The effects of the soft block fraction and H-bond state in thermoplastic polyurethanes on autonomous entropy-driven scratch closure and barrier restoration are studied. To this aim, comparable polyurethanes with different segmentation states are applied as organic coatings on plain carbon steel plates, scratched under very well-controlled conditions, and the scratch closure and sealing kinetics are studied in detail. The scratch closure is measured optically, while the barrier restoration is probed by the accelerated cyclic electrochemical technique (ACET). Scratch closure, attributed to entropic elastic recovery (EER), is followed in a marked two-step process by barrier restoration governed by local viscous flow and the state of the interfacial hydrogen bonding. Polyurethanes with a lower soft phase fraction lead to a higher urea/urethane ratio, which in turn influences the healing efficiency of each healing step. Interestingly, softer polyurethanes leading to efficient crack closure were unable to sufficiently restore barrier properties. The present work highlights the critical role of the soft/hard block and urea/urethane H-bond state content on crack closure and barrier restoration of anticorrosive organic coatings and points at design rules for the design of more efficient corrosion-protective self-healing polyurethanes.

The use of rheology and terminal flow relaxation times to predict healing behavior at long healing times is by now quite well accepted. In this work we go one step further and explore the use of macro-rheology (in particular the stored work of deformation) to predict the early stage interfacial healing properties (fracture resistance) of a set of self-healing polyurethanes. The interfacial healing is measured by single edge notch fracture experiments, using short healing times and a low healing temperature to exclude the effect of long range molecular motion on mechanical properties restoration. The systems based on aromatic diisocyanates show high fracture resistance after healing, while very limited restoration of the mechanical properties is observed for aliphatic and cycloaliphatic based polyurethanes. Linear sweep rheology and time-temperature-superposition allow obtaining the macro-rheological master curve and the mechanical relaxation spectra (H(t)). The application of a recently established deconvolution protocol to the H(t) gives the characteristic relaxation times and stored works of deformation associated to individual dynamic processes such as segmental motion, reversible bonds, and terminal flow. It is found that the calculated stored works of deformation related to the reversible bond relaxation reproduce the trend observed by fracture resistance at healed interfaces and reveal a qualitative correspondence between reversible bonds work of deformation and interfacial healing fracture resistance. Moreover, the method seems to point to the existence of a threshold interfacial work of deformation below which no efficient load transfer can be observed.

In this work, we propose the use of regular branching of polyurethanes as a way to regulate chain dynamics and govern crystallization in highly dense hydrogen-bonded systems. As a result, robust and healable polyurethanes can be obtained. To this end, we synthesized a range of aliphatic propane diol derivatives with alkyl branches ranging from butyl (C4) to octadecanyl (C18). The series of brush polyurethanes was synthesized by polyaddition of the diols and hexamethylene diisocyanate. Polyurethanes with very short (C 4) and very long (C = 18) brush lengths did not lead to any significant healing due to crystallization. An intermediate amorphous regime appears for polymers with middle branch lengths (C = 4 to 8) showing a fine control of material toughness. For these systems, the side chain length regulates tube dilation, and significant macroscopic healing of cut samples was observed and studied in detail using melt rheology and tensile testing. Despite the high healing degrees observed immediately after repair, it was found that samples with medium to long length brushes lost their interfacial strength at the healed site after being heated to the healing temperature for some time after the optimal time to reach full healing. Dedicated testing suggests that annealed samples, while keeping initial tackiness, are not able to completely heal the cut interface. We attribute such behavior to annealing-induced interfacial crystallization promoted by the aliphatic branches. Interestingly, no such loss of healing due to annealing was observed for samples synthesized with C4 and C7 diols, which is identified as the optimal healing regime. These results point at the positive effect of branching on healing, provided that a critical chain length is not surpassed, as well as the need to study healing behavior long after the optimal healing times.

Starting from experimental macro-rheological data, we develop a fitting protocol that succeeded in the separation of the overlapping relaxation phenomena in the dissipative regime for a set of intrinsic healing polymers healing most effectively near their glass transition temperature T _g . To allow for a proper deconvolution, the rheological master curves are converted to a relaxation spectrum (H(τ)) and this is fitted using an optimized mechanical model, e.g. the Maxwell-Weichert model. The deconvolution of overlapping segmental mobility and reversible interactions is successfully demonstrated for a set of polyimide and polyamide polymers containing none, one and two reversible dynamic features near-T _g . Through the fitting parameters, the relaxation timescale of each feature and their apparent process enthalpies are obtained. The quantitative data obtained using the fitting protocol are then compared to macroscopic healing results. As a result, a clear correspondence between the energy stored by the system to accomplish reversible (e.g. H-bonds, π-π) and chain interdiffusion relaxation transitions and the healing efficiency of such polymers are obtained. The implementation of this protocol allows for a clearer identification of the relevant mechanisms in self-healing polymers and paves the way for the development of more efficiently healable polymeric systems.

The global increase of the environmental consciousness led to a rapid interest of the scientific community in the exploration of novel bio-based materials. To date several high-quality reviews on the topic of bio-based polymers in general and coatings in particular have been published. However their main focus has been on reporting different raw organic materials used, specific application fields or particular final products. Due to that approach the existing reviews nearly or completely fail in identifying and analysing the potential uniqueness of bio-based raw materials to implement new or better functions to polymeric coatings. The current review offers an overview of the peculiar effect of the bio-based raw component on different coating properties, a characteristic that we like to call the “bio-touch“. The review highlights the relation between the bio-based element and the property achieved. The aim is not to report all the approaches and advances existing, but to critically analyse the main and most successful approaches pointing out possible intrinsic weakness.