Quantitative analysis of the debonding structure of soft adhesives

We experimentally investigate the growth dynamics of cavities nucleating during the first stages of debonding of three different model adhesives. The material properties of these adhesives range from a more liquid-like material to a soft viscoelastic solid and are carefully characterized by small strain oscillatory shear rheology as well as large strain uniaxial extension. The debonding experiments are performed on a probe tack set-up. Using high contrast images of the debonding process and precise image analysis tools we quantify the total projected area of the cavities, the average cavity shape and growth rate and link these observations to the material properties. These measurements are then used to access corrected effective stress and strain curves that can be directly compared to the results from the uniaxial extension

Harnessing entropy to enhance toughness in reversibly crosslinked polymer networks

Reversible crosslinking is a design paradigm for polymeric materials, wherein they are microscopically reinforced with chemical species that form transient crosslinks between the polymer chains. Besides the potential for self-healing, recent experimental work suggests that freely diffusing reversible crosslinks in polymer networks, such as gels, can enhance the toughness of the material without substantial change in elasticity. This presents the opportunity for making highly elastic materials that can be strained to a large extent before rupturing. Here, we employ Gaussian chain theory, molecular simulation, and polymer self-consistent field theory for networks to construct an equilibrium picture for how reversible crosslinks can toughen a polymer network without affecting its linear elasticity. Maximisation of polymer entropy drives the reversible crosslinks to bind preferentially near the permanent crosslinks in the network, leading to local molecular reinforcement without significant alteration of the network topology. In equilibrium conditions, permanent crosslinks share effectively the load with neighbouring reversible crosslinks, forming multi-functional crosslink points. The network is thereby globally toughened, while the linear elasticity is left largely unaltered. Practical guidelines are proposed to optimise this design in experiment, along with a discussion of key kinetic and timescale considerations

pH/Temperature control of interpolymer complexation between poly(acrylic acid) and weak polybases in aqueous solutions

International audienc

A critical local energy release rate criterion for fatigue fracture of elastomers

International audienc

Mechanics of an adhesive tape in a zero degree peel test: effect of large deformation and material nonlinearity

International audienceThe common pressure sensitive adhesive (PSA) tape is a composite consisting of a stiff backing layer and a soft adhesive layer. A simple and common way to test how adhesive tapes respond to large shear deformations is the zero degree peel test. Because the backing is very stiff compared to the adhesive layer, the region where the adhesive layer is subjected to large shear can be hundreds of times its thickness. We use a large deformation hyperelastic model to study the stress and deformation fields in the adhesive layer in this test. We present a closed-form solution for the stress field in the adhesive layer and use this solution to determine how load is transferred from the backing layer to the adhesive. Our analytical model is then compared with finite element results, and except for a small region near the peel front, the predicted stress and deformation agree well with the finite element model. Interestingly, we find very different results from the classical linear theory established by Kaelble. In particular for large deformations, our analysis shows that the lateral stresses (parallel to the rigid substrate) are much larger than the shear stress in the adhesive layer. The discrepancy in the stress state and the deformation state with the linear theory is particularly large near the peel front, which we study with a finite element model. These new results will be very useful to interpret experiments and in particular to identify the high stress regions where failure is likely to initiate in zero-degree peel tests also called shear resistance tests in the PSA industry

Hierarchical Sticker and Sticky Chain Dynamics in Self-Healing Butyl Rubber Ionomers

We present a detailed comparison of the microscopic dynamics and the macroscopic mechanical behavior of novel butyl rubber ionomers with tunable dynamics of sparse sticky imidazole-based sidegroups that form clusters of about 20 units separated by essentially unperturbed chains. This material platform shows promise for application as self-healing elastomers. Size and thermal stability of the ionic clusters were probed by small-angle X-ray scattering, and the chain and sticker dynamics were studied by a combination of broadband dielectric spectroscopy (BDS) and advanced NMR methods. The results are correlated with the rheological behavior characterized by dynamic-mechanical analysis (DMA). While the NMR-detected chain relaxation and DMA results agree quantitatively and confirm relevant aspects of the sticky-reptation picture on a microscopic level, we stress and explain that apparent master curves are of limited use for such a comparison. The cluster-related relaxation time detected by BDS is much shorter than the elastic chain relaxation time, although the weak conductivity does follow the latter. The systematic trends across the sample series suggest that all relaxations are dominated by a cluster-related activation barrier, but also that the BDS-based cluster relaxation does not seem to be directly associated with the effective sticker lifetime. Nonlinear stress-strain experiments demonstrate a reduction of sticker lifetime on stretching and that the stored stress and the elastic recovery depend on the deformation rate. © 2019 American Chemical Society

Hierarchical Sticker and Sticky Chain Dynamics in Self-Healing Butyl Rubber Ionomers

We present a detailed comparison of the microscopic dynamics and the macroscopic mechanical behavior of novel butyl rubber ionomers with tunable dynamics of sparse sticky imidazole-based sidegroups that form clusters of about 20 units separated by essentially unperturbed chains. This material platform shows promise for application as self-healing elastomers. Size and thermal stability of the ionic clusters were probed by small-angle X-ray scattering, and the chain and sticker dynamics were studied by a combination of broadband dielectric spectroscopy (BDS) and advanced NMR methods. The results are correlated with the rheological behavior characterized by dynamic-mechanical analysis (DMA). While the NMR-detected chain relaxation and DMA results agree quantitatively and confirm relevant aspects of the sticky-reptation picture on a microscopic level, we stress and explain that apparent master curves are of limited use for such a comparison. The cluster-related relaxation time detected by BDS is much shorter than the elastic chain relaxation time, although the weak conductivity does follow the latter. The systematic trends across the sample series suggest that all relaxations are dominated by a cluster-related activation barrier, but also that the BDS-based cluster relaxation does not seem to be directly associated with the effective sticker lifetime. Nonlinear stress-strain experiments demonstrate a reduction of sticker lifetime on stretching and that the stored stress and the elastic recovery depend on the deformation rate. © 2019 American Chemical Society

Hierarchical Sticker and Sticky Chain Dynamics in Self-Healing Butyl Rubber Ionomers

We present a detailed comparison of the microscopic dynamics and the macroscopic mechanical behavior of novel butyl rubber ionomers with tunable dynamics of sparse sticky imidazole-based sidegroups that form clusters of about 20 units separated by essentially unperturbed chains. This material platform shows promise for application as self-healing elastomers. Size and thermal stability of the ionic clusters were probed by small-angle X-ray scattering, and the chain and sticker dynamics were studied by a combination of broadband dielectric spectroscopy (BDS) and advanced NMR methods. The results are correlated with the rheological behavior characterized by dynamic-mechanical analysis (DMA). While the NMR-detected chain relaxation and DMA results agree quantitatively and confirm relevant aspects of the sticky-reptation picture on a microscopic level, we stress and explain that apparent master curves are of limited use for such a comparison. The cluster-related relaxation time detected by BDS is much shorter than the elastic chain relaxation time, although the weak conductivity does follow the latter. The systematic trends across the sample series suggest that all relaxations are dominated by a cluster-related activation barrier, but also that the BDS-based cluster relaxation does not seem to be directly associated with the effective sticker lifetime. Nonlinear stress-strain experiments demonstrate a reduction of sticker lifetime on stretching and that the stored stress and the elastic recovery depend on the deformation rate. © 2019 American Chemical Society