In this paper we describe various limited-stretch models of nonlinear rubber elasticity, each dependent on only the first invariant of the left Cauchy-Green strain tensor and having only two independent material constants. The models are described as limited-stretch, or restricted elastic, because the strain energy and stress response become infinite at a finite value of the first invariant. These models describe well the limited stretch of the polymer chains of which rubber is composed. We discuss Gent's model which is the simplest limited-stretch model and agrees well with experiment. Various statistical models are then described: the one-chain, three-chain, four-chain and Arruda-Boyce eight-chain models, all of which involve the inverse Langevin function. A numerical comparison between the three-chain and eight-chain models is provided. Next, we compare various models which involve approximations to the inverse Langevin function with the exact inverse Langevin function of the eight-chain model. A new approximate model is proposed that is as simple as Cohen's original model but significantly more accurate. We show that effectively the eight-chain model may be regarded as a linear combination of the neo-Hookean and Gent models. Treloar's model is shown to have about half the percentage error of our new model but it is much more complicated. For completeness a modified Treloar model is introduced but this is only slightly more accurate than Treloar's original model. For the deformations of uniaxial tension, biaxial tension, pure shear and simple shear we compare the accuracy of these models, and that of Puso, with the eight-chain model by means of graphs and a table. Our approximations compare extremely well with models frequently used and described in the literature, having the smallest mean percentage error over most of the range of the argument.
The solution of the many-body statistical mechanical theory of elasticity formulated by James and Guth in the 1940s is presented. The remarkable aspect of the solution is that it gives an elastic free energy that is essentially equivalent to that developed by Flory over a period of several decades.
Classical network elasticity theories are based on the concept of flexible volumeless polymers fixed into a network in which there are no excluded volume, or even topological interactions, and where the chains explore accessible configurations by Brownian motion. In this type of model, the elasticity of the network derives from the entropic changes arising from a displacement of the network junction positions. The shortcoming of this approach is clear from the observation that unswollen rubbery materials are nearly incompressible, reflecting the existence of strong intermolecular interactions …
Rubber elasticity is the archetype of the entropic force emerging from the second law of thermodynamics; numerous experimental and theoretical studies on natural and synthetic rubbers have shown that the elasticity originates mostly from entropy change with deformation. Similarly, in polymer gels containing a large amount of solvent, it has also been postulated that the shear modulus (the modulus of rigidity) $G$, which is a kind of modulus of elasticity, is approximately equivalent to the entropy contribution $G_S$, but this has yet to be verified experimentally. In this study, we measure the…
We numerically examine the nonlinear rubber elasticity of topologically constrained polymer networks. We propose a simple and effective model based on Graessley and Pearson's topological model (GP model) for describing the topological effect. The main point is to take account of a nonequilibrium effect in the synthesis process of the polymer network. We introduce a new parameter $γ$ to describe entropic contributions from the entanglement of polymer loops, which may be determined from the structural characteristics of the sample. The model is evaluated in the light of experimental data under u…
We revisit an iconic deformation of non-linear elasticity: the inflation of a rubber spherical thin shell. We use the 3-parameter Mooney and Gent-Gent (GG) phenomenological models to explain the stretch-strain curve of a typical inflation, as these two models cover a wide spectrum of known models for rubber, including the Varga, Mooney-Rivlin, one-term Ogden, Gent-Thomas and Gent models. We find that the basic physics of inflation exclude the Varga, one-term Ogden and Gent-Thomas models. We find the link between the exact solution of non-linear elasticity and the membrane and Young-Laplace the…
The classical theory of rubber elasticity fails in the regime of large deformation. The un- derlying physical mechanism has been under debate for long time. In this work, we test the recently proposed mechanism of thermal elastic fluctuations by Xing, Goldbart and Radzi- hovsky1 against the biaxial stress-strain data of three distinct polymer networks with very different network structures, synthesized by Urayama2 and Kawabata3 respectively. We find that both the two parameters version and the one-parameter version of the XGR theory provide satisfactory description of the elasticity in whole d…
A great variety of models can describe the non-linear response of rubber to uni-axial tension. Yet an in-depth understanding of the successive stages of large extension is still lacking. We show that the response can be broken down in three steps, which we delineate by relying on a simple formatting of the data, the so-called Mooney transform. First, the small-to-moderate regime, where the polymeric chains unfold easily and the Mooney plot is almost linear. Second, the strain-hardening regime, where blobs of bundled chains unfold to stiffen the response in correspondence to the "upturn" of the…
A nonlinear small-strain elastic theory is constructed from a systematic expansion in Biot strains, truncated at quadratic order. The primary motivation is the desire for a clean separation between stretching and bending energies for shells, which appears to arise only from reduction of a bulk energy of this type. An approximation of isotropic invariants, bypassing the solution of a quartic equation or computation of tensor square roots, allows stretches, rotations, stresses, and balance laws to be written in terms of derivatives of position. Two-field formulations are also presented. Extensio…
Two semi-infinite bodies made of prestressed, homogeneous, Bell-constrained, hyperelastic materials are perfectly bonded along a plane interface. The half-spaces have been subjected to finite pure homogeneous predeformations, with distinct stretch ratios but common principal axes, and such that the interface is a common principal plane of strain. Constant loads are applied at infinity to maintain the deformations and the influence of these loads on the propagation of small-amplitude interface (Stoneley) waves is examined. In particular, the secular equation is found and necessary and sufficien…
The effect of network chain distribution on mechanical behavior of elastomers is one of the long standing problems in rubber mechanics. The classical theory of rubber elasticity is built upon the assumption of entropic elasticity of networks whose constitutive strands are of uniform length. The kinetic theories for vulcanization, computer simulations, and indirect experimental measurements all indicate that the microstructure of vulcanizates is made of polymer strands with a random distribution of length. The polydispersity in strand length is expected to control the mechanical strength of rub…
The two approaches to analyzing the large strain behavior of rubbery networks are phenomenologically, using strain energy functions drawn from continuum mechanics, and molecular models, which apply statistical mechanics to compute the effect of chain orientation on the entropy. The early rubber elasticity models ignored intermolecular interactions, whereas later developments ("constraint models") included the effect of entanglements or steric constraints on the mechanical stress. These constitutive equations for rubber elasticity are compared to experimental results, and the connection of netw…
The stability of a Bell-constrained half-space in compression is studied. To this end, the propagation of Rayleigh waves on the surface of the material when it is maintained in a static state of triaxial prestrain is considered. The prestrain is such that the free surface of the half-space is a principal plane of deformation. The exact secular equation is established for surface waves traveling in a principal direction of strain with attenuation along the principal direction normal to the free plane. As the half-space is put under increasing compressive loads, the speed of the wave eventually …
The effect of network chain distribution on the mechanical behavior of elastomers is one of the long-standing problems in rubber mechanics. The classical theory of rubber elasticity is built upon the assumption of entropic elasticity of networks whose constitutive strands are of uniform length. The kinetic theories for vulcanization, computer simulations, and indirect experimental measurements all indicate that the microstructure of vulcanizates is made of polymer strands with a random distribution of length. The polydispersity in strand length is expected to control the mechanical strength of…
Floppy Networks (FNs) provide valuable insight into the origin of anomalous mechanical and thermal properties in soft matter systems, from polymers, rubber, and biomolecules to glasses and granular materials. Here, we use the very same FN concept to construct a quantitative microscopic theory of empty perovskites, a family of crystals with ReO$_3$ structure, which exhibit a number of unusual properties. One remarkable example is ScF$_3$, which shows a near-zero-temperature structural instability and large negative thermal expansion (NTE). We trace these effects to an FN-like crystalline archit…
The second invariant of the left Cauchy-Green deformation tensor $\mathbf{B}$ (or right $\mathbf{C}$) has been argued to play a fundamental role in nonlinear elasticity. Generalized neo-Hookean materials, which depend only on the first invariant, lead to universal relations that conflict with experimental data, fail to display important mechanical behaviors (such as the Poynting effect in simple shear), and may not provide a satisfactory link with the mesoscale. However, the second invariant term is not a higher order strain contribution to the energy, which lead us to reflect on what is incom…
In this work we will derive an anisotropic generalisation of the finitely extensible chain model, due to Kuhn and Grün, which is well known in rubber elasticity. This provides a chain energy that couples elastic behaviour to a probability distribution describing the orientations of liquid crystal monomers within a main chain elastomer. The key point is to invoke a maximum relative entropy assumption on the distribution of bond angles in an observed chain. The chain energy's fourth order Taylor expansion is also given, which couples to the second and fourth moments of the nematic distribution f…
DNA nanotubes are tubular structures composed of DNA crossover molecules. We present a bottom up approach for construction and characterization of these structures. Various possible topologies of nanotubes are constructed such as 6-helix, 8-helix and tri-tubes with different sequences and lengths. We have used fully atomistic molecular dynamics simulations to study the structure, stability and elasticity of these structures. Several nanosecond long MD simulations give the microscopic details about DNA nanotubes. Based on the structural analysis of simulation data, we show that 6-helix nanotube…
We examine how the distribution of contour lengths and the high-stretch stiffening of individual chain segments affect the macroscopic shear modulus of flexible polymer gels, using a 2D numerical model, in which polymer segments form a triangular network and disorder is introduced by varying their contour lengths. We show that in the relevant parameter range: (i) the non-affine contribution to the shear modulus is negligible, i.e. the Born approximation is satisfactory; (ii) the shear modulus is dominated by the contribution originating from equilibrium chain tensions. Moreover, mechanical equ…
Liquid crystal elastomers are rubber-like solids with liquid crystalline mesogens (stiff, rod-like molecules) incorporated either into the main chain or as a side chain of the polymer. These solids display a range of unusual thermo-mechanical properties as a result of the coupling between the entropic elasticity of rubber and the orientational phase transitions of liquid crystals. One of these intriguing properties is the soft behavior, where it is able to undergo significant deformations with almost no stress. While the phenomenon is well-known, it has largely been examined in the context of …
We provide a unified theory for the high force elasticity of biopolymers solely in terms of the persistence length, $ξ_p$, and the monomer spacing, $a$. When the force $f>\fh \sim k_BTξ_p/a^2$ the biopolymers behave as Freely Jointed Chains (FJCs) while in the range $\fl \sim k_BT/ξ_p < f < \fh$ the Worm-like Chain (WLC) is a better model. We show that $ξ_p$ can be estimated from the force extension curve (FEC) at the extension $x\approx 1/2$ (normalized by the contour length of the biopolymer). After validating the theory using simulations, we provide a quantitative analysis of the FECs for a…
The flexibility and the extension along the direction of the force are shown to be related to the bubble number fluctuation and the average number of bubbles respectively, when the strands of the DNA are subjected to a force along the same direction, here we call a stretching force. The force-temperature phase diagram shows the existence of a tricritical point (TCP), where the first-order force induced zipping transition becomes continuous. On the other hand, when the forces are being applied in opposite directions, here we call an unzipping force, the transition remains first-order,with the p…
We present an atomistic model of pillared DNA nanotubes (DNTs) and their elastic properties which will facilitate further studies of these nanotubes in several important nanotechnological and biological applications. In particular, we introduce a computational design to create an atomistic model of a 6-helix DNT (6HB) along with its two variants, 6HB flanked symmetrically by two double helical DNA pillars (6HB+2) and 6HB flanked symmetrically by three double helical DNA pillars (6HB+3). Analysis of 200 ns all-atom simulation trajectories in the presence of explicit water and ions shows that th…
The diluted kagome lattice, in which bonds are randomly removed with probability $1-p$, consists of straight lines that intersect at points with a maximum coordination number of four. If lines are treated as semi-flexible polymers and crossing points are treated as crosslinks, this lattice provides a simple model for two-dimensional filamentous networks. Lattice-based effective medium theories and numerical simulations for filaments modeled as elastic rods, with stretching modulus $μ$ and bending modulus $κ$, are used to study the elasticity of this lattice as functions of $p$ and $κ$. At $p=1…
Motivated by the increased interest in modeling nondissipative materials by constitutive relations more general than those from Cauchy elasticity, we initiate the study of a class of stretch-limited elastic strings: the string cannot be compressed smaller than a certain length less than its natural length nor elongated larger than a certain length greater than its natural length. In particular, we consider equilibrium states for a string suspended between two points under the force of gravity (catenaries). We study the locations of the supports resulting in tensile states containing both exten…
We analyze the stretching elasticity of a wormlike chain with a tension discontinuity resulting from a Hookean spring connecting its backbone to a fixed point. The elasticity of isolated semiflexible filaments has been the subject in a significant body of literature, primarily because of its relevance to the mechanics of biological matter. In real systems, however, these filaments are usually part of supramolecular structures involving cross-linkers or molecular motors which cause tension discontinuities. Our model is intended as a minimal structural element incorporating such a discontinuity.…
