TY - JOUR
T1 - Microkinetic modeling of the autoxidative curing of an alkyd and oil-based paint model system
AU - Oakley, Lindsay H.
AU - Casadio, Francesca
AU - Shull, Kenneth R
AU - Broadbelt, Linda J
N1 - Funding Information:
Financial support from the National Science Foundation (DMR-1241667) is gratefully acknowledged.
Publisher Copyright:
© 2015, Springer-Verlag Berlin Heidelberg.
PY - 2015/7/31
Y1 - 2015/7/31
N2 - Elucidating the curing and aging mechanisms of alkyd and other oil-based paints is valuable for the fields of conservation and bio-based coatings. Recent research has demonstrated the limitations of artificial aging in predicting the actual properties of paints that are hundreds of years old. Kinetic modeling offers pathways to develop a realistic and dynamic description of the composition of these oil-based paint coatings and facilitates the exploration of the effects of various environmental conditions on their long-term chemical stability. This work presents the construction of a kinetic Monte Carlo framework from elementary steps for the cobalt-catalyzed autoxidative curing of an ethyl linoleate model system up to the formation of single cross-links. Kinetic correlations for reaction families of similar chemistry are employed to reduce the number of parameters required to calculate rate constants in Arrhenius form. The model, developed from mechanisms proposed in the literature, shows good agreement with experiment for the formation of primary products in the early stages of curing. The model has also revealed that the mechanisms proposed in the literature for the formation of secondary products, such as volatile aldehydes, are still not well established, and alternative routes are under evaluation.
AB - Elucidating the curing and aging mechanisms of alkyd and other oil-based paints is valuable for the fields of conservation and bio-based coatings. Recent research has demonstrated the limitations of artificial aging in predicting the actual properties of paints that are hundreds of years old. Kinetic modeling offers pathways to develop a realistic and dynamic description of the composition of these oil-based paint coatings and facilitates the exploration of the effects of various environmental conditions on their long-term chemical stability. This work presents the construction of a kinetic Monte Carlo framework from elementary steps for the cobalt-catalyzed autoxidative curing of an ethyl linoleate model system up to the formation of single cross-links. Kinetic correlations for reaction families of similar chemistry are employed to reduce the number of parameters required to calculate rate constants in Arrhenius form. The model, developed from mechanisms proposed in the literature, shows good agreement with experiment for the formation of primary products in the early stages of curing. The model has also revealed that the mechanisms proposed in the literature for the formation of secondary products, such as volatile aldehydes, are still not well established, and alternative routes are under evaluation.
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U2 - 10.1007/s00339-015-9363-1
DO - 10.1007/s00339-015-9363-1
M3 - Article
AN - SCOPUS:84947035313
VL - 121
SP - 869
EP - 878
JO - Applied Physics A: Materials Science and Processing
JF - Applied Physics A: Materials Science and Processing
SN - 0947-8396
IS - 3
ER -