skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: A kinetic theory for the mechanics and remodeling of transient anisotropic networks
We present a statistically-based theoretical framework to describe the mechanical response of dynamically crosslinked semi-flexible polymer networks undergoing finite deformation. The theory starts from a statistical description, via a distribution function, of the chain conformation and orientation. Assuming a so-called tangent affine deformation of the chains, this distribution is then allowed to evolve in time due to a combination of elastic network distortion and a permanent chain reconfiguration enabled by dynamic crosslinks. After presenting the evolution law for the chain distribution function, we reduce the theory to the evolution of the network conformation tensor in both its natural and current state. With this model, we use classical thermodynamics to determine how the stored elastic energy, energy dissipation, and true stress evolve in terms of the network conformation. We show that the model degenerates to classical anisotropic hyperelastic models when crosslinks are permanent, while we recover the classical form of the transient network theory (that describes hyper-viscoelasticity) when chains are fully flexible. Theoretical predictions are then illustrated and compared to the literature for both basic model problems and biomechanically relevant situations  more » « less
Award ID(s):
2023179
PAR ID:
10565402
Author(s) / Creator(s):
; ;
Publisher / Repository:
Elsevier
Date Published:
Journal Name:
Journal of the Mechanics and Physics of Solids
Volume:
190
Issue:
C
ISSN:
0022-5096
Page Range / eLocation ID:
105713
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    Dynamic networks contain crosslinks that re-associate after disconnecting, imparting them with viscoelastic properties. While continuum approaches have been developed to analyze their mechanical response, these approaches can only describe their evolution in an average sense, omitting local, stochastic mechanisms that are critical to damage initiation or strain localization. To address these limitations, we introduce a discrete numerical model that mesoscopically coarse-grains the individual constituents of a dynamic network to predict its mechanical and topological evolution. Each constituent consists of a set of flexible chains that are permanently cross-linked at one end and contain reversible binding sites at their free ends. We incorporate nonlinear force–extension of individual chains via a Langevin model, slip-bond dissociation through Eyring's model, and spatiotemporally-dependent bond attachment based on scaling theory. Applying incompressible, uniaxial tension to representative volume elements at a range of constant strain rates and network connectivities, we then compare the mechanical response of these networks to that predicted by the transient network theory. Ultimately, we find that the idealized continuum approach remains suitable for networks with high chain concentrations when deformed at low strain rates, yet the mesoscale model proves necessary for the exploration of localized stochastic events, such as variability of the bond kinetics, or the nucleation of micro-cavities that likely conceive damage and fracture. 
    more » « less
  2. We study the collective elastic behavior of semiflexible polymer solutions in a nematic liquid-crystalline state using polymer field theory. Our polymer field-theoretic model of semiflexible polymer solutions is extended to include second-order fluctuation corrections to the free energy, permitting the evaluation of the Frank elastic constants based on orientational order fluctuations in the nematic state. Our exact treatment of wormlike chain statistics permits the evaluation of behavior from the nematic state, thus accurately capturing the impact of single-chain behavior on collective elastic response. Results for the Frank elastic constants are presented as a function of aligning field strength and chain length, and we explore the impact of conformation fluctuations and hairpin defects on the twist, splay, and bend moduli. Our results indicate that the twist elastic constant Ktwist is smaller than both bend and splay constants (Kbend and Ksplay, respectively) for the entire range of polymer rigidity. Splay and bend elastic constants exhibit regimes of dominance over the range of chain stiffness, where Ksplay > Kbend for flexible polymers (large-N limit) while the opposite is true for rigid polymers. Theoretical analysis also suggests the splay modulus tracks exactly to that of the end-to-end distance in the transverse direction for semiflexible polymers at intermediate to large-N. These results provide insight into the role of conformation fluctuations and hairpin defects on the collective response of polymer solutions. 
    more » « less
  3. Liquid crystal elastomers (LCEs) are a class of smart elastomers exhibiting unusual mechanical behavior, including large energy dissipation and soft elasticity under uniaxial tensile loading. LCEs are composed of liquid crystal molecules, called mesogens, linked by a network of polymer chains. During deformation, the mesogens orient in the direction of the loading, leading to soft elasticity, which is an increase in strain at constant stress. The combination of mesogen rotation and intrinsic polymer viscoelasticity leads to a nonlinear viscoelastic soft elastic behavior. The aim of this paper is to investigate the coupling between the viscoelastic mechanisms and soft elasticity in main chain LCEs. We propose a rheological model in which the mesogen rotation during deformation is represented by a reversible slider while viscoelastic relaxation mechanisms are modeled as series of Maxwell elements coupled or decoupled with mesogen rotation. Fitting this model to experimental data demonstrate that the coupling between polymer chain viscoelasticity and mesogen rotation is partial, i.e. the long-time relaxation mechanisms are coupled and the short-time relaxation mechanisms are decoupled from mesogen rotation. Furthermore, we show that the viscosity of mesogen rotation is not necessary to properly predict the elastic modulus during the soft elasticity but it is needed to properly predict the initiation of the phenomenon. \end{abstract} 
    more » « less
  4. Abstract A hydrogel is often fabricated from preexisting polymer chains by covalently crosslinking them into a polymer network. The crosslinks make the hydrogel swell‐resistant but brittle. This conflict is resolved here by making a hydrogel from a dough. The dough is formed by mixing long polymer chains with a small amount of water and photoinitiator. The dough is then homogenized by kneading and annealing at elevated temperatures, during which the crowded polymer chains densely entangle. The polymer chains are then sparsely crosslinked into a polymer network under an ultraviolet lamp, and submerged in water to swell to equilibrium. The resulting hydrogel is both swell‐resistant and tough. The hydrogel also has near‐perfect elasticity, high strength, high fatigue resistance, and low friction. The method is demonstrated with two widely used polymers, poly(ethylene glycol) and cellulose. These hydrogels have never been made swell‐resistant, elastic, and tough before. The method is generally applicable to synthetic and natural polymers, and is compatible with industrial processing technologies, opening doors to the development of sustainable, high‐performance hydrogels. 
    more » « less
  5. In this paper, we derive a dynamic surface elasticity model for the two-dimensional midsurface of a thin, three-dimensional, homogeneous, isotropic, nonlinear gradient elastic plate of thickness ℎ. The resulting model is parameterized by five, conceivably measurable, physical properties of the plate, and the stored surface energy reduces to Koiter’s plate energy in a singular limiting case. The model corrects a theoretical issue found in wave propagation in thin sheets and, when combined with the author’s theory of Green elastic bodies possessing gradient elastic material boundary surfaces, removes the singularities present in fracture within traditional/classical models. Our approach diverges from previous research on thin shells and plates, which primarily concentrated on deriving elasticity theories for material surfaces from classical three-dimensional Green elasticity. This work is the first in rigorously developing a surface elasticity model based on a parent nonlinear gradient elasticity theory. 
    more » « less