Styrene–butyl acrylate (S–BuA) copolymers were synthesized by nitroxide-mediated controlled radical polymerization using an alkoxyamine as an initiator. Using different synthetic methodologies, statistical copolymers were be obtained by batch nitroxide mediated polymerization while the gradient composition was a forced gradient by continuous addition of S during BuA polymerization (semi-batch process). These gradient copolymers have been studied by ¹H NMR and size exclusion chromatography to characterize the gradient composition molecular structure. The evolution of the composition was correlated with the glass transition temperature (T_g) of the copolymers. The gradient copolymers exhibit one T_g with a value in between the T_g of polystyrene and poly(butyl acrylate), indicating that the materials did not present well defined microphase separation. Specific organization at the air–polymer interface of such copolymers has also been demonstrated by comparison between classical and attenuated total reflection (ATR) Fourier transform infra-red spectra. This bulk soft matter assembly was confirmed by AFM analysis, which showed a different morphology at the surface and in the bulk following removal of the top layer. Moreover, for the most well defined gradient composition, a specific nano-structuring was demonstrated by small angle neutron scattering. The preliminary rheological properties of these gradient copolymers were studied and are discussed in relation with their molecular structure.

This work deals with the study of the viscoelastic and adherence properties of pressure-sensitive adhesive (PSA) formulations dedicated to medical applications. We have developed a specific viscoelastic substrate to measure the adherence properties of PSAs that mimics adhesion on human skin. In the present article, we describe several experiments dedicated to a better understanding of adhesion on viscoelastic substrates without discussing specifically the case of human skin. In this way, we have studied different model adhesive formulations based on real medical formulations, and we have related the rheological behavior to the adherence properties obtained on different substrates to study the various specific effects due to the viscoelasticity of soft substrates. We propose from this study a failure criterion that allows one to derive a reasonable estimate of the peeling transition rate from cohesive to interfacial or stick–slip failure.

In this work, polycaprolactone–polyethylene glycol (PCL–PEG) based waterborne polyurethane–urea (WBPUU) inks have been developed for an extrusion-based 3D printing technology. The WBPUU, synthesized from an optimized ratio of hydrophobic polycaprolactone diol and hydrophilic polyethylene glycol (0.2:0.8) in the soft segment, is able to form a physical gel at low solid contents. WBPUU inks with different solid contents have been synthesized. The rheology of the prepared systems was studied and the WBPUUs were subsequently used in the printing of different pieces to demonstrate the relationship between their rheological properties and their printing viability, establishing an optimal window of compositions for the developed WBPUU based inks. The results showed that the increase in solid content results in more structured inks, presenting a higher storage modulus as well as lower tan δ values, allowing for the improvement of the ink’s shape fidelity. However, an increase in solid content also leads to an increase in the yield point and viscosity, leading to printability limitations. From among all printable systems, the WBPUU with a solid content of 32 wt% is proposed to be the more suitable ink for a successful printing performance, presenting both adequate printability and good shape fidelity, which leads to the realization of a recognizable and accurate 3D construct and an understanding of its relationship with rheological parameters.