Adhesion and non-linear rheology of adhesives with supramolecular crosslinking points

Soft supramolecular materials are promising for the design of innovative and highly tunable adhesives. These materials are composed of polymer chains functionalized by strongly interacting moieties, sometimes called "stickers". In order to systematically investigate the effect of the presence of associative groups on the debonding properties of a supramolecular adhesive, a series of supramolecular model systems has been characterized by probe-tack tests. These model materials, composed of linear and low dispersity poly(butylacrylate) chains functionalized in the middle by a single tri-urea sticker, are able to self-associate by six hydrogen bonds and range in molecular weight (M n) between 5 and 85 kg/mol. The linear rheology and the nanostructure of the same materials (called "PnBA3U") was the object of a previous study 1,2. At room temperature, the association of polymers via hydrogen bonds induces the formation of rod-like aggregates structured into bundles for M n \textless{} 40kg/mol and the behavior of a soft elastic material was observed (G'\textgreater{}\textgreater{}G "and G'~$\omega$ 0). For higher M n , the filaments were randomly oriented and polymers displayed a crossover towards viscous behavior although terminal relaxation was not reached in the experimental frequency window. All these materials show however similar adhesive properties characterized by a cohesive mode of failure and low debonding energies (W adh \textless{}40J/m 2 for a debonding speed of 100$\mu$m/s). The debonding mechanisms observed during the adhesion tests have been investigated in detail with an Image tools analysis developed by our group 3. The measure of the projected area covered by cavities growing in the adhesive layer during debonding can be used to estimate the true stress in the walls of the cavities and thus, to characterize the in-situ large strain deformation of the thin layer during the adhesion test itself. This analysis revealed in particular that the PnBA3U materials with M n \textless{} 40 kg/mol soften very markedly at large deformation like yield stress fluids, explaining the low adhesion energies measured for these viscoelastic gels.

Pattern Formation During Deformation of a Confined Viscoelastic Layer: From a Viscous Liquid to a Soft Elastic Solid

We study pattern formation during tensile deformation of confined viscoelastic layers. The use of a model system (PDMS with different degrees of crosslinking) allows us to go continuously from a viscous liquid to an elastic solid. We observe two distinct regimes of fingering instabilities: a regime called "elastic" with interfacial crack propagation where the fingering wavelength only scales with the film thickness, and a bulk regime called "viscoelastic" where the fingering instability shows a Saffman-Taylor-like behavior. We find good quantitative agreement with theory in both cases and present a reduced parameter describing the transition between the two regimes and allowing to predict the observed patterns over the whole range of viscoelastic properties.Comment: 4 pages, 7 figures, typos corrected, figure 5 replace

A new sighting study for the fixed concentration procedure to allow for gender differences

The fixed concentration procedure (FCP) has been proposed as an alternative to the median lethal concentration (LC50) test (organisation for economic co-operation and development (OECD) test guideline [TG] 403) for the assessment of acute inhalation toxicity. The FCP tests animals of a single gender (usually females) at a number of fixed concentration levels in a sequential fashion. It begins with a sighting study that precedes the main FCP study and is used to determine the main study starting concentration. In this paper, we propose a modification to the sighting study and suggest that it should be conducted using both male and female animals, rather than just animals of a single gender. Statistical analysis demonstrates that, when females are more sensitive, the new procedure is likely to give the same classification as the original FCP, whereas, if males are more sensitive, the new procedure is much less likely to lead to incorrect classification into a less toxic category. If there is no difference in the LC50 for females and males, the new procedure is slightly more likely to classify into a more stringent class than the original FCP. Overall, these results show that the revised sighting study ensures gender differences in sensitivity do not significantly impact on the performance of the FCP, supporting its use as an alternative test method for assessing acute inhalation toxicity

Cavitation-induced force transition in confined viscous liquids under traction

We perform traction experiments on simple liquids highly confined between parallel plates. At small separation rates, we observe a simple response corresponding to a convergent Poiseuille flow. Dramatic changes in the force response occur at high separation rates, with the appearance of a force plateau followed by an abrupt drop. By direct observation in the course of the experiment, we show that cavitation accounts for these features which are reminiscent of the utmost complex behavior of adhesive films under traction. Surprisingly enough, this is observed here in purely viscous fluids.Comment: Submitted to Physical Review Letters on May 31, 2002. Related informations on http://www.crpp.u-bordeaux.fr/tack.htm

Interdigitation between surface-anchored polymer chains and an elastomer : consequences for adhesion promotion

We study the adhesion between a cross-linked elastomer and a flat solid surface where polymer chains have been end-grafted. To understand the adhesive feature of such a system, one has to study both the origin of the grafted layer interdigitation with the network, and the end-grafted chains extraction out of the elastomer when it comes unstuck from the solid surface. We shall tackle here the first aspect for which we develop a partial interdigitation model that lets us analytically predict a critical surface grafting density $\sigma^{*} \simeq P^{{1/10}}N^{-{3/5}}$ beyond which the layer no longer interdigitates with the elastomer. We then relate this result with recent adhesion measurements

Quantifying Rate-and Temperature-Dependent Molecular Damage in Elastomer Fracture

Elastomers are highly valued soft materials finding many applications in the engineering and biomedical fields for their ability to stretch reversibly to large deformations. Yet their maximum extensibility is limited by the occurrence of fracture, which is currently still poorly understood. Because of a lack of experimental evidence, current physical models of elastomer fracture describe the rate and temperature dependence of the fracture energy as being solely due to viscoelastic friction, with chemical bond scission at the crack tip assumed to remain constant. Here, by coupling new fluorogenic mechanochemistry with quantitative confocal microscopy mapping, we are able to quantitatively detect, with high spatial resolution and sensitivity, the scission of covalent bonds as ordinary elastomers fracture at different strain rates and temperatures. Our measurements reveal that, in simple networks, bond scission, far from being restricted to a constant level near the crack plane, can both be delocalized over up to hundreds of micrometers and increase by a factor of 100, depending on the temperature and stretch rate. These observations, permitted by the high fluorescence and stability of the mechanophore, point to an intricate coupling between strain-rate-dependent viscous dissipation and strain-dependent irreversible network scission. These findings paint an entirely novel picture of fracture in soft materials, where energy dissipated by covalent bond scission accounts for a much larger fraction of the total fracture energy than previously believed. Our results pioneer the sensitive, quantitative, and spatially resolved detection of bond scission to assess material damage in a variety of soft materials and their applications. © 2020 authors. Published by the American Physical Society

The Slowly Formed Guiselin Brush

We study polymer layers formed by irreversible adsorption from a polymer melt. Our theory describes an experiment which is a ``slow'' version of that proposed by Guiselin [Europhys. Lett., v. 17 (1992) p. 225] who considered instantaneously irreversibly adsorbing chains and predicted a universal density profile of the layer after swelling with solvent to produce the ``Guiselin brush.'' Here we ask what happens when adsorption is not instantaneous. The classic example is chemisorption. In this case the brush is formed slowly and the final structure depends on the experiment's duration, $t_{final}$. We find the swollen layer consists of an inner region of thickness $z^* \sim t_{final}^{-5/3}$ with approximately constant density and an outer region extending up to height $h \sim N^{5/6}$ which has the same density decay $\sim z^{-2/5}$ as for the Guiselin case.Comment: 7 pages, submitted to Europhysics Letter

Quantifying and mapping covalent bond scission during elastomer fracture

Many new soft but tough rubbery materials have been recently discovered and new applications such as flexible prosthetics, stretchable electrodes or soft robotics continuously emerge. Yet, a credible multi-scale quantitative picture of damage and fracture of these materials has still not emerged, due to our fundamental inability to disentangle the irreversible scission of chemical bonds along the fracture path from dissipation by internal molecular friction. Here, by coupling new fluorogenic mechanochemistry with quantitative confocal microscopy mapping, we uncover how many and where covalent bonds are broken as an elastomer fractures. Our measurements reveal that bond scission near the crack plane can be delocalized over up to hundreds of micrometers and increase by a factor of 100 depending on temperature and stretch rate, pointing to an intricated coupling between strain rate dependent viscous dissipation and strain dependent irreversible network scission. These findings paint an entirely novel picture of fracture in soft materials, where energy dissipated by covalent bond scission accounts for a much larger fraction of the total fracture energy than previously believed. Our results pioneer the sensitive, quantitative and spatially-resolved detection of bond scission to assess material damage in a variety of soft materials and their applications

NEW DESCRIPTORS TO CHARACTERIZE POROUS MATERIALS

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Molecular weight effects on chain pull-out fracture of reinforced polymeric interfaces

Using Brownian dynamics, we simulate the fracture of polymer interfaces reinforced by diblock connector chains. We find that for short chains the interface fracture toughness depends linearly on the degree of polymerization $N$ of the connector chains, while for longer chains the dependence becomes $N^{3/2}$. Based on the geometry of initial chain configuration, we propose a scaling argument that accounts for both short and long chain limits and crossover between them.Comment: 5 pages, 3 figure