A molecular interpretation of the toughness of multiple network elastomers at high temperature.

SignificanceSoft materials can be toughened by creating dissipative mechanisms in stretchy matrixes. Yet using them over a wide range of temperatures requires dissipative mechanisms independent of stretch rate or temperature. We show that sacrificial covalent bonds in multiple network elastomers are most useful in toughening elastomers at high temperature and act synergistically with viscoelasticity at lower temperature. We do not attribute this toughening mechanism only to the scission of bonds during crack propagation but propose that the highly stretched network diluted in a stretchy matrix acts by simultaneously stiffening the elastomer and delaying the localization of bond scission and the propagation of a crack. Such a toughening mechanism has never been proposed for elastomers and should guide network design.

Self-adhesion of uncrosslinked poly(butadiene-co-acrylonitrile), i.e. nitrile rubber, an inhomogeneous and associative polymer.

Nitrile rubber (i.e., NBR) is a crosslinked copolymer of butadiene and acrylonitrile that finds widespread use in the automotive and aerospace industry as it sustains large, reversible deformations while resisting swelling by petrochemical fuels. We recently demonstrated that this material has a drift in composition due to the difference in reactivity between acrylonitrile and butadiene monomers during emulsion copolymerisation. Thus, although NBR is often thought of as a random copolymer, it does experience thermodynamic driving forces for self-assembly and kinetic barriers for processing like those of block copolymers.1 Here, we illustrate how such drift in composition hinders interdiffusion and prevents self-adhesion. The key result is that contacting uncrosslinked NBR (i) in the melt, (ii) in the presence of tackifiers, or (iii) in the presence of organic solvents promotes interdiffusion and enables self-adhesion. However, the contact times required for self-adhering, tc ∼ O(100 h), are orders of magnitude above those needed for non-polar synthetic rubbers like styrene-butadiene rubber (i.e., SBR) of comparable molecular weights and glass transition temperatures, tc ∼ O(100 s), unveiling the dramatic effect of compositional inhomogeneities and physical associations on polymer interdiffusion and large-strain mechanical properties. For example, when welded with organic solvents, the self-adhesion energy of NBR continues to increase after the solvent has evaporated because of polymer nanostructuring.

Effect of temperature, rate, and molecular weight on the failure behavior of soft block copoly(ether-ester) thermoplastic elastomers.

Thermoplastic elastomers (TPEs) based on multiblock copolymers are an important class of engineering polymers. They are widely used in many applications where flexibility and durability are required and are seen as a sustainable (recyclable) alternative to thermoset rubbers. While their high-temperature mechanical behavior has received recent interest, few studies have explored their fracture and fatigue behavior. Understanding how the temperature and rate-dependence of the deformation behavior at both a local and global scale influences the fatigue resistance and failure behavior is critical when designing with these materials. In this study, the failure behavior in tensile, fracture, and fatigue of well-characterized, industrially relevant, model block copoly(ether-ester) based TPEEs were evaluated over a wide range of temperatures, deformation rates, and molecular weights. Small changes in temperature or rate are shown to result in a sharp transition between a highly deformable and notch resistant response, to a more brittle and strongly notch-sensitive response. This behavior surprisingly manifests itself as a threshold strain below which the cracks do not propagate in fatigue and increasing deformation rates decreases the materials toughness in fracture tests, whereas in tensile tests the opposite is observed. The change from homogenous to inhomogeneous stress fields for tensile and fracture experiments coupled with the viscoelasticity and strain-dependent morphology of TPEs explains why a different rate dependency is observed. Strain and stress delocalization is key to achieve high toughness. Digital Image Correlation is used to measure the size and time dependence of the process zone. Comparison with micromechanical models developed for soft, elastic, and tough double network gels highlights the dominance of high strain properties for toughness and explains the strong molecular weight dependence. However, to understand the rate dependence, the characteristic times for stress transfer from the crack tip and the time to nucleate failure must be compared. The results presented in this study demonstrate the complex effect of loading conditions on the intrinsic failure mechanisms of the TPE material, and provide a first attempt at rationalizing that behavior.

Mesoscale bicontinuous networks in self-healing hydrogels delay fatigue fracture.

Load-bearing biological tissues, such as muscles, are highly fatigue-resistant, but how the exquisite hierarchical structures of biological tissues contribute to their excellent fatigue resistance is not well understood. In this work, we study antifatigue properties of soft materials with hierarchical structures using polyampholyte hydrogels (PA gels) as a simple model system. PA gels are tough and self-healing, consisting of reversible ionic bonds at the 1-nm scale, a cross-linked polymer network at the 10-nm scale, and bicontinuous hard/soft phase networks at the 100-nm scale. We find that the polymer network at the 10-nm scale determines the threshold of energy release rate G0 above which the crack grows, while the bicontinuous phase networks at the 100-nm scale significantly decelerate the crack advance until a transition Gtran far above G0 In situ small-angle X-ray scattering analysis reveals that the hard phase network suppresses the crack advance to show decelerated fatigue fracture, and Gtran corresponds to the rupture of the hard phase network.

Mechanochemical tools for polymer materials.

Mechanochemistry provides a unique approach to investigate macroscopic deformation, failure and healing of polymer materials. The development of mechanophores - molecular units that respond to mechanical force - has been instrumental in the success of this endeavor. This review aims to provide a critical evaluation of the large variety of mechanophores reported in literature, and to assess the molecular and macroscopic factors that determine their activation. Applications in materials science are highlighted, and challenges in polymer mechanochemistry are discussed.

Correction: Mechanochemical tools for polymer materials.

Correction for 'Mechanochemical tools for polymer materials' by Yinjun Chen et al., Chem. Soc. Rev., 2021, 50, 4100-4140, DOI: 10.1039/D0CS00940G.

3D fluorescent mapping of invisible molecular damage after cavitation in hydrogen exposed elastomers.

Elastomers saturated with gas at high pressure suffer from cavity nucleation, inflation, and deflation upon rapid or explosive decompression. Although this process often results in undetectable changes in appearance, it causes internal damage, hampers functionality (e.g., permeability), and shortens lifetime. Here, we tag a model poly(ethyl acrylate) elastomer with π-extended anthracene-maleimide adducts that fluoresce upon network chain scission, and map in 3D the internal damage present after a cycle of gas saturation and rapid decompression. Interestingly, we observe that each cavity observable during decompression results in a damaged region, the shape of which reveals a fracture locus of randomly oriented penny-shape cracks (i.e., with a flower-like morphology) that contain crack arrest lines. Thus, cavity growth likely proceeds discontinuously (i.e., non-steadily) through the stable and unstable fracture of numerous 2D crack planes. This non-destructive methodology to visualize in 3D molecular damage in polymer networks is novel and serves to understand how fracture occurs under complex 3D loads, predict mechanical aging of pristine looking elastomers, and holds potential to optimize cavitation-resistance in soft materials.

Mechanics of elastomeric molecular composites.

A classic paradigm of soft and extensible polymer materials is the difficulty of combining reversible elasticity with high fracture toughness, in particular for moduli above 1 MPa. Our recent discovery of multiple network acrylic elastomers opened a pathway to obtain precisely such a combination. We show here that they can be seen as true molecular composites with a well-cross-linked network acting as a percolating filler embedded in an extensible matrix, so that the stress-strain curves of a family of molecular composite materials made with different volume fractions of the same cross-linked network can be renormalized into a master curve. For low volume fractions (<3%) of cross-linked network, we demonstrate with mechanoluminescence experiments that the elastomer undergoes a strong localized softening due to scission of covalent bonds followed by a stable necking process, a phenomenon never observed before in elastomers. The quantification of the emitted luminescence shows that the damage in the material occurs in two steps, with a first step where random bond breakage occurs in the material accompanied by a moderate level of dissipated energy and a second step where a moderate level of more localized bond scission leads to a much larger level of dissipated energy. This combined use of mechanical macroscopic testing and molecular bond scission data provides unprecedented insight on how tough soft materials can damage and fail.

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.

Time dependent fracture of soft materials: linear versus nonlinear viscoelasticity.

Toughness of soft materials such as elastomers and gels depends on their ability to dissipate energy and to reduce stress concentration at the crack tip. The primary energy dissipation mechanism is viscoelasticity. Most analyses and models of fracture are based on linear viscoelastic theory (LVT) where strains are assumed to be small and the relaxation mechanisms are independent of stress or strain history. A well-known paradox is that the size of the dissipative zone predicted by LVT is unrealistically small. Here we use a physically based nonlinear viscoelastic model to illustrate why the linear theory breaks down. Using this nonlinear model and analogs of crack problems, we give a plausible resolution to this paradox. In our model, viscoelasticity arises from the breaking and healing of physical cross-links in the polymer network. When the deformation is small, the kinetics of bond breaking and healing are independent of the strain/stress history and the model reduces to the standard linear theory. For large deformations, localized bond breaking damages the material near the crack tip, reducing stress concentration and dissipating energy at the same time. The damage zone size is a new length scale which depends on the strain required to accelerate bond breaking kinetics. These effects are illustrated by considering two cases with stress concentrations: the evolution of spherical damage in a viscoelastic body subjected to internal pressure, and a zero degree peel test.

Thermally Triggered Injectable Underwater Adhesives.

A novel bioinspired underwater adhesive based on the injectable aqueous solution of a graft copolymer with a thermoresponsive backbone is reported, which turns into a sticky hydrogel just below body temperature. With this topology, the collapse of the backbones upon the thermal transition leads to the formation of a percolating network of strong hydrophobic domains. Similar to pressure-sensitive adhesives (PSAs), the hydrogel goes through fibrillation and extensive energy dissipation in large deformations, giving it an edge over conventional chemical hydrogels, which are typically elastic and inherently nonsticky. This capability comes from the hydrophobic nanoscaffold, which resists large deformations to minimize its contact with water. Since hydrophobic interactions are not weakened in water, the behavior of the hydrogel is maintained in aqueous medium. Chemistry-insensitive adhesion of this hydrogel offers a major advantage over current injectable adhesives, which rely on in situ chemical crosslinking reactions with tissues.

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 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.

Tuning the Interactions in Multiresponsive Complex Coacervate-Based Underwater Adhesives.

In this work, we report the systematic investigation of a multiresponsive complex coacervate-based underwater adhesive, obtained by combining polyelectrolyte domains and thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) units. This material exhibits a transition from liquid to solid but, differently from most reactive glues, is completely held together by non-covalent interactions, i.e., electrostatic and hydrophobic. Because the solidification results in a kinetically trapped morphology, the final mechanical properties strongly depend on the preparation conditions and on the surrounding environment. A systematic study is performed to assess the effect of ionic strength and of PNIPAM content on the thermal, rheological and adhesive properties. This study enables the optimization of polymer composition and environmental conditions for this underwater adhesive system. The best performance with a work of adhesion of 6.5 J/m2 was found for the complex coacervates prepared at high ionic strength (0.75 M NaCl) and at an optimal PNIPAM content around 30% mol/mol. The high ionic strength enables injectability, while the hydrated PNIPAM domains provide additional dissipation, without softening the material so much that it becomes too weak to resist detaching stress.

Simple model on debonding of soft adhesives.

We propose a simple theoretical model describing the debonding process of soft adhesives in the probe-tack test. In this model, the expansion dynamics of interfacial cavities is determined by the balance between the strain energy release rate and the rate-dependent fracture energy. As a result, we obtain analytical solutions for the cavity size, stress-strain curve, peak stress, strain at the peak stress, maximum strain, as well as the adhesion energy. Furthermore, we discuss the validity of our theoretical results by comparing them with experiments.

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.

Molecular Weight Dependence of Interdiffusion and Adhesion of Polymers at Short Contact Times.

The autohesion and subsequent debonding of thin layers of three linear and monodisperse random copolymers of styrene-butadiene (SBR) with molecular weights varying between 30 and 75 times the average molecular weight between entanglements Me were investigated using a carefully controlled tack adhesion testing device in conjunction with a fast camera setup over a range of contact times tc (10 ms to 10 s) much shorter in comparison to the terminal relaxation times of the polymers. The evolution of the stress-strain curves and debonding mechanisms with increasing contact time was examined, and the work required to debond the layers was found to be strongly dependent on molecular weight at long contact times, but not at short contact times. We propose a cutoff contact time of 300 ms, corresponding to 104 times the entanglement time τe after which molecular weight becomes important in controlling the interdiffusion process and the debonding mechanisms of the tack test. For contact times over 300 ms, the debonding energy plotted as a function of tc normalized by the reptation time τrep, collapses onto a master curve. Below this threshold tc, by comparing the adhesion of SBR on itself with the adhesion of SBR on glass, we also show that interdiffusion plays a part in adhesion of two identical polymer layers even at the shortest contact times, where the interdiffusion is controlled by the number of entanglements formed which scales with 1/√N.

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.

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.

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.

Probing pH-responsive interactions between polymer brushes and hydrogels by neutron reflectivity.

We investigated the effect of specific interactions on the structure of interfaces between a brush and a hydrogel on the polymer chain length scale. We used a model system for which the interactions between the brush and the gel are switchable. We synthesized weak polyelectrolyte brushes of poly(acrylic acid) and hydrogels of polyacrylamide and poly(N,N-dimethylacrylamide) which interact solely when the poly(acrylic acid) is mainly in its acidic form. The monomer density profiles of the poly(acrylic acid) brush immersed in pure deuterium oxide (D2O) or in contact with a D2O-swollen gel were determined by neutron reflectivity. At pH 2 when the brush is in its neutral form, it interacts with the gel by hydrogen bonds while at pH 9 when the brush is a polyelectrolyte it is not interacting with the gel. Our results show that the presence of interactions with the gel at pH 2 increases the swelling ratio of the brush relative to that in pure D2O, meaning that the brushes exhibit conformations which are more extended from the surface than in the absence of interactions.