An official website of the United States government
The mechanical properties of a polymer network reflect the collective behavior of all of the constituent strands within the network. These strands comprise a distribution of states, and a central question is how the deformation and tension experienced by a strand is influenced by strand length. Here, we address this question through the use of mechanophore force probes with discrete molecular weights. Probe strands, each bearing a mechanochromic spiropyran (SP), were prepared through an iterative synthetic strategy, providing uniform PDMS-functionalized SP force probes with molecular weights of 578, 1170, and 2356 g/mol. The probes were each doped (9 mM) into the same silicone elastomer matrix. Upon stretching, the materials change color, consistent with the expected conversion of SP to merocyanine (MC). The critical strain at which measurable mechanochromism is observed is correlated with the strain hardening of the matrix, but it is independent of the molecular length of the probe strand. When a network with activated strands is relaxed, the color dissipates, and the rate of decoloration varies as a function of the relaxing strain ((ε_r ) ̅); faster decoloration occurs at lower (ε_r ) ̅. The dependence of decoloration rate on (ε_r ) ̅ is taken to reflect the effect of residual tension in the once-activated strands on the reversion reaction of MC to SP, and the effect of that residual tension is indistinguishable across the three molecular lengths examined. The combination of discrete strand synthesis and mechanochromism provides a foundation to further test and develop molecular-based theories of elasticity and fracture in polymer networks.
more »
« less
Contribution of Unbroken Strands to the Fracture of Polymer Networks
We present a modified Lake–Thomas theory that accounts for the molecular details of network connectivity upon crack propagation in polymer networks. This theory includes not only the energy stored in the breaking network strands (bridging strands) but also the energy stored in the tree-like structure of the strands connecting the bridging strands to the network continuum, which remains intact as the crack propagates. The energy stored in each of the generations of this tree depends nonmonotonically on the generation index due to the nonlinear elasticity of the stretched network strands. Further, the energy required to break a single bridging strand is not necessarily dominated by the energy stored in the bridging strand itself but in the higher generations of the tree. We describe the effect of mechanophores with stored length on the energy stored in the tree-like structure. In comparison with the “strong” mechanophores that can only be activated in the bridging strand, “weak” mechanophores that can be activated both in the bridging strand and in other generations could provide more energy dissipation due to their larger contribution to higher generations of the tree.
more »
« less
- Award ID(s):
- 2116298
- PAR ID:
- 10400729
- Date Published:
- Journal Name:
- Macromolecules
- ISSN:
- 0024-9297
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Claudins are cell-cell adhesion proteins within tight junctions that connect epithelial cells together. Claudins polymerize into a network of strand-like structures within the membrane of adjoining cells and create ion channels that control paracellular permeability to water and small molecules. Tight junction morphology and barrier function is tissue specific and regulated by claudin subtypes. Here, we present a molecular dynamics study of claudin-15 strands within lipid membranes and the role of a single-point mutation (A134P) on the third transmembrane helix (TM3) of claudin-15 in determining the morphology of the strand. Our results indicate that the A134P mutation significantly affects the lateral flexibility of the strands, increasing the persistence length of claudin-15 strands by a factor of three. Analyses of claudin-claudin contact in our μ second-long trajectories show that the mutation does not alter the intermolecular contacts (interfaces) between claudins. However, the dynamics and frequency of interfacial contacts are significantly affected. The A134P mutation introduces a kink in TM3 of claudin-15 similar to the one observed in claudin-3 crystal structure. The kink on TM3 skews the rotational flexibility of the claudins in the strands and limits their fluctuation in one direction. This asymmetric movement in the context of the double rows reduces the lateral flexibility of the strand and leads to higher persistence lengths of the mutant.more » « less
-
Slide-ring gels are polymer networks with cross-links that can slide along the chains. In contrast to conventional unentangled networks with cross-links fixed along the chains, the slide-ring networks are strain-softening and distribute tension much more uniformly between their strands due to the so-called “pulley effect”. The sliding of cross-links also reduces the elastic modulus in comparison with the modulus of conventional networks with the same number density of cross-links and elastic strands. We develop a single-chain model to account for the redistribution of monomers between network strands of a primary chain. This model takes into account both the pulley effect and fluctuations in the number of monomers per network strand. The pulley effect leads to modulus reduction and uniform tension redistribution between network strands, while fluctuations in the number of strand monomers dominate the strain-softening, the magnitude of which decreases upon network swelling and increases upon deswelling.more » « less
-
We use coarse-grained molecular dynamics simulations to study deformation of networks and gels of linear and brush strands in both linear and nonlinear deformation regimes under constant pressure conditions. The simulations show that the Poisson ratio of networks and gels could exceed 0.5 in the nonlinear deformation regime. This behavior is due to the ability of the network and gel strands to sustain large reversible deformation, which, in combination with the finite strand extensibility results in strand alignment and monomer density, increases with increasing strand elongation. We developed a nonlinear network and gel deformation model which defines conditions for the Poisson ratio to exceed 0.5. The model predictions are in good agreement with the simulation results.more » « less
-
Abstract Infaunal organisms mix sediments through burrowing, ingestion and egestion, enhancing fluxes of nutrients and oxygen, yet the mechanisms underlying bioturbation remain unresolved. Burrows are extended through muddy sediments by fracture, and we hypothesize that the cohesive properties of sediments play an important but unexplored role in resisting bioturbation. Specifically, we suggest that crack branching, tortuosity, and microcracking are important in freeing particles from the cohesive matrix, and that the sediment properties that affect these processes are important predictors of bioturbation. We use finite element modeling and simplified, mechanics‐based models to explore the relative importance of sediment mechanical properties and worm behaviors in determining crack propagation paths. Our results show that crack propagation direction depends on variability in fracture toughness, and that applying more force to one side of the burrow wall, simulating “steering” behavior, has surprisingly little effect on crack propagation direction. Burrowers instead steer by choosing among crack branches. Paths created by burrowing worms in natural sediments are mostly straight with some crack branching, consistent with modeling results. Crack branching also requires sufficient stored elastic energy to drive two cracks, and worms can exert larger forces resulting in more stored energy in stiffer sediments. This implies that more crack branching and consequently more particle mixing occurs in heterogeneous sediments with low fracture toughness relative to stiffness. Whether sediments with greater potential for crack branching also experience higher bioturbation remains to be tested, but these results indicate that material properties of sediments may be important in resisting or facilitating bioturbation.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.macromol.2c02139
