Photo-polymerisation variables influence the structure and subsequent thermal response of dental resin matrices


Objective The structure of the polymer phase of dental resin-based-composites is highly sensitive to photo-polymerisation variables. The objective of this study was to understand how different polymer structures, generated with different photo-polymerisation protocols, respond to thermal perturbation. Methods Experimental resins were prepared from a series of Bis-GMA/TEGDMA blends (40/60, 50/50 and 60/40 wt.%), with either Camphorquinone/DMAEMA or Lucirin TPO as the photo-initiator system. Resins were photo-polymerised, in a disc geometry, at either relatively ‘high’ (3000 mW cm−2 for 6 s) or ‘low’ (300 mW cm−2 for 60 s) irradiances ensuring matched radiant exposures (18 J cm−2). Specimens were heated, from 20−160 °C at a rate of 5 °C min−1, whilst simultaneous synchrotron X-ray scattering measurements were taken at 5 °C increments to determine changes in polymer chain segment extension and medium-range order as a function of temperature. For each unique resin composition (n = 3), differential scanning calorimetry was used to measure glass transition temperatures using the same heating protocol. A paired t-test was used to determine significant differences in the glass transition temperature between irradiance protocols and photo-initiator chemistry at ɑ = 0.05. Results Resins pre-polymerised through the use of TPO and or high irradiances demonstrated a reduced rate of chain extension indicative of lower thermal expansion and a larger decrease in relative order when heated below the glass transition temperature. Above the transition temperature, differences in the rate of chain extension were negligible, but slower converted systems showed greater relative order. There was no significant difference in the glass transition temperature between different photo-initiator systems or irradiance protocols. Significance The evolution of chain extension and medium-range order during heating is dependent on the initial polymer structure which is influenced by photo-polymerisation variables. Less ordered systems, generated at faster rates of reactive group conversion displayed reduced chain extension below the glass transition temperature and maintained lower order throughout heating.

Publication DOI:
Divisions: College of Engineering & Physical Sciences > School of Informatics and Digital Engineering > Electrical and Electronic Engineering
Additional Information: © 2020, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International Funding: Science and Technology Facilities Council(award no. ST/L502510/1) and the Royal College of Surgeons of England Small Grants Scheme(Faculty of Dentistry).
Uncontrolled Keywords: Differential scanning calorimetry,Fourier Transform Infrared Spectroscopy,Photo-polymerisation,Polymer structure,Resin matrices,Synchrotron X-ray scattering,Thermal perturbation,Materials Science(all),Dentistry(all),Mechanics of Materials
Publication ISSN: 0109-5641
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Related URLs: https://linking ... 109564119309443 (Publisher URL)
http://www.scop ... tnerID=8YFLogxK (Scopus URL)
PURE Output Type: Article
Published Date: 2020-03
Published Online Date: 2020-01-07
Accepted Date: 2020-01-01
Authors: Sirovica, Slobodan
Guo, Yilan
Guan, Raymond
Skoda, Maximilian W.a.
Palin, William M.
Morrell, Alexander P.
Romanyk, Dan L.
Martin, Richard A. (ORCID Profile 0000-0002-6013-2334)
Addison, Owen

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