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 characterised 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.Comment: 5 pages, 5 figures, with 6 pages SI appende

Associative bond swaps in molecular dynamics

We implement a three-body potential to model associative bond swaps, and release it as part of the HOOMD-blue software. The use of a three-body potential to model swaps has been proven to be effective and has recently provided useful insights into the mechanics and dynamics of adaptive network materials such as vitrimers. It is elegant because it can be used in plain molecular dynamics simulations without the need for topology-altering Monte Carlo steps, and naturally represents typical physical features such as slip-bond behavior. It is easily tunable with a single parameter to control the average swap rate. Here, we show how associative bond swaps can be used to speed up the equilibration of systems that self-assemble by avoiding traps and pitfalls, corresponding to long-lived metastable configurations. Our results demonstrate the possibilities of these swaps not only for modeling systems that are associative by nature, but also for increasing simulation efficiency in other systems that are modellable in HOOMD-blue

Stability of jammed packings I: the rigidity length scale

In 2005, Wyart et al. (Europhys. Lett., 72 (2005) 486) showed that the low frequency vibrational properties of jammed amorphous sphere packings can be understood in terms of a length scale, called l*, that diverges as the system becomes marginally unstable. Despite the tremendous success of this theory, it has been difficult to connect the counting argument that defines l* to other length scales that diverge near the jamming transition. We present an alternate derivation of l* based on the onset of rigidity. This phenomenological approach reveals the physical mechanism underlying the length scale and is relevant to a range of systems for which the original argument breaks down. It also allows us to present the first direct numerical measurement of l*.Comment: 8 pages, 5 figure

Jammed frictionless discs: connecting local and global response

By calculating the linear response of packings of soft frictionless discs to quasistatic external perturbations, we investigate the critical scaling behavior of their elastic properties and non-affine 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 $\ell^*$ up to which the response of the system is dominated by the local packing disorder. This length scale, which we observe directly, diverges as $1/\Delta z$, where $\Delta z$ 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 non-affine displacements of the particles using the \emph{displacement angle distribution}, a local measure for the amount of relative sliding, and analyze the connection between local relative displacements and the elastic moduli.Comment: 19 pages, 15 figures, submitted to Phys. Rev.

Rigidity percolation on the square lattice

The square lattice with central forces between nearest neighbors is isostatic with a subextensive number of floppy modes. It can be made rigid by the random addition of next-nearest neighbor bonds. This constitutes a rigidity percolation transition which we study analytically by mapping it to a connectivity problem of two-colored random graphs. We derive an exact recurrence equation for the probability of having a rigid percolating cluster and solve it in the infinite volume limit. From this solution we obtain the rigidity threshold as a function of system size, and find that, in the thermodynamic limit, there is a mixed first-order-second-order rigidity percolation transition at the isostatic point.Comment: 6 pages, 3 figure

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 non-affine 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.Comment: 4 pages, 3 figures. v2: Added new results; removed part of discussion; changed Fig.

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 linear 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

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 $\gamma^\star$, 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, we confirm previously reported critical scaling of the modulus. In the sub-critical 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 nascent state of self stress.Comment: 6 pages, 6 figue

Critical and non-critical 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 \gtrsim omega^*(p,mu) to a linear growth for omega \lesssim omega^*(p,mu). We show that omega^* is proportional to Delta z, the excess number of contacts per grains relative to the minimally allowed, isostatic value. For zero and infinitely large friction, typical packings at the jamming threshold have Delta z -> 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.Comment: 4 pages, 4 figures; discussion update

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.</p