Understanding the role of crosslink density and linear viscoelasticity on the shear failure of pressure-sensitive-adhesives.

Pressure-sensitive-adhesives (PSAs) are ubiquitous in electronic, automobile, packaging, and biomedical applications due to their ability to stick to numerous surfaces without undergoing chemical reactions. Although these materials date back to the 1850s with the development of surgical tapes based on natural rubber, their resistance to shear loads remains challenging to predict from molecular design. This work investigates the role of crosslink density on the shear resistance of model PSAs based on poly(2-ethylhexyl acrylate-co-acrylic acid) physically crosslinked with aluminum acetylacetonate. The key result is that crosslinking PSAs leads to notable stress concentrations ahead of the peel front, as well as a transition from cohesive to adhesive failure. The shear stress distributions, as evaluated by means of a linearly viscoelastic shear lag model, suggest that this transition is related to the evolution of the ratio of the load transfer length to the bond length as dictated by the mechanical properties of the backing and adhesive layers, and the geometry of the tape.

Bridging steady-state and stick-slip fracture propagation in glassy polymers.

Both an experimental and a theoretical investigation of fracture propagation mechanisms acting at the process zone scale in glassy polymers are presented. The main aim is to establish a common modeling for different kinds of glassy polymers presenting either steady-state fracture propagation or stick-slip fracture propagation or both, depending on loading conditions and sample shapes. From the experimental point of view, new insights are provided by the in situ AFM measurements of viscoplastic strain fields acting within the micrometric process zone in a brittle epoxy resin, which highlight an extremely slow unexpected steady-state regime with finite plastic strains of about 30% around a blunt crack tip, accompanied by propagating shear lips. From the theoretical point of view, we apply to glassy polymers some recently developed models for describing soft dissipative fracture that are pertinent with the observed finite strains. We propose a unified modeling of fracture energy for both the steady-state and stick-slip fracture propagation based on the evaluation of energy dissipation density at a characteristic strain rate induced in the process zone by a competition between the crack propagation velocity and the macroscopic sample loading rate.

Why is mechanical fatigue different from toughness in elastomers? The role of damage by polymer chain scission.

Although elastomers often experience 10 to 100 million cycles before failure, there is now a limited understanding of their resistance to fatigue crack propagation. We tagged soft and tough double-network elastomers with mechanofluorescent probes and quantified damage by sacrificial bond scission after crack propagation under cyclic and monotonic loading. Damage along fracture surfaces and its spatial localization depend on the elastomer design, as well as on the applied load (i.e., cyclic or monotonic). The key result is that reversible elasticity and strain hardening at low and intermediate strains dictates fatigue resistance, whereas energy dissipation at high strains controls toughness. This information serves to engineer fatigue-resistant elastomers, understand fracture mechanisms, and reduce the environmental footprint of the polymer industry.

Linking peel and tack performances of pressure sensitive adhesives.

The performances of Pressure Sensitive Adhesives (PSA) are generally evaluated using different loading geometries such as tack, peel and shear tests. It is difficult to link the behaviors of PSAs in these different geometries, and to predict the result of one test from another, because the confinement of a soft and dissipative material prevents the use of standard fracture mechanics, which separates the interface debonding behavior from the dissipation associated with the bulk deformation. We present here an original experimental investigation based on the modeling strategy proposed by Creton and Ciccotti[1]. Using instrumented versions of both peel and tack measurements, we compared the adherence performances of a series of model PSAs based on styrene-isoprene block copolymers, while identifying the mesoscale mechanisms at play during debonding. This analysis method allows us to model the contribution of the large strain rheology of the PSAs in the total work of debonding. We clearly show that both the adherence performances and local mechanisms can be closely related between peel and tack when considering both similar confinement and a similar strain rate of the fibrils that are spontaneously formed during debonding. While the overall adherence properties change by a factor of 3 between the different samples, the peel tests only present a minor +20% bias in adherence, which can be attributed to the combination of a 10% increase in the average stress and a 10% increase in the maximum strain of the fibrils. This improvement in the understanding of the PSA performances opens the way to a more sound mechanical design of PSA based joints.

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

The 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.

Anisotropic Superattenuation of Capillary Waves on Driven Glass Interfaces.

Metrological atomic force microscopy measurements are performed on the silica glass interfaces of photonic band-gap fibers and hollow capillaries. The freezing of attenuated out-of-equilibrium capillary waves during the drawing process is shown to result in a reduced surface roughness. The roughness attenuation with respect to the expected thermodynamical limit is determined to vary with the drawing stress following a power law. A striking anisotropic character of the height correlation is observed: glass surfaces thus retain a structural record of the direction of the flow to which the liquid was submitted.

Large strain viscoelastic dissipation during interfacial rupture in laminated glass.

In the dynamic rupture of laminated glass, it is essential to maximize energy dissipation. To investigate the mechanisms of energy dissipation, we have experimentally studied the delamination and stretching of a polymeric viscoelastic interlayer sandwiched between glass plates. We find that there is a velocity and temperature domain in which delamination fronts propagate in a steady state manner. At lower velocities, fronts are unstable, while at higher velocities, the polymer ruptures. Studying the influence of the interlayer thickness, we have shown that the macroscopic work of fracture during the delamination of the interlayer can be divided in two main components: (1) a near crack work of fracture which is related to the interfacial rupture and to the polymer deformation in the crack vicinity. (2) A bulk stretching work, which relates to the stretching of the interlayer behind the delamination front. Digital image correlation measurements showed that the characteristic length scale over which this stretching occurs is of the order of the interlayer thickness. Finally, an estimate of the bulk stretching work was provided, based on a simple uniaxial tensile test.

Inertial and stick-slip regimes of unstable adhesive tape peeling.

We present an experimental characterization of the detachment front unstable dynamics observed during the peeling of pressure sensitive adhesives. We use an experimental set-up specifically designed to control the peeling angle θ and the peeled tape length L, while peeling an adhesive tape from a flat substrate at a constant driving velocity V. High-speed imaging allows us to report the evolution of the period and amplitude of the front oscillations, as well as the relative durations of their fast and slow phases, as a function of the control parameters V, L and θ. Our study shows that, as the driving velocity or the peeling angle increases, the oscillations of the peeling front progressively evolve from genuine "stick-slip" oscillations, made of alternating long stick phases and very brief slip phases, to sinusoidal oscillations of amplitude twice the peeling velocity. We propose a model which, taking into account the peeling angle-dependent kinetic energy cost to accelerate and decelerate the peeled tape, explains the transition from the "stick-slip" to the "inertial" regime of the dynamical instability. Using independent direct measurements of the effective fracture energy of the adhesive-substrate joint, we show that our model quantitatively accounts for the two regimes of the unstable dynamics.

Fracture and adhesion of soft materials: a review.

Soft materials are materials with a low shear modulus relative to their bulk modulus and where elastic restoring forces are mainly of entropic origin. A sparse population of strong bonds connects molecules together and prevents macroscopic flow. In this review we discuss the current state of the art on how these soft materials break and detach from solid surfaces. We focus on how stresses and strains are localized near the fracture plane and how elastic energy can flow from the bulk of the material to the crack tip. Adhesion of pressure-sensitive-adhesives, fracture of gels and rubbers are specifically addressed and the key concepts are pointed out. We define the important length scales in the problem and in particular the elasto-adhesive length Γ/E where Γ is the fracture energy and E is the elastic modulus, and how the ratio between sample size and Γ/E controls the fracture mechanisms. Theoretical concepts bridging solid mechanics and polymer physics are rationalized and illustrated by micromechanical experiments and mechanisms of fracture are described in detail. Open questions and emerging concepts are discussed at the end of the review.

Multiscale Stick-Slip Dynamics of Adhesive Tape Peeling.

Using a high-speed camera, we follow the propagation of the detachment front during the peeling of an adhesive tape from a flat surface. In a given range of peeling velocity, this front displays a multiscale unstable dynamics, entangling two well-separated spatiotemporal scales, which correspond to microscopic and macroscopic dynamical stick-slip instabilities. While the periodic release of the stretch energy of the whole peeled ribbon drives the classical macro-stick-slip, we show that the micro-stick-slip, due to the regular propagation of transverse dynamic fractures discovered by Thoroddsen et al. [Phys. Rev. E 82, 046107 (2010)], is related to a high-frequency periodic release of the elastic bending energy of the adhesive ribbon concentrated in the vicinity of the peeling front.

Rate-dependent elastic hysteresis during the peeling of pressure sensitive adhesives.

The modelling of the adherence energy during peeling of Pressure Sensitive Adhesives (PSA) has received much attention since the 1950's, uncovering several factors that aim at explaining their high adherence on most substrates, such as the softness and strong viscoelastic behaviour of the adhesive, the low thickness of the adhesive layer and its confinement by a rigid backing. The more recent investigation of adhesives by probe-tack methods also revealed the importance of cavitation and stringing mechanisms during debonding, underlining the influence of large deformations and of the related non-linear response of the material, which also intervenes during peeling. Although a global modelling of the complex coupling of all these ingredients remains a formidable issue, we report here some key experiments and modelling arguments that should constitute an important step forward. We first measure a non-trivial dependence of the adherence energy on the loading geometry, namely through the influence of the peeling angle, which is found to be separable from the peeling velocity dependence. This is the first time to our knowledge that such adherence energy dependence on the peeling angle is systematically investigated and unambiguously demonstrated. Secondly, we reveal an independent strong influence of the large strain rheology of the adhesives on the adherence energy. We complete both measurements with a microscopic investigation of the debonding region. We discuss existing modellings in light of these measurements and of recent soft material mechanics arguments, to show that the adherence energy during peeling of PSA should not be associated to the propagation of an interfacial stress singularity. The relevant deformation mechanisms are actually located over the whole adhesive thickness, and the adherence energy during peeling of PSA should rather be associated to the energy loss by viscous friction and by rate-dependent elastic hysteresis.

Intermittent stick-slip dynamics during the peeling of an adhesive tape from a roller.

We study experimentally the fracture dynamics during the peeling at a constant velocity of a roller adhesive tape mounted on a freely rotating pulley. Thanks to a high speed camera, we measure, in an intermediate range of peeling velocities, high frequency oscillations between phases of slow and rapid propagation of the peeling fracture. This so-called stick-slip regime is well known as the consequence of a decreasing fracture energy of the adhesive in a certain range of peeling velocity coupled to the elasticity of the peeled tape. Simultaneously with stick slip, we observe low frequency oscillations of the adhesive roller angular velocity which are the consequence of a pendular instability of the roller submitted to the peeling force. The stick-slip dynamics is shown to become intermittent due to these slow pendular oscillations which produce a quasistatic oscillation of the peeling angle while keeping constant the peeling fracture velocity (averaged over each stick-slip cycle). The observed correlation between the mean peeling angle and the stick-slip amplitude questions the validity of the usually admitted independence with the peeling angle of the fracture energy of adhesives.

Capillary force between wetted nanometric contacts and its application to atomic force microscopy.

We extend to the case of perfect wetting the exact calculation of Orr et al. (J. Fluid. Mech. 1975, 67, 723) for a pendular ring connecting two dry surfaces. We derive an approximate analytical expression for the capillary force between two highly curved surfaces covered by a wetting liquid film. The domain of validity of this expression is assessed and extended by a custom-made numerical simulation based on the full exact mathematical description. In the case of attractive liquid-solid van der Waals interactions, the capillary force increases monotonically with decreasing vapor pressure up to several times its saturation value. This accurate description of the capillary force makes it possible to estimate the adhesion force between wet nanoparticles; it can also be used to quantitatively interpret pull-off forces measured by atomic force microscopy.