Autonomous through-thickness scratch repair (healing) in coatings requires scratch closure and interfacial molecular sealing. Although qualitative aspects of the first stage of self-healing have been addressed, quantitative description enabling the control over the healing process need further understanding. In this work the polymer-architecture-dependent stored entropic energy during deformation is quantified using the rubber elasticity theory and correlated to the scratch closure degree experimentally observed in microscopic measurements. Using well-defined thermoplastic healing polyurethanes with variable soft phase fraction contents these studies show that pressure-free damage closure of scratches maintaining mechanical integrity during healing is governed by the capability of the polymer to store entropic energy during damage. The storage (and release) of energy is controlled by varying the damage and healing temperatures in relation to the specific viscoelastic length transition (TVLT) and the glass transition temperature (Tg). Damage closure increases linearly with the entropy release and is controlled by two parameters of the network, the junction density and damping factor. If mechanical damage does not lead to storage of mechanical energy healing does not occur.@en

Shape memory polymers (SMPs) are dynamic materials able to recover previously defined shapes when activated by external stimuli. The most common stimulus is thermal energy applied near thermal transitions in polymers, such as glass transition (T_g) and melting (T_m) temperatures. The magnitude of the geometrical changes as well as the amount of force and energy that a SMP can output are critical properties for many applications. While typically deformation steps in the shape memory cycles (SMC) are performed at temperatures well above thermal transitions used to activate shape changes, significantly greater amounts of strain, stress, and mechanical energy can be stored in T_g-based SMPs when deformed near their T_g. Since maximum shape memory storage capacity can be appraised by evaluating the viscoelastic length transitions (VLTs) in a single dynamic mechanical analysis (DMA) experiment, this study correlates VLTs with the measured storage capacities obtained from stress-strain experiments for a broad range of well-defined crosslinked acrylates, epoxies, and polyurethanes. This systematic approach allows for assessment of crosslink/junction density (ν_j), viscoelasticity, and chemical composition effects on maximum deformability, and enables predictions of the magnitude of shape memory properties across a wide variety of polymers. These studies demonstrate that the maximum storable strain (ε-store_max) can be accurately predicted using junction density (ν_j) and shape memory factor (SMF), the latter accounting for the contribution of chemical makeup.

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