The viscoelastic and viscoplastic behavior of low-density polyethylene

Three series of tensile tests with constant cross-head speeds (ranging from 5 to 200 mm/min), tensile relaxation tests (at strains from 0.03 to 0.09) and tensile creep tests (at stresses from 2.0 to 6.0 MPa) are performed on low-density polyethylene at room temperature. Constitutive equations are derived for the time-dependent response of semicrystalline polymers at isothermal deformation with small strains. A polymer is treated as an equivalent heterogeneous network of chains bridged by temporary junctions (entanglements, physical cross-links and lamellar blocks). The network is thought of as an ensemble of meso-regions linked with each other. The viscoelastic behavior of a polymer is modelled as thermally-induced rearrangement of strands (separation of active strands from temporary junctions and merging of dangling strands with the network). The viscoplastic response reflects mutual displacement of meso-domains driven by macro-strains. Stress–strain relations for uniaxial deformation are developed by using the laws of thermodynamics. The governing equations involve five material constants that are found by fitting the observations. Fair agreement is demonstrated between the experimental data and the results of numerical simulation. It is shown that observations in conventional creep tests reflect not only the viscoelastic, but also the viscoplastic behavior of an ensemble of meso-regions.     

Constitutive equations in finite viscoplasticity of semicrystalline polymers

Three series of uniaxial tensile tests with constant strain rates are performed at room temperature on isotactic polypropylene and two commercial grades of low-density polyethylene with different molecular weights. Constitutive equations are derived for the viscoplastic behavior of semicrystalline polymers at finite strains. A polymer is treated as an equivalent network of strands bridged by permanent junctions. Two types of junctions are introduced: affine whose micro-deformation coincides with the macro-deformation of a polymer, and non-affine that slide with respect to their reference positions. The elastic response of the network is attributed to elongation of strands, whereas its viscoplastic behavior is associated with sliding of junctions. The rate of sliding is proportional to the average stress in strands linked to non-affine junctions. Stress–strain relations in finite viscoplasticity of semicrystalline polymers are developed by using the laws of thermodynamics. The constitutive equations are applied to the analysis of uniaxial tension, uniaxial compression and simple shear of an incompressible medium. These relations involve three adjustable parameters that are found by fitting the experimental data. Fair agreement is demonstrated between the observations and the results of numerical simulation. It is revealed that the viscoplastic response of low-density polyethylene in simple shear is strongly affected by its molecular weight.     

Modeling the response of filled elastomers at finite strains by rigid-rod networks

Summary  A constitutive model is developed for the isothermal response of particle-reinforced elastomers at finite strains. An amorphous rubbery polymer is treated as a network of long chains bridged to permanent junctions. A strand between two neighboring junctions is thought of as a sequence of rigid segments connected by bonds. In the stress-free state, a bond may be in one of two stable conformations: flexed and extended. The mechanical energy of a bond in the flexed conformation is treated as a quadratic function of the local strain, whereas that of a bond in the extended conformation is neglected. An explicit expression is developed for the free energy of a network. Stress–strain relations and kinetic equations for the concentrations of bonds in various conformations are derived using the laws of thermodynamics. In the case of small strains, these relations are reduced to the constitutive equation for the standard viscoelastic solid. At finite strains, the governing equations are determined by four adjustable parameters which are found by fitting experimental data in uniaxial tensile, compressive and cyclic tests. Fair agreement is demonstrated between the observations for several filled and unfilled rubbery polymers and the results of numerical simulation. We discuss the effects of the straining state, filler content, crosslink density and temperature on the adjustable constants. Received 3 January 2001; accepted for publication 12 July 2001     

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.     

The effect of temperature on the viscoelastic behavior of linear low-density polyethylene

Summary Observations are reported on linear low-density polyethylene in isothermal torsional oscillation and relaxation tests at various temperatures ranging from room temperature to 110 C. Constitutive equations are derived for the viscoelastic response of a semicrystalline polymer at small strains. The polymer is treated as an equivalent network of strands bridged by junctions (entanglements, physical cross-links on the surfaces of crystallites and lamellar blocks). The network is thought of as an ensemble of meso-regions with various potential energies for rearrangement of strands. Two types of meso-domains are introduced: active, where strands separate from temporary junctions as they are excited by thermal fluctuations, and passive, where detachment of strands is prevented by the surrounding macromolecules. The time-dependent behavior of the ensemble reflects separation of active strands from their junctions and merging of dangling strands with the network. Stress–strain relations are developed by using the laws of thermodynamics. The governing equations involve six material constants that are found by fitting the experimental data. The study focuses on the effects of (i) temperature, (ii) the deformation mode (torsion versus bending), and (iii) the loading program (oscillations versus relaxation) on the adjustable parameters.This work was partially supported by the West Virginia Research Challenge Grant Program     

Constitutive equations in finite elasticity of rubbers

A constitutive model is derived for the elastic behavior of rubbers at arbitrary three-dimensional deformations with finite strains. An elastomer is thought of as an incompressible network of flexible chains bridged by permanent junctions that move affinely with the bulk material. With reference to the concept of constrained junctions, the chain ends are assumed to be located at some distances from appropriate junctions. These distances are not fixed, but are altered under deformation. An explicit expression is developed for the distribution function of vectors between junctions (an analog of the end-to-end distribution function for a flexible chain with fixed ends). An analytical formula is obtained for the strain energy density of a polymer network, when the ratio of the mean-square distance between the ends of a chain and appropriate junctions is small compared with the mean-square end-to-end distance of chains. Stress–strain relations are derived by using the laws of thermodynamics. The governing equations involve three adjustable parameters with transparent physical meaning. These parameters are found by fitting experimental data on plain and particle-reinforced elastomers. The model ensures good agreement between the observations at uniaxial tension and the results of numerical simulation, as well as an acceptable prediction of stresses at uniaxial compression, simple shear and pure shear, when its parameters are found by matching observations at uniaxial tensile tests.     

The effect of annealing on the viscoplastic response of semicrystalline polymers at finite strains

A constitutive model is developed for the viscoplastic behavior of a semicrystalline polymer at finite strains. A solid polymer is treated as an equivalent heterogeneous network of chains bridged by permanent junctions (physical cross-links, entanglements and lamellar blocks). The network is thought of as an ensemble of meso-regions linked with each other. In the sub-yield region of deformations, junctions between chains in meso-domains slide with respect to their reference positions (which reflects sliding of nodes in the amorphous phase and fine slip of lamellar blocks). Above the yield point, this sliding process is accompanied by displacements of meso-domains in the ensemble with respect to each other (which reflects coarse slip and disintegration of lamellar blocks). To account for the orientation of lamellar blocks in the direction of maximal stresses and formation of micro-fibrils in the post-yield region of deformations (which is observed as strain-hardening of specimens) elastic moduli are assumed to depend on the principal invariants of the right Cauchy–Green tensor for the viscoplastic flow. Stress–strain relations for a semicrystalline polymer are derived by using the laws of thermodynamics. The constitutive equations are determined by six adjustable parameters that are found by matching observations in uniaxial tensile tests on injection-molded isotactic polypropylene at elongations up to 80%. Prior to testing, the specimens were annealed at various temperatures ranging from 110 to 163 °C. Fair agreement is demonstrated between the experimental data and the results of numerical simulation. The effect of annealing temperature on the material parameters is studied in detail.     

A Constitutive Model in Finite Viscoelasticity of Particle-reinforced Rubbers

Two series of tensile relaxation tests are performed on natural rubber filled with high abrasion furnace black. To fit observations, constitutive equations are derived for the nonlinear viscoelastic behavior of a particle-reinforced elastomer. A filled rubber is modeled as a composite medium, where inclusions with low concentrations of junctions are randomly distributed in the host matrix. The inclusions are treated as equivalent networks of macromolecules, where strands can separate from temporary junctions as they are thermally agitated. The bulk medium is thought of as a permanent network of chains. Unlike conventional concepts of transient networks, the concentration of strands in inclusions is assumed to be affected by mechanical factors: under active loading, inter-chain interactions weaken and some strands that were prevented from detachment from their junctions in a stress-free compound become free to separate from the junctions in a deformed medium. Unloading strengthens interactions between macromolecules, which results in an increase in the number of permanent strands. By using the laws of thermodynamics, stress–strain relations for a particle-reinforced rubber are developed. Adjustable parameters in the constitutive equations are found by fitting the experimental data. It is demonstrated that mechanical pre-loading and annealing of specimens at an elevated temperature noticeably affect concentrations of inclusions with various activation energies for rearrangement of strands.     

Finite viscoplasticity of non-affine networks: stress overshoot under shear

A constitutive model is derived for the viscoplastic behavior of polymers at finite strains. A polymer is treated as an equivalent network of chains bridged by permanent junctions. The elastic response of the network is attributed to elongation of strands, whereas its plastic behavior is associated with sliding of junctions with respect to their reference positions. A new kinetic equation is proposed that expresses the rate of sliding of junctions in terms of the Cauchy stress tensor. Constitutive equations for an equivalent non-affine network are developed by using the laws of thermodynamics, where internal dissipation of energy reflects two processes at the micro-level: sliding of chains along entanglements and friction of strands between junctions. A similarity is revealed between these relations and the pom-pom model. The governing equations are applied to study stress overshoot at simple shear of an incompressible medium. Adjustable parameters in the stress-strain relations are found by fitting experimental data on polycarbonate melt reinforced with short glass fibers and polystyrene solution. Fair agreement is demonstrated between the observations and the results of numerical simulation.Received: 6 January 2003, Accepted: 28 April 2003     

A micro-mechanical model for the response of filled elastomers at finite strains

Constitutive equations are developed for the isothermal response of particle-reinforced elastomers at finite strains. A rubbery polymer is treated as a network of chains bridged by junctions. A strand between two junctions is thought of as a series of inextensible segments linked by bonds. Two stable conformations are ascribed to a bond: flexed and extended. Deformation of a specimen induces transition of bonds from their flexed conformation to the extended conformation. A concept of trapped entanglements is adopted, according to which not all junctions are active in the stress-free state. Under straining, some entanglements are transformed from their passive (dangling) state to the active state, which results in a decrease in the average length of a strand. Stress–strain relations for an elastomer and kinetic equations for the rate of transition of bonds from their flexed conformation to the extended conformation are derived by using the laws of thermodynamics. Simple phenomenological equations are suggested for the evolution of the number of active entanglements. The model is determined by five adjustable parameters which are found by fitting experimental data in uniaxial tensile tests. Fair agreement is demonstrated between the results of numerical simulation and observations for a polysulfide elastomer reinforced with polystyrene particles and two natural rubber vulcanizates with different cross-linkers.     

Polymer Networks with Slip-links: 2. Constitutive Equations for a Cross-linked Network

Stress–strain relations are derived for the mechanical response of elastomers at arbitrary three-dimensional deformations with finite strains. An elastomer is treated as an incompressible network of chains bridged by permanent (chemical cross-links and physical cross-links whose lifetime exceeds the characteristic time of deformation) and temporary (entanglements modeled as slip-links) junctions. Two types of chains are introduced in the network to distinguish between permanent and temporary nodes. Type-I chains have free ends, and their motion at the micro-level is constrained by a random number of slip-links. Type-II chains are Gaussian chains permanently connected to the network. Concentration of type-I chains is fixed, while the number of type-II chains per unit volume can change under deformation. The governing equations involve two (networks with constant concentrations of type-II chains) or three (networks where the content of type-II chains is affected by mechanical factors) material parameters. These parameters are found by fitting observations on rubbers, thermoplastic–elastomers, and thermoplastic-elastomer composites. Good agreement is demonstrated between the experimental data in uniaxial tensile tests and the results of numerical simulation at elongations up to 1,000%. It is shown that the adjustable parameters are affected by chemical composition and molecular architecture of polymers in a physically plausible way.     

Finite viscoelasticity of filled rubber: experiments and numerical simulation

Summary  Constitutive equations are derived for the viscoelastic behavior of particle-re-inforced elastomers at isothermal deformation with finite strain. A filled rubber is thought of as a composite medium where inclusions with high and low concentrations of junctions between chains are randomly distributed in the bulk material. The characteristic length of the inhomogeneities is assumed to be small compared to the size of the specimen and substantially exceed the radius of gyration for macromolecules. Inclusions with high concentration of junctions are associated with regions of suppressed mobility of chains that surround isolated clusters and/or the secondary network of filler. Regions with low concentration of junctions arise during the preparation process due to a heterogeneity in the spatial distribution of the cross-linker and the filler. With reference to the concept of transient networks, the time-dependent response of an elastomer is attribute d to thermally activated rearrangement of strands in the domains with low concentration of junctions. Stress–strain relations for particle-reinforced rubber are developed by using the laws of thermodynamics. Adjustable parameters in the constitutive equations are found by fitting experimental data in tensile relaxation tests for several grades of unfilled and carbon black-filled rubber. It is demonstrated that even at moderate finite deformations (with axial elongations up to 100%), the characteristic rate of relaxation is noticeably affected by strain. Unlike glassy polymers, where the rate of relaxation increases with longitudinal strain, the growth of the elongation ratio results in a decrease in the relaxation rate for natural rubber (unfilled or particle-reinforced). The latter may be explained by (partial) crystallization of chains in the regions with low concentration of junctions. Received 16 October 2001; accepted for publication 25 June 2002 Present address: A. D. Drozdov Department of Production, Aalborg University, Fibigerstraede 16, DK-9220 Aalborg, Denmark We would like to express our gratitude to Dr. K. Fuller (TARRC, UK) for providing us with rubber specimens and to Prof. P. Haupt and Dr. S. Hartmann (University of Kassel, Germany) for sending their experimental data. We are indebted to Mr. G. Seifritz for his assistance in performing mechanical tests. ADD acknowledges stimulating discussions with Prof. N. Aksel (University of Bayreuth, Germany).     

The nonlinear viscoelastic response of carbon black-filled natural rubbers

Three series of tensile relaxation tests are performed on natural rubber filled with various amounts of carbon black. The elongation ratio varies in the range from λ=2.0 to 3.5. Constitutive equations are derived for the nonlinear viscoelastic behavior of filled elastomers. Applying a homogenization method, we model a particle-reinforced rubber as a transient network of macromolecules bridged by junctions (physical and chemical cross-links, entanglements and filler clusters). The network is assumed to be strongly heterogeneous at the meso-level: it consists of passive regions, where rearrangement of chains is prevented by surrounding macromolecules and filler particles, and active domains, where active chains separate from temporary nodes and dangling chains merge with the network as they are thermally agitated. The rate of rearrangement obeys the Eyring equation, where different active meso-domains are characterized by different activation energies. Stress–strain relations for a particle-reinforced elastomer are derived by using the laws of thermodynamics. Adjustable parameters in the constitutive equations are found by fitting experimental data. It is demonstrated that the filler content strongly affects the rearrangement process: the attempt rate for separation of strands from temporary nodes increases with elongation ratio at low fractions of carbon black (below the percolation threshold) and decreases with λ at high concentrations of filler.     

Modelling the viscoplastic response of polyethylene in uniaxial loading–unloading tests

Two series of uniaxial cyclic tests are performed on low-density polyethylene at room temperature. In the first series of experiments, injection-molded specimens are stretched to several maximal strains ε_max in the region of sub-yield deformations with a constant cross-head speed, mm/min, and retracted down to the zero stress with the same strain rate. In the other series, loading–unloading tests are carried out with the maximal strain ε_max=0.10 and cross-head speeds ranging from 5 to 200 mm/min. A constitutive model is derived for the viscoplastic behavior of a semicrystalline polymer at small strains. A polymer is modelled as an equivalent network of chains bridged by permanent junctions (entanglements, physical cross-links on the surfaces of crystallites and lamellar blocks). The network is treated as an ensemble of meso-regions connected by links (crystalline lamellae). Deformation of a specimen induces sliding of junctions with respect to their reference positions both at active loading and unloading (this process reflects sliding of junctions in amorphous regions and fine slip of crystalline lamellae). At retraction, sliding of junctions is accompanied by mutual displacements of meso-domains (that reflects coarse slip and fragmentation of lamellar blocks). The constitutive equations are determined by 5 adjustable parameters that are found by matching the experimental stress–strain curves.     

The viscoelastic behavior of melts of virgin and recycled polycarbonate reinforced with short glass fibers

Three series of shear oscillatory tests are performed on polycarbonate melts reinforced with short glass fibers at the temperatures T₁=250 and T₂=290 °C. The content of glass fibers ranges from 0 to 20 wt.%. In the first series, virgin polycarbonate is used, in the other series, dynamic tests are performed on recycled polymer, whereas in the third series, a mixture of virgin with recycled polycarbonates is employed. Constitutive equations are derived for the viscoelastic behavior of a polymer melt at isothermal deformations with small strains. A polymer is treated as an equivalent transient network of strands that rearrange at random times as they are agitated by thermal fluctuations. The time-dependent response of a network is determined by four adjustable parameters that are found by fitting the experimental data. Excellent agreement is demonstrated between the observations and the results of numerical simulation. The study focuses on the effects of temperature and filler content on the material constants in the stress–strain relations.     

Cyclic viscoelastoplasticity and low-cycle fatigue of polymer composites

Observations are reported on a polymer composite (polyamide-6 reinforced with short glass fibers) in tensile relaxation tests with various strains, tensile creep tests with various stresses, and cyclic tests with a stress-controlled program (ratcheting with a fixed maximum stress and various minimum stresses). Constitutive equations are developed in cyclic viscoelastoplasticity of polymer composites. Adjustable parameters in the stress–strain relations are found by fitting observations in relaxation tests and cyclic tests (16 cycles of loading–unloading). It is demonstrated that the model correctly predicts experimental data in creep tests and dependencies of maximum and minimum strains per cycle on number of cycles up to fatigue fracture of specimens. The influence of strain rate and minimum stress on number of cycles to failure is studied numerically.     

Stress–strain relations for hydrogels under multiaxial deformation

Constitutive equations are derived for the elastic response of swollen elastomers and hydrogels under an arbitrary deformation with finite strains. An expression is developed for the free energy density of a polymer network based on the Flory concept of flexible chains with constrained junctions and solvent-dependent reference configuration. The importance of introduction of a reference configuration evolving under swelling is confirmed by the analysis of experimental data on nanocomposite hydrogels subjected to swelling and drying. Adjustable parameters in the stress–strain relations are found by fitting observations on swollen elastomers, chemical gels (linked by covalent bonds and sliding cross-links), and physical gels under uniaxial stretching, equi-biaxial tension, and pure shear. Good agreement is demonstrated between the observations and results of numerical simulation. A pronounced difference is revealed between the effect of solvent content on elastic moduli of chemical and physical gels.     

Polymer Networks with Slip-links: 1. Constitutive Equations for an Uncross-linked Network

Constitutive equations are derived for the mechanical response of polymers at three-dimensional deformations with finite strains. A polymer is treated as an incompressible network of flexible chains with free ends whose motion at the micro-level is constrained by a random number of slip-links. The slip-links move affinely with macro-deformation, whereas chains can slide with respect to slip-links. When a free end of a chain slides through a slip-link, the slip-link disappears. Stress–strain relations are developed by using the laws of thermodynamics. They involve only one material constant with a transparent physical meaning.     

Viscoelasticity and viscoplasticity of polypropylene/polyethylene blends

Observations are reported on polypropylene/polyethylene blends with various concentrations of components in uniaxial tensile tests with constant strain rates, relaxation tests, and creep tests at room temperature. A model is developed for the viscoelastic and viscoplastic responses of polymer blends at arbitrary three-dimensional deformation with small strains. Material constants in the constitutive equations are determined by fitting the experimental data. It is found that all adjustable parameters evolve with blend composition following an analog of the rule of mixture. Lifetime of blends under condition of creep rupture is evaluated by numerical simulation.     

A theory for large deformation and damage of interpenetrating polymer networks

Elastomers and gels can be formed by interpenetrating two polymer networks on a molecular scale. This paper develops a theory to characterize the large deformation and damage of interpenetrating polymer networks. The theory integrates an interpenetrating network model with the network alteration theory. The interpenetration of one network stretches polymer chains in the other network and reduces its chain density, significantly affecting the initial modulus, stiffening and damage properties of the resultant elastomers and gels. Double-network hydrogels, a special type of interpenetrating polymer network, have demonstrated intriguing mechanical properties including high fracture toughness, Mullins effects, and necking instability. These properties have been qualitatively attributed to the damage of polymer networks. Using the theory, we quantitatively illustrate how the interplay between polymer-chain stiffening and damage-induced softening can cause the Mullins effect and necking instability. The theory is further implemented into a finite-element model to simulate the initiation and propagation of necking instability in double-network hydrogels. The theoretical and numerical results are compared with experimental data from multiple cyclic compressive and tensile tests.