Reducing residual stress in photopolymerized composites by grafting high-mobility polymer chains onto the filler-matrix interface

3D/4D printing of thermosets, composites and hydrogels, lithographic procedures and dental resins are important examples of applications that rely on light-driven polymerization supported on substrates. Adhesion between the polymer and substrate during photopolymerization (and even between printed layers) can restrict the usual polymerization shrinkage, leading to the generation of residual stresses. These residual stresses can result in poor-quality products due to the presence of cracks and occurrence of warpage. In this work, silica nano-particles were incorporated into photopolymerizable dimethacrylate based networks. These nanoparticles had their surface modified by grafting polymer chains with high mobility at usual room temperatures (low glass transition temperature polymer) and with high affinity towards the polymer matrix in order to test the hypothesis that these high-mobility chains could be helpful in dissipating stress and energy generated during photopolymerization in conditions in which the polymerization shrinkage is restricted. The nanoparticles and composites were analyzed via: electron microscopy (SEM), thermal analysis and mechanical bending tests. The evolution of the monomer-to-polymer conversion during photopolymerization was monitored using real-time infrared (FTIR) spectroscopy. To determine the residual stress generated by the polymerization at restricted contraction conditions, a universal mechanical testing machine was adapted and used. The results showed that silica nanoparticles with grafted high-mobility polymer chains that were able to interpenetrate and interact with the dimethacrylate based networks led to the production of composites having higher mechanical properties and lower polymerization stresses than composites containing only silanized nanoparticles and nanoparticles having immiscible polymer grafts towards the dimethacrylate based network. Results indicate that the modifications of the interface of composites developed in this work can be useful in the formulation of materials with improved mechanical properties and stability regarding polymerization shrinkage and residual stress that can lead to higher-quality products obtained in processes that employ light-driven polymerization supported on substrates or that occur on sequential polymerized layers, such as 3D/4D printing, lithography and in dental applications.