Stress relaxation in tunable gels.

Hydrogels are a staple of biomaterials development. Optimizing their use in e.g. drug delivery or tissue engineering requires a solid understanding of how to adjust their mechanical properties. Here, we present a numerical study of a class of hydrogels made of 4-arm star polymers with a combination of covalent and reversible crosslinks. This design principle combines the flexibility and responsivity associated with reversible linkers with stability provided by chemical crosslinks. In molecular dynamics simulations of such hybrid gel networks, we observe that the strength of the reversible bonds can tune the material from solid to fluid. We identify at what fraction of reversible bonds this tunability is most pronounced, and find that the stress relaxation time of the gels in this tunable regime is set directly by the average lifetime of the reversible bonds. As our design is easy to realize in the already widely-used tetraPEG gel setting, our work will provide guidelines to improve the mechanical performance of biomedical gels.

Self-stresses control stiffness and stability in overconstrained disordered networks.

We investigate the interplay between prestress and mechanical properties in random elastic networks. To do this in a controlled fashion, we introduce an algorithm for creating random free-standing frames that support exactly one state of self-stress. By multiplying all the bond tensions in this state of self-stress by the same number-which with the appropriate normalization corresponds to the physical prestress inside the frame-we systematically evaluate the linear mechanical response of the frame as a function of prestress. After proving that the mechanical moduli of affinely deforming frames are rigorously independent of prestress, we turn to nonaffinely deforming frames. In such frames, prestress has a profound effect on linear response: not only can it change the values of the linear modulus-an effect we demonstrate to be related to a suppressive effect of prestress on nonaffinity-but prestresses also generically trigger a bistable mechanical response. Thus, prestress can be leveraged to both augment the mechanical response of network architectures on the fly, and to actuate finite deformations. These control modalities may be of use in the design of both novel responsive materials and soft actuators.

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.

Two-dimensional crystals of star polymers: a tale of tails.

The formation of non-hexagonal crystalline structures by the organisation of colloidal nanoparticles often involves the use of complex particles with anisotropic shape or interactions or the imposition of non-uniform external fields. Here we explore how unusual symmetries can be created using experimentally realistic particles that interact through isotropic and purely repulsive potentials. In particular, we use simulations to explore the phase behavior of two-dimensional systems of star polymers. We uncover how the tail of the pair potential has a large role in dictating the phase behavior. Star polymers interacting in the far field with a Gaussian potential only form hexagonal phases, while an exponential tail gives rise to stable primitive oblique and honeycomb lattices. We identify the ratio in strength between long and short range interactions and the nature of the transition between these regimes as crucial parameters to predict when non-hexagonal crystals of star polymers can be stable. This leads to experimental design rules for creating star polymers which should exhibit unusual lattice formation.

Dynamics of Vitrimers: Defects as a Highway to Stress Relaxation.

We propose a coarse-grained model to investigate stress relaxation in star-polymer networks induced by dynamic bond-exchange processes. We show how the swapping mechanism, once activated, allows the network to reconfigure, exploring distinct topological configurations, all of them characterized by complete extent of reaction. Our results reveal the important role played by topological defects in mediating the exchange reaction and speeding up stress relaxation. The model provides a representation of the dynamics in vitrimers, a new class of polymers characterized by bond-swap mechanisms which preserve the total number of bonds, as well as in other bond-exchange materials.

Geometry and the onset of rigidity in a disordered network.

Disordered spring networks that are undercoordinated may abruptly rigidify when sufficient strain is applied. Since the deformation in response to applied strain does not change the generic quantifiers of network architecture, the number of nodes and the number of bonds between them, this rigidity transition must have a geometric origin. Naive, degree-of-freedom-based mechanical analyses such as the Maxwell-Calladine count or the pebble game algorithm overlook such geometric rigidity transitions and offer no means of predicting or characterizing them. We apply tools that were developed for the topological analysis of zero modes and states of self-stress on regular lattices to two-dimensional random spring networks and demonstrate that the onset of rigidity, at a finite simple shear strain γ^{★}, coincides with the appearance of a single state of self-stress, accompanied by a single floppy mode. The process conserves the topologically invariant difference between the number of zero modes and the number of states of self-stress but imparts a finite shear modulus to the spring network. Beyond the critical shear, the network acquires a highly anisotropic elastic modulus, resisting further deformation most strongly in the direction of the rigidifying shear. We confirm previously reported critical scaling of the corresponding differential shear modulus. In the subcritical regime, a singular value decomposition of the network's compatibility matrix foreshadows the onset of rigidity by way of a continuously vanishing singular value corresponding to the nascent state of self-stress.

Self-Consistent Field Lattice Model for Polymer Networks.

A lattice model based on polymer self-consistent field theory is developed to predict the equilibrium statistics of arbitrary polymer networks. For a given network topology, our approach uses moment propagators on a lattice to self-consistently construct the ensemble of polymer conformations and cross-link spatial probability distributions. Remarkably, the calculation can be performed "in the dark", without any prior knowledge on preferred chain conformations or cross-link positions. Numerical results from the model for a test network exhibit close agreement with molecular dynamics simulations, including when the network is strongly sheared. Our model captures nonaffine deformation, mean-field monomer interactions, cross-link fluctuations, and finite extensibility of chains, yielding predictions that differ markedly from classical rubber elasticity theory for polymer networks. By examining polymer networks with different degrees of interconnectivity, we gain insight into cross-link entropy, an important quantity in the macroscopic behavior of gels and self-healing materials as they are deformed.

Rigidity loss in disordered systems: three scenarios.

We reveal significant qualitative differences in the rigidity transition of three types of disordered network materials: randomly diluted spring networks, jammed sphere packings, and stress-relieved networks that are diluted using a protocol that avoids the appearance of floppy regions. The marginal state of jammed and stress-relieved networks are globally isostatic, while marginal randomly diluted networks show both overconstrained and underconstrained regions. When a single bond is added to or removed from these isostatic systems, jammed networks become globally overconstrained or floppy, whereas the effect on stress-relieved networks is more local and limited. These differences are also reflected in the linear elastic properties and point to the highly effective and unusual role of global self-organization in jammed sphere packings.

Divalent cation-dependent formation of electrostatic PIP2 clusters in lipid monolayers.

Polyphosphoinositides are among the most highly charged molecules in the cell membrane, and the most common polyphosphoinositide, phosphatidylinositol-4,5-bisphosphate (PIP(2)), is involved in many mechanical and biochemical processes in the cell membrane. Divalent cations such as calcium can cause clustering of the polyanionic PIP(2), but the origin and strength of the effective attractions leading to clustering has been unclear. In addition, the question of whether the ion-mediated attractions could be strong enough to alter the mechanical properties of the membrane, to our knowledge, has not been addressed. We study phase separation in mixed monolayers of neutral and highly negatively charged lipids, induced by the addition of divalent positively charged counterions, both experimentally and numerically. We find good agreement between experiments on mixtures of PIP(2) and 1-stearoyl-2-oleoyl phosphatidylcholine and simulations of a simplified model in which only the essential electrostatic interactions are retained. In addition, we find numerically that under certain conditions the effective attractions can rigidify the resulting clusters. Our results support an interpretation of PIP(2) clustering as governed primarily by electrostatic interactions. At physiological pH, the simulations suggest that the effective attractions are strong enough to give nearly pure clusters of PIP(2) even at small overall concentrations of PIP(2).

Measurement of correlations between low-frequency vibrational modes and particle rearrangements in quasi-two-dimensional colloidal glasses.

We investigate correlations between low-frequency vibrational modes and rearrangements in two-dimensional colloidal glasses composed of thermosensitive microgel particles, which readily permit variation of the sample packing fraction. At each packing fraction, the particle displacement covariance matrix is measured and used to extract the vibrational spectrum of the "shadow" colloidal glass (i.e., the particle network with the same geometry and interactions as the sample colloid but absent damping). Rearrangements are induced by successive, small reductions in the packing fraction. The experimental results suggest that low-frequency quasilocalized phonon modes in colloidal glasses, i.e., modes that present low energy barriers for system rearrangements, are spatially correlated with rearrangements in this thermal system.

Rotational and translational phonon modes in glasses composed of ellipsoidal particles.

The effects of particle shape on the vibrational properties of colloidal glasses are studied experimentally. "Ellipsoidal glasses" are created by stretching polystyrene spheres to different aspect ratios and then suspending the resulting ellipsoidal particles in water at a high packing fraction. By measuring displacement correlations between particles, we extract vibrational properties of the corresponding "shadow" ellipsoidal glass with the same geometric configuration and interactions as the "source" suspension but without damping. Low-frequency modes in glasses composed of ellipsoidal particles with major-to-minor axis aspect ratios of ~1.1 are observed to have predominantly rotational character. In contrast, low-frequency modes in glasses of ellipsoidal particles with larger aspect ratios (~3.0) exhibit a mixed rotational and translational character. All glass samples were characterized by a distribution of particles with different aspect ratios. Interestingly, even within the same sample it was found that small-aspect-ratio particles participate relatively more in rotational modes, while large-aspect-ratio particles tend to participate relatively more in translational modes.

Low-frequency vibrations of soft colloidal glasses.

We conduct experiments on two-dimensional packings of colloidal thermosensitive hydrogel particles whose packing fraction can be tuned above the jamming transition by varying the temperature. By measuring displacement correlations between particles, we extract the vibrational properties of a corresponding "shadow" system with the same configuration and interactions, but for which the dynamics of the particles are undamped. The vibrational properties are very similar to those predicted for zero-temperature sphere packings and found in atomic and molecular glasses; there is a boson peak at low frequency that shifts to higher frequency as the system is compressed above the jamming transition.

Spotted vesicles, striped micelles and Janus assemblies induced by ligand binding.

Selective binding of multivalent ligands within a mixture of polyvalent amphiphiles provides, in principle, a simple mechanism for driving domain formation in self-assemblies. Divalent cations are shown here to crossbridge polyanionic amphiphiles, which thereby demix from neutral amphiphiles and form spots or rafts within vesicles as well as stripes within cylindrical micelles. Calcium- and copper-crossbridged domains of synthetic block copolymers or natural lipid (phosphatidylinositol-4,5-bisphosphate) possess tunable sizes, shapes and/or spacings that can last for years. Lateral segregation in these 'ligand-responsive Janus assemblies' couples weakly to curvature and proves to be restricted within phase diagrams to narrow regimes of pH and cation concentration that are centred near the characteristic binding constants for polyacid interactions. Remixing at high pH is surprising, but a theory for strong lateral segregation shows that counterion entropy dominates electrostatic crossbridges, thus illustrating the insights gained into ligand-induced pattern formation within self-assemblies.

Jammed frictionless disks: Connecting local and global response.

By calculating the linear response of packings of soft frictionless disks to quasistatic external perturbations, we investigate the critical scaling behavior of their elastic properties and nonaffine deformations as a function of the distance to jamming. Averaged over an ensemble of similar packings, these systems are well described by elasticity, while in single packings we determine a diverging length scale l* up to which the response of the system is dominated by the local packing disorder. This length scale, which we observe directly, diverges as 1/Deltaz , where Deltaz is the difference between contact number and its isostatic value, and appears to scale identically to the length scale which had been introduced earlier in the interpretation of the spectrum of vibrational modes. It governs the crossover from isostatic behavior at the small scale to continuum behavior at the large scale; indeed we identify this length scale with the coarse graining length needed to obtain a smooth stress field. We characterize the nonaffine displacements of the particles using the displacement angle distribution, a local measure for the amount of relative sliding, and analyze the connection between local relative displacements and the elastic moduli.

Tail of the contact force distribution in static granular materials.

We numerically study the distribution P(f) of contact forces in frictionless bead packs, by averaging over the ensemble of all possible force network configurations. We resort to umbrella sampling to resolve the asymptotic decay of P(f) for large f , and determine P(f) down to values of order 10{-45} for ordered and disordered systems in two (2D) and three dimensions (3D). Our findings unambiguously show that, in the ensemble approach, the force distributions decay much faster than exponentially: P(f) approximately exp(-cf(alpha)}) , with alpha approximately 2.0 for 2D systems, and alpha approximately 1.7 for 3D systems.

Critical and noncritical jamming of frictional grains.

We probe the nature of the jamming transition of frictional granular media by studying their vibrational properties as a function of the applied pressure p and friction coefficient mu. The density of vibrational states exhibits a crossover from a plateau at frequencies omega > or similar to omega*(p,mu) to a linear growth for omega < or similar to omega*(p,mu). We show that omega* is proportional to Deltaz, the excess number of contacts per grain relative to the minimally allowed, isostatic value. For zero and infinitely large friction, typical packings at the jamming threshold have Deltaz-->0, and then exhibit critical scaling. We study the nature of the soft modes in these two limits, and find that the ratio of elastic moduli is governed by the distance from isostaticity.

Sheared force networks: anisotropies, yielding, and geometry.

A scenario for the yielding of granular matter is presented by considering the ensemble of force networks for a given contact network and applied shear stress tau. As tau is increased, the probability distribution of contact forces becomes highly anisotropic, the difference between average contact forces along minor and major axes grows, and the allowed networks span a shrinking subspace of all force networks. Eventually, contacts start to break, and at the maximal shear stress the packing becomes effectively isostatic. The size of the allowed subspace exhibits simple scaling properties, which lead to a prediction for the yield stress for packings of an arbitrary contact number.

Critical scaling in linear response of frictionless granular packings near jamming.

We study the origin of the scaling behavior in frictionless granular media above the jamming transition by analyzing their linear response. The response to local forcing is non-self-averaging and fluctuates over a length scale that diverges at the jamming transition. The response to global forcing becomes increasingly nonaffine near the jamming transition. This is due to the proximity of floppy modes, the influence of which we characterize by the local linear response. We show that the local response also governs the anomalous scaling of elastic constants and contact number.

Ensemble theory for force networks in hyperstatic granular matter.

An ensemble approach for force networks in static granular packings is developed. The framework is based on the separation of packing and force scales, together with an a priori flat measure in the force phase space under the constraints that the contact forces are repulsive and balance on every particle. In this paper we will give a general formulation of this force network ensemble, and derive the general expression for the force distribution P(f). For small regular packings these probability densities are obtained in closed form, while for larger packings we present a systematic numerical analysis. Since technically the problem can be written as a noninvertible matrix problem (where the matrix is determined by the contact geometry), we study what happens if we perturb the packing matrix or replace it by a random matrix. The resulting P(f) 's differ significantly from those of normal packings, which touches upon the deep question of how network statistics is related to the underlying network structure. Overall, the ensemble formulation opens up a different perspective on force networks that is analytically accessible, and which may find applications beyond granular matter.