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The failure resistance of polymer networks dictates their utility as material candidates across industries. However, relating the key length scales driving crack growth to molecular mechanisms remains a key bottleneck in predicting and designing against fracture. The fractocohesive length—defined in terms of the ratio of fracture energy to the specific work to rupture—of a material correlates with the length scale of energy dissipation and controls fracture resistance. Although the Lake–Thomas model predicts the fractocohesive length of a perfect polymer network to match the undeformed mesh size, real soft materials exhibit values that far exceed this prediction. Here, we report extraordinarily high fractocohesive lengths in polymer-like networks with and without defects. We find that even perfect networks can have fractocohesive lengths orders of magnitude higher than the undeformed mesh size due to highly nonlinear chain behavior giving rise to nonlocal effects during fracture. Introducing defects further increases the fractocohesive length. We identify quantitative relations between nonlinear chain mechanics, defect length, defect density, and fractocohesive length. Overall, strain-stiffening chain behavior, defect density, and defect size independently correlate with larger fractocohesive lengths in polymer-like networks, and their individual effects can be collapsed into a single power law scaling. These outcomes point the way towards improved physics-informed design of soft yet tough polymers and metamaterials. 

Gels made of telechelic polymers connected by reversible cross-linkers are a versatile design platform for biocompatible viscoelastic materials. Their linear response to a step strain displays a fast, near-exponential relaxation when using low-valence cross-linkers, while larger supramolecular cross-linkers bring about much slower dynamics involving a wide distribution of timescales whose physical origin is still debated. Here, we propose a model where the relaxation of polymer gels in the dilute regime originates from elementary events in which the bonds connecting two neighboring cross-linkers all disconnect. Larger cross-linkers allow for a greater average number of bonds connecting them but also generate more heterogeneity. We characterize the resulting distribution of relaxation timescales analytically and accurately reproduce stress relaxation measurements on metal-coordinated hydrogels with a variety of cross-linker sizes including ions, metal-organic cages, and nanoparticles. Our approach is simple enough to be extended to any cross-linker size and could thus be harnessed for the rational design of complex viscoelastic materials. 

The FENE-P (Finitely-Extensible Nonlinear Elastic) dumbbell constitutive equation is widely used in simulations and stability analyses of free and wall-bounded viscoelastic shear flows due to its relative simplicity and accuracy in predicting macroscopic properties of dilute polymer solutions. The model contains three independent material parameters, which expressed in dimensionless form correspond to a Weissenberg number (Wi), i.e., the ratio of the dumbbell relaxation time scale to a characteristic flow time scale, a finite extensibility parameter (L), corresponding to the ratio of the fully extended dumbbell length to the root mean square end-to-end separation of the polymer chain under equilibrium conditions, and a solvent viscosity ratio. An exact solution for the rheological predictions of the FENE-P model in steady simple shear flow is available [Sureshkumar et al., Phys Fluids (1997)], but the resulting nonlinear and nested set of equations do not readily reveal the key shear-thinning physics that dominates at high Wi as a result of the finite extensibility of the polymer chain. In this note we review a simple way of evaluating the steady material functions characterizing the nonlinear evolution of the polymeric contributions to the shear stress and first normal stress difference as the shear rate increases, provide asymptotic expansions as a function of Wi , and show that it is in fact possible to construct universal master curves for these two material functions as well as the corresponding stress ratio. Steady shear flow experiments on three highly elastic dilute polymer solutions of different finite extensibilities also follow the identified master curves. The governing dimensionless parameter for these master curves is Wi/L and it is only in strong shear flows exceeding Wi/L > 1 that the effects of finite extensibility of the polymer chains dominate the evolution of polymeric stresses in the flow field. We suggest that reporting the magnitude of Wi/L when performing stability analyses or simulating shear-dominated flows with the FENE-P model will help clarify finite extensibility effects. 

The interplay between viscoelasticity and inertia in dilute polymer solutions at high deformation rates can result in inertioelastic instabilities. The nonlinear evolution of these instabilities generates a state of turbulence with significantly different spatiotemporal features compared to Newtonian turbulence, termed elastoinertial turbulence (EIT). We ex- plore EIT by studying the dynamics of a submerged planar jet of a dilute aqueous polymer solution injected into a quiescent tank of water using a combination of schlieren imaging and laser Doppler velocimetry (LDV). We show how fluid elasticity has a nonmonotonic effect on the jet stability depending on its magnitude, creating two distinct regimes in which elastic effects can either destabilize or stabilize the jet. In agreement with linear stability analyses of viscoelastic jets, an inertioelastic shear-layer instability emerges near the edge of the jet for small levels of elasticity, independent of bulk undulations in the fluid column. The growth of this disturbance mode destabilizes the flow, resulting in a turbulence transition at lower Reynolds numbers and closer to the nozzle compared to the conditions required for the transition to turbulence in a Newtonian jet. Increasing the fluid elasticity merges the shear-layer instability into a bulk instability of the jet column. In this regime, elastic tensile stresses generated in the shear layer act as an “elastic membrane” that partially stabilizes the flow, retarding the transition to turbulence to higher levels of inertia and greater distances from the nozzle. In the fully turbulent state far from the nozzle, planar viscoelastic jets exhibit unique spatiotemporal features associated with EIT. The time-averaged angle of jet spreading, an Eulerian measure of the degree of entrainment, and the centerline velocity of the jets both evolve self-similarly with distance from the nozzle. The autocovariance of the schlieren images in the fully turbulent region of the jets shows coherent structures that are elongated in the streamwise direction, consistent with the suppression of streamwise vortices by elastic stresses. These coherent structures give a higher spectral energy to small frequency modes in EIT characterized by LDV measurements of the velocity fluctuations at the jet centerline. Finally, our LDV measurements reveal a frequency spectrum characterized by a −3 power-law exponent, different from the well-known −5/3 power-law exponent characteristic of Newtonian turbulence. 

Arrested soft materials such as gels and glasses exhibit a slow stress relaxation with a broad distribution of relaxation times in response to linear mechanical perturbations. Although this macroscopic stress relaxation is an essential feature in the application of arrested systems as structural materials, consumer products, foods, and biological materials, the microscopic origins of this relaxation remain poorly understood. Here, we elucidate the microscopic dynamics underlying the stress relaxation of such arrested soft materials under both quiescent and mechanically perturbed conditions through X-ray photon correlation spectroscopy. By studying the dynamics of a model associative gel system that undergoes dynamical arrest in the absence of aging effects, we show that the mean stress relaxation time measured from linear rheometry is directly correlated to the quiescent superdiffusive dynamics of the microscopic clusters, which are governed by a buildup of internal stresses during arrest. We also show that perturbing the system via small mechanical deformations can result in large intermittent fluctuations in the form of avalanches, which give rise to a broad non-Gaussian spectrum of relaxation modes at short times that is observed in stress relaxation measurements. These findings suggest that the linear viscoelastic stress relaxation in arrested soft materials may be governed by nonlinear phenomena involving an interplay of internal stress relaxations and perturbation-induced intermittent avalanches.