Influence of microstructural parameters on mechanical behavior of polymer gels

The swelling deformation behavior of polymer gels is often described in terms of the Flory–Rehner framework, in which the Flory–Rehner free energy function is based on the simplest affine network model, does not take entanglements into account. However, the real polymer networks have many chain entanglements. In this paper, a new hybrid free energy function composed of the Edwards–Vilgis slip-link model and the Flory–Huggins solution theory is presented for the prediction of the influence of chain entanglements on mechanical behavior of gels. The simulation results of mechanical behavior in free swelling, uniaxial extension, biaxial constraint and simple shear are presented. It is shown that in the nonentangled state, this new hybrid free energy function reduces to the Flory–Rehner free energy function; in the entangled state, the influence of entanglements on the mechanical behavior of gels is significant, the more entangled networks exhibit higher stress.     

缠结拓扑限制作用对凝胶杆屈曲的影响

当前对聚合物凝胶失稳现象的研究大多是基于Flory-Rehner弹性凝胶理论,并未考虑凝胶网络链段相互缠绕引起的物理交联对凝胶弹性网络自由能的影响．因此,本文采用了一个新的,包含网络缠结拓扑限制作用的凝胶自由能函数,在此基础上计算交联网链数密度与滑动环数密度的比值、不可伸展参数、滑移参数对聚合物凝胶的折合增量模量的影响,并给出了不同长细比凝胶杆的临界屈曲应力．研究结果表明：交联网链数密度与滑动环数密度的比值、不可伸展参数越大,增量模量越大,而滑移参数越大,增量模量越小;凝胶杆的长细比越大,临界屈曲应力越小．     

The chemo-mechanical coupling behavior of hydrogels incorporating entanglements of polymer chains

To describe precisely the chemo-mechanical coupling behavior of hydrogels, a general form of free energy density function is presented by considering chain entanglements and functionality of junctions. We use the chemical potential of the solvent and the deformation gradient of the network as the independent variables of the developed free energy function, and implement this material model in the finite element package, ABAQUS, to analyze several examples of chemo-mechanical equilibrium deformation behaviors of hydrogels. The influence of chain entanglements and junction functionality on the chemo-mechanical behavior of hydrogels is addressed based on our simulation. With the coded subroutine UHYPER, this work may provide a numerical tool to study complex phenomena in hydrogels.     

A theory of coupled diffusion and large deformation in polymeric gels

A large quantity of small molecules may migrate into a network of long polymers, causing the network to swell, forming an aggregate known as a polymeric gel. This paper formulates a theory of the coupled mass transport and large deformation. The free energy of the gel results from two molecular processes: stretching the network and mixing the network with the small molecules. Both the small molecules and the long polymers are taken to be incompressible, a constraint that we enforce by using a Lagrange multiplier, which coincides with the osmosis pressure or the swelling stress. The gel can undergo large deformation of two modes. The first mode results from the fast process of local rearrangement of molecules, allowing the gel to change shape but not volume. The second mode results from the slow process of long-range migration of the small molecules, allowing the gel to change both shape and volume. We assume that the local rearrangement is instantaneous, and model the long-range migration by assuming that the small molecules diffuse inside the gel. The theory is illustrated with a layer of a gel constrained in its plane and subject to a weight in the normal direction. We also predict the scaling behavior of a gel under a conical indenter.     

Characterization of polyacrylamide gels as an elastic model for food gels

Serving as an elastic model system for food gels, characteristics of polyacrylamide (PAAm) gels were investigated using small amplitude and large deformation rheological tests. The PAAm gels displayed elastic or viscoelastic behavior depending on network crosslink density. For elastic PAAm gels, the rheological properties obeyed the theory of rubber elasticity; whereas for viscoelastic PAAm gels, shear modulus depended on temperature. The elastic PAAm gel fracture parameters did not change with deformation rate (0.2–5.5 s^–1), indicating insignificant viscous flow during deformation. Fracture stress was correlated with gel monomer concentration, whereas the fracture strain remained constant regardless of the monomer concentration. In addition, the stress was linearly proportioned with strain up to fracture, indicating that PAAm gels did not experience finite network chain extensibility during large deformation. Consequently, the fracture of PAAm gels did not result from the extensional limitation of network chains, nor did gel fracture result from the nonlinear force–distance relationship between polymer connections. Purportedly, the fracture of PAAm gels was caused by external force overcoming the gel cohesive forces, and low strength of PAAm gels compared to rubbers caused fracture prior to experiencing nonlinear stress-strain deformation.Paper No. FSR04-20 of the Journal Series of the North Carolina Agricultural Research Service, Raleigh, NC 27695-7643. The use of trade names does not imply endorsement by the North Carolina Agricultural Research Service of products named, nor criticisms of similar ones not mentioned.     

Molecular simulation guided constitutive modeling on finite strain viscoelasticity of elastomers

Viscoelasticity characterizes the most important mechanical behavior of elastomers. Understanding the viscoelasticity, especially finite strain viscoelasticity, of elastomers is the key for continuation of their dedicated use in industrial applications. In this work, we present a mechanistic and physics-based constitutive model to describe and design the finite strain viscoelastic behavior of elastomers. Mathematically, the viscoelasticity of elastomers has been decomposed into hyperelastic and viscous parts, which are attributed to the nonlinear deformation of the cross-linked polymer network and the diffusion of free chains, respectively. The hyperelastic deformation of a cross-linked polymer network is governed by the cross-linking density, the molecular weight of the polymer strands between cross-linkages, and the amount of entanglements between different chains, which we observe through large scale molecular dynamics (MD) simulations. Moreover, a recently developed non-affine network model (Davidson and Goulbourne, 2013) is confirmed in the current work to be able to capture these key physical mechanisms using MD simulation. The energy dissipation during a loading and unloading process of elastomers is governed by the diffusion of free chains, which can be understood through their reptation dynamics. The viscous stress can be formulated using the classical tube model (Doi and Edwards, 1986); however, it cannot be used to capture the energy dissipation during finite deformation. By considering the tube deformation during this process, as observed from the MD simulations, we propose a modified tube model to account for the finite deformation behavior of free chains. Combing the non-affine network model for hyperelasticity and modified tube model for viscosity, both understood by molecular simulations, we develop a mechanism-based constitutive model for finite strain viscoelasticity of elastomers. All the parameters in the proposed constitutive model have physical meanings, which are signatures of polymer chemistry, physics or dynamics. Therefore, parametric materials design concepts can be easily gleaned from the model, which is also demonstrated in this study. The finite strain viscoelasticity obtained from our simulations agrees qualitatively with experimental data on both un-vulcanized and vulcanized rubbers, which captures the effects of cross-linking density, the molecular weight of the polymer chain and the strain rate.     

A thermo-mechanically coupled theory for fluid permeation in elastomeric materials: Application to thermally responsive gels

An elastomeric gel is a cross-linked polymer network swollen with a solvent, and certain gels can undergo large reversible volume changes as they are cycled about a critical temperature. We have developed a continuum-level theory to describe the coupled mechanical deformation, fluid permeation, and heat transfer of such thermally responsive gels. In discussing special constitutive equations we limit our attention to isotropic materials, and consider a model based on a Flory–Huggins model for the free energy change due to mixing of the fluid with the polymer network, coupled with a non-Gaussian statistical–mechanical model for the change in configurational entropy—a model which accounts for the limited extensibility of polymer chains. We have numerically implemented our theory in a finite element program. We show that our theory is capable of simulating swelling, squeezing of fluid by applied mechanical forces, and thermally responsive swelling/de-swelling of such materials.     

A theory of amorphous solids undergoing large deformations,with application to polymeric glasses

This paper develops a continuum theory for the elastic–viscoplastic deformation of amorphous solids such as polymeric and metallic glasses. Introducing an internal-state variable that represents the local free-volume associated with certain metastable states, we are able to capture the highly non-linear stress–strain behavior that precedes the yield-peak and gives rise to post-yield strain softening. Our theory explicitly accounts for the dependence of the Helmholtz free energy on the plastic deformation in a thermodynamically consistent manner. This dependence leads directly to a backstress in the underlying flow rule, and allows us to model the rapid strain-hardening response after the initial yield-drop in monotonic deformations, as well as the Bauschinger-type reverse-yielding phenomena typically observed in amorphous polymeric solids upon unloading after large plastic deformations. We have implemented a special set of constitutive equations resulting from the general theory in a finite-element computer program. Using this finite-element program, we apply the specialized equations to model the large-deformation response of the amorphous polymeric solid polycarbonate, at ambient temperature and pressure. We show numerical results to some representative problems, and compare them against corresponding results from physical experiments.     

DYNAMIC MODEL OF SELF-OSCILLATING GELS AND THE CONTROLLABILITY ANALYSIS

自振荡凝胶是一类在Belousov-Zhabotinsky化学反应（BZ反应）驱动下能够产生周期性收缩和膨胀大变形的智能软材料,简称为BZ凝胶,在微型激励器、传感器、药物释放、仿生材料等领域有着广泛的应用前景。基于BZ化学反应的Oregonator模型以及凝胶变形的力平衡方程,建立了由二阶微分方程表示的BZ凝胶的简化动力学模型,并通过对BZ凝胶的振荡动力学模型的分析,发现其在动力学相轨迹空间内呈现出稳定的周期性极限环振荡,进而利用改进的打靶法求得了BZ凝胶的振荡周期解,系统研究了反应物浓度、催化剂效率和链状高分子的亲水性等可控系统参数对其振荡形式、周期和幅值的影响。结果表明,只有在特定的系统参数取值下,BZ凝胶才能发生持续的周期性振荡;随着这些参数的改变,BZ凝胶的振荡形式、周期和幅值均产生规律性变化。证明了对自振荡凝胶实施周期性调控在理论上是可行的。     

网链缠结对凝胶薄膜起皱的影响

凝胶薄膜在变形时易发生屈曲、起皱等失稳现象,这在凝胶薄膜的应用中是非常重要的．近年来,针对凝胶薄膜的屈曲、起皱失稳行为,越来越多的科研人员尝试从力学角度进行分析．但是大多数的研究是基于Flory-Rehner弹性凝胶理论,未考虑凝胶网链缠结引起的物理交联对凝胶自由能的影响,模型精度不高．本文采用Edwards-Vilgis所提出的Slip-link模型对平面内起皱的凝胶薄膜进行分析,研究了不伸展参数、滑移参数对聚合物凝胶增量模量的影响以及不伸展参数、滑移参数、基底材料泊松比对凝胶薄膜起皱时的临界波长和临界应力的影响．结果表明：化学势在一定范围内变化时,随着化学势的增加,增量模量、临界波长、临界应力减小;不可伸长参数越大,增量模量、临界波长及临界应力越大;滑移参数越大,增量模量、临界波长及临界应力越小．     

Mechanics of inhomogeneous large deformation of photo-thermal sensitive hydrogels

A polymer network can imbibe copious amounts of solvent and swell, the resulting state is known as a gel. Depending on its constituents, a gel is able to deform under the influence of various external stimuli, such as temperature, pH-value and light. In this work, we investigate the photo-thermal mechanics of deformation of temperature sensitive hydrogels impregnated with light-absorbing nano-particles. The field theory of photo-thermal sensitive gels is developed by incorporating effects of photochemical heating into the thermodynamic theory of neutral and temperature sensitive hydrogels. This is achieved by considering the equilibrium thermodynamics of a swelling gel through a variational approach. The phase transition phenomenon of these gels, and the factors affecting their deformations, are studied. To facilitate the simulation of large inhomogeneous deformations subjected to geometrical constraints, a finite element model is developed using a user-defined subroutine in ABAQUS, and by modeling the gel as a hyperelastic material. This numerical approach is validated through case studies involving gels undergoing phase coexistence and buckling when exposed to irradiation of varying intensities, and as a microvalve in microfluidic application.     

Modeling of the pH-sensitive behavior of an ionic gel in the presence of diffusion

In this paper, we develop a model for swelling of an ionic gel in a solvent of varying pH and diffusion of the solvent through the swollen gel by applying a variational method originally presented by Baek and Srinivasa (Int. J. Nonlinear Mech. 39 (2004) 201). The approach presented here, based on the balance laws of a single continuum with mass diffusion and ionic chemical reactions, delivers system equations and boundary conditions by assuming two constitutive scalar functions for the free energy of the system and the rate of dissipation, instead of assuming osmotic pressure, electrostatic repulsive force, etc. In the equilibrium case, the model describes pH-dependent behavior and the effect of other counterions on the swelling of ionic gels. In the non-equilibrium case, it accounts for the pH-dependent mass flux through ionic gels. Moreover, the model shows that the mass flux can be induced by the gradient of chemical potential, the concentration of the mobile species and ionic charges. This model is applied to a typical carboxylated copolymer gel, and compared with an experiment for equilibrium swelling, and predicts the pH-dependence for a pressure-induced mass flux.     

A coupled theory of fluid permeation and large deformations for elastomeric materials

An elastomeric gel is a cross-linked polymer network swollen with a solvent (fluid). A continuum-mechanical theory to describe the various coupled aspects of fluid permeation and large deformations (e.g., swelling and squeezing) of elastomeric gels is formulated. The basic mechanical force balance laws and the balance law for the fluid content are reviewed, and the constitutive theory that we develop is consistent with modern treatments of continuum thermodynamics, and material frame-indifference. In discussing special constitutive equations we limit our attention to isotropic materials, and consider a model for the free energy based on a Flory-Huggins model for the free energy change due to mixing of the fluid with the polymer network, coupled with a non-Gaussian statistical-mechanical model for the change in configurational entropy—a model which accounts for the limited extensibility of polymer chains. As representative examples of application of the theory, we study (a) three-dimensional swelling-equilibrium of an elastomeric gel in an unconstrained, stress-free state; and (b) the following one-dimensional transient problems: (i) free-swelling of a gel; (ii) consolidation of an already swollen gel; and (iii) pressure-difference-driven diffusion of organic solvents across elastomeric membranes.     

Yielding characterization of waxy gels by energy dissipation

The rheological behaviors of yield stress fluids are commonly interpreted from the energy perspective, yet this perspective has rarely been applied for waxy gel. In this study, we calculated the energy dissipated into the waxy gel caused by viscous strain during the deformation process with the aid of a well-tested elasto-viscoplastic thixotropic model. The energy dissipation shows a power-law dependence on the strain regardless of the stress ramping rate. The energy dissipation has been shown to be useful to characterize the ductility of waxy gel, that is, the larger the energy is dissipated during fracture, the more ductile the waxy gel is. When the waxy gel is induced to the same strain by different stress ramping rate, the energy dissipation during the deformation process shows little dependence on the stress ramping rate. However, if during the loading process the stress is increased to the same value by different ramping rate, a higher stress ramping rate causes lower energy dissipation. These findings are helpful to elucidate the widely observed experimental observation for waxy gels that the measured yield stress depends on the stress ramping rate whereas the measured yield strain shows little dependence.     

The “decaying springs” model for irreversibility in polymer melts

In this work, entanglements in a polymer melt are modeled as a system of parallel springs which form and decay spontaneously. The springs are assumed to be nonlinear, and a certain fraction of them is torn apart by a certain strain.Based on these assumptions, a model of behavior in simple shear is developed. This model is shown to predict a behavior comprising that of a Wagner fluid, and is generalized to a tensorial model of single integral type. The integrand depends on a product of a material function, modeling reversible behavior, and a material functional which takes irreversible processes into account.Irreversibility of network disentanglement, which may occur when deformation changes or reverses direction, can be modeled in this way. It is shown that the two well-known Wagner constitutive equations with and without irreversibility assumptions are special cases of the model developed. In case of a deformation which does not change directions, the new material function and the material functional are multiplied to yield Wagner's damping function.When the rate of spring formation is a function of temperature, the developed model is shown to predict thermorheologically simple behavior. A constitutive equation for non-isothermal flow of polymers is developed with this assumption.     

The effect of large deformation and material nonlinearity on gel indentation

A gel, an aggregate of polymers with solvents, has dual attributes of solid and liquid as solvent migrates in and out of the polymer network. Indentation has recently been used to characterize the mechanical properties of gels. This paper evaluates the effects of large deformation and material nonlinearity on gel indentation through theoretical modeling and finite element analysis. It is found that large deformation significantly affects the interpretation of the experimental observations and the classical relation between indentation force and depth has limitations for large deformation. The material nonlinearity does not play a very important role on indentation experiment so that the poroelasticity is a good approximation. Based on these observations, this paper proposes an alternative approach to measure the mechanical properties of gels, namely, uniaxial compression experiment.     

Spatial representation of evolving anisotropy at large strains

A phenomenological model for evolving anisotropy at large strains is presented. The model is formulated using spatial quantities and the anisotropic properties of the material is modeled by including structural variables. Evolution of anisotropy is accounted for by introducing substructural deformation gradients which are linear maps similar to the usual deformation gradient. The evolution of the substructural deformation gradients is governed by the substructural plastic velocity gradients in a manner similar to that for the continuum. Certain topics related to the numerical implementation are discussed and a simple integration scheme for the local constitutive equations is developed. To demonstrate the capabilities of the model it is implemented into a finite element code. Two numerical examples are considered: deformation of uniform plate with circular hole and the drawing of a cup. In the two examples it is assumed that initial cubic material symmetry applies to both the elastic and plastic behavior. To be specific, a polyconvex Helmholtz free energy function together with a yield function of quadratic type is adopted.     

Constitutive equations for non-affine polymer networks with slippage of chains

A model is derived for isothermal three-dimensional deformation of polymers with finite strains. A polymer fluid is treated as a permanent network of chains bridged by junctions (entanglements). Macro-deformation of the medium induces two motions at the micro-level: (i) sliding of junctions with respect to their reference positions that reflects non-affine deformation of the network, and (ii) slippage of chains with respect to entanglements that is associated with unfolding of back-loops. Constitutive equations are developed by using the laws of thermodynamics. Three important features characterize the model: (i) the symmetry of relations between the elongation of strands and an appropriate configurational tensor, (ii) the strong nonlinearity of the governing equations, and (iii) the account for the volumetric deformation of the network induced by stretching of chains. The governing equations are applied to the numerical analysis of extensional and shear flows. It is demonstrated that the model adequately describes the time-dependent response of polymer melts observed in conventional rheological tests.     

Micromechanics and macromechanics of carbon nanotube-enhanced elastomers

The effects of carbon nanotubes on the mechanical behavior of elastomeric materials is investigated. The large deformation uniaxial tension and uniaxial compression stress-strain behaviors of a representative elastomer are first presented. This elastomer is then reinforced with multi-wall carbon nanotubes (MWNTs) and the influence of weight fraction of MWNTs on the large deformation behavior of the resulting composite is quantified. The initial stiffness and subsequent strain-induced stiffening at large strains are both found to increase with MWNT content. The MWNTs are also found to increase both the tensile strength and the tensile stretch at break. A systematic approach for reducing the experimental data to isolate the MWNT contribution to the strain energy of the composite is presented. A constitutive model for the large strain deformation behavior of MWNT-elastomer composites is then developed. The effects of carbon nanotubes are modeled via a constitutive element which tracks the stretching and rotation of a distribution of wavy carbon nanotubes. The MWNT strain energy contribution is due to the bending/unbending of the initial waviness and provides the increase in initial stiffness as well as the retention and further enhancement of the increase in stiffness with large strains. The model is shown to track the stretching and rotation of the CNTs with macroscopic strain as well as predict the dependence of the macroscopic stress-strain behavior on the MWNT content for both uniaxial tension and uniaxial compression.