Structural evidence that the polymerization rate dictates order and intrinsic strain generation in photocured methacrylate biomedical polymers

Research output: Contribution to journalArticlepeer-review


  • Slobodan Sirovica
  • Maximilian W. A. Skoda
  • Maciej Podgorski
  • Paul B. J. Thompson
  • Yilan Guo
  • Andrew J. Smith
  • Karun Dewan
  • Richard A. Martin

Colleges, School and Institutes

External organisations

  • XMaS The UK CRG, ESRF-The European Synchrotron
  • Aston University
  • University of Alberta
  • Diamond Light Source
  • Maria Curie-Skłodowska University
  • University of Colorado at Boulder
  • ISIS Pulsed Neutron and Muon Source


The influence of reaction rate on the evolving polymer structure of photo-activated dimethacrylate biomedical resins was investigated using neutron and in situ synchrotron X-ray scattering with simultaneous Fourier-transform-near-infrared spectroscopy. Previous studies have correlated the degree of reactive group conversion with mechanical properties, but the impact of polymerization rate on the resultant polymer structure is unknown. Here, we demonstrate that the medium-range structural order at the functional end groups of these materials is dependent on the reaction rate. Accelerating polymerization increases correlation lengths in the methacrylate end groups but reduces the medium-range structural order per converted vinyl bond when compared with more slowly polymerized systems. At faster rates of polymerization, the conformation of atoms at the reacting end group can become fixed into the polymer structure at the onset of autodeceleration, storing residual strain. Neutron scattering confirms that the structural differences observed are reproduced at longer length scales. This effect is not as prominent in systems polymerized at slower rates despite similar final degrees of reactive group conversion. Results suggest that current interpretations of these materials, which extrapolate mechanical properties from conversion, may be incomplete. Accelerating polymerization can introduce structural differences, which will dictate residual strain and may ultimately explain the discrepancies in the predictive modeling of the mechanical behavior of these materials using conventional techniques.


Original languageEnglish
Pages (from-to)5377-5388
Number of pages12
Issue number14
Early online date10 Jul 2019
Publication statusPublished - 23 Jul 2019