epoxy

Adhesives Measured Using Non‐ Contact Ultrasonic Transducers. AIP Conference

Proceedings, 2003. 657(1): p. 1049-1055.

Nawab, Y., et al., Characterization of the cure shrinkage, reaction kinetics, bulk modulus and

thermal conductivity of thermoset resin from a single experiment. Journal of Materials Science,

48(6): p. 2394-2403.


  • There are currently no refbacks.