Modeling the Evolution of Crosslinked and Extractable Material in an Oil‐Based Paint Model System

Abstract

The construction of mechanistic models for the autoxidation of fatty acid or ester substrates found in oil paint binders is a challenging undertaking due to the complexity of the large crosslinked species that form, and the small molecules that volatilize. Building models that capture this product diversity are made possible by automating the process of network generation. This work presents a microkinetic model for the autoxidation of ethyl linoleate catalyzed by cobalt(II) 2-ethyl hexanoate. The mechanism size was controlled by using a rate-based criterion to include the most kinetically relevant reactions from among the millions of possible reactions generated. The resulting model was solved and compared to experimental metrics. Quantities such as hexanal production and the consumption of unsaturated moieties were in good agreement with experiment. Finally, the model was used to explore the effect of the catalyst concentration and temperature on key measurables.

A Review on Lignin Liquefaction: Advanced Characterization of Structure and Microkinetic Modeling

“…One emerging approach to achieve this is through the development of a microkinetic framework for describing thermochemical conversion. Microkinetic analysis has previously been used to study a wide array of subjects, including heterogeneous catalysis, 46,47 oxidation chemistry, 48−52 autoxidation, 53,54 and coal pyrolysis. 55−62 Our overall goal is to review modeling and experimental research addressing components relevant to the creation of a microkinetic framework to describe lignin liquefaction reactions, with emphasis given to those methods that provide ready-to-use data for a computational lignin pyrolysis model.…”

How Science Can Contribute to the Remedial Conservation of Cultural Heritage

“…[7] Analytical tools can gain great support from modeling and theoretical chemistry, which can be employed to construct mechanisms for the degradative reactivity of art materials. [8] Diagnosis also links to preventive conservation when enhanced sensors [9] are used to monitor the presence of pollutants in museum environments and art storages. In principle, the citizens themselves could contribute to analysis campaigns of CH through smartphone diagnostics.…”

“…Current challenges involve the development of newer non‐invasive techniques [5] with high spatial resolution, [6] and portable instruments to allow feasible analysis of precious works [7] . Analytical tools can gain great support from modeling and theoretical chemistry, which can be employed to construct mechanisms for the degradative reactivity of art materials [8] . Diagnosis also links to preventive conservation when enhanced sensors [9] are used to monitor the presence of pollutants in museum environments and art storages.…”

New Members of the National Academy of Engineering

“…The scientific motivation driving the work in the Broadbelt group is unraveling complexity in reacting systems, with specific interest in biomass conversion, heterogeneous and homogeneous catalysis of hydrocarbon conversion, novel biochemical pathways, and polymerization/depolymerization kinetics. Her communication on the evolution of crosslinked and extractable material in an oil‐based paint model system was published in Angewandte Chemie 's Special Issue on Heritage Science Plus Analytical Chemistry, Spectroscopy, and Bioanalysis.…”