Coarse-grained models for frontal photopolymerization with evolving conversion profile
File(s)FPPevolve_PolymerInt_rev.pdf (882.48 KB)
Accepted version
Author(s)
Purnama, AR
Hennessy, MG
Vitale, A
Cabral, JT
Type
Journal Article
Abstract
We introduce a series of ‘minimal’ models to describe a common light-driven directional solidification process, known as frontal photopolymerization (FPP), focusing on experimental observables: the solidification kinetics, light attenuation and spatiotemporal monomer-to-polymer conversion. Specifically, we focus on FPP propagation that yields conversion profiles that are not invariant with time, and which cannot be simply described by the presence of mass or heat diffusion. The models are assessed against experimental data for the photopolymerization of a model trimethacrylate system. We find that the simplest model, comprising a single equation of motion for the conversion fraction ϕ and a generalized Beer–Lambert law, can only describe the experimental data by assuming an unphysical variation in optical absorption. Introducing a ϕ-dependent reaction constant Keff is found to require a time dependence, regardless of the functional form in ϕ. We conclude by introducing a ‘minimal’ chemical model, which is based on a simple three-step reaction scheme involving the spatiotemporal evolution of the photoinitiator fraction, relative fraction of radicals and monomer conversion fraction, that is able to capture the experimental data with a small number of parameters and under reasonable FPP assumptions. Our framework provides important predictive ability for ubiquitous solidification and patterning processes, including three-dimensional printing, via photopolymerization.
Date Issued
2017-03-22
Date Acceptance
2017-02-02
Citation
POLYMER INTERNATIONAL, 2017, 66 (6), pp.752-760
ISSN
0959-8103
Publisher
WILEY
Start Page
752
End Page
760
Journal / Book Title
POLYMER INTERNATIONAL
Volume
66
Issue
6
Copyright Statement
© 2017 Society of Chemical Industry. This is the accepted version of the following article: Purnama, A. R., Hennessy, M. G., Vitale, A. and Cabral, J. T. (2017), Coarse-grained models for frontal photopolymerization with evolving conversion profile. Polym. Int, 66: 752–760. doi:10.1002/pi.5344, which has been published in final form at https://dx.doi.org/10.1002/pi.5344
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000403239200003&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Grant Number
EP/L022176/1
Subjects
Science & Technology
Physical Sciences
Polymer Science
photopolymerization
minimal model
front propagation
patterning
OPTICAL ATTENUATION
0301 Analytical Chemistry
0904 Chemical Engineering
0912 Materials Engineering
Polymers
Publication Status
Published