Relaxational interactions and viscoelasticity of polymer melts: Part II. Rheological properties in shear and elongational flows

The rheological equation of state derived in Part I on the basis of relaxation equations of chain dynamics is analyzed for the steady and transient shear and uniaxial elongational flows of monodisperse polymers. The effect of superslow relaxation processes associated with basic macro-molecular motions that occur on a characteristic scale essentially greater than the so-called distance between entanglements was investigated in these flows. It is shown that the relaxation times in the region of linear and non-linear viscoelasticity are self-consistent. Theoretical predictions are in good agreement with the experimental data for melts of nearly monodisperse flexible polymers.     

Relaxation and viscoelastic properties of complex polymer systems

Dynamic behavior of various polymer melts is studied on the basis of a comparison of viscoelastic properties with the information obtained from dielectric spectroscopy. The experimental observations are compared with results of computer simulation of corresponding systems. The studies include simple melts of linear chains, block copolymer systems of miscible components, as well as the behavior of melts with molecular objects of complex topology-like stars or microgels. In the case of polyisoprene linear chain melts an equivalence of terminal relaxation times determined from mechanical and dielectric measurements is demonstrated. Using linear block copolymers of isoprene and butadiene, relaxation times of chain fragments (isoprene blocks) in relation to relaxation times of whole copolymer chains are determined and compared with theory and simulation. Both the experimentally determined block relaxation times and relaxation times of chain fragments in simulated linear chain melts show a disagreement with predictions of the reptation theory. In the case of multiarm star polymers and microgel melts, the slow relaxation modes observed in viscoelastic spectra are assigned to cooperative translational motions detected in corresponding simulated systems in which an ordering of such molecules is demonstrated. This suggests that the terminal relaxation in multiarm star or microgel melts is governed by another relaxation mechanism than in linear chain melts. High efficiency of the Cooperative Motion Algorithm in simulation of dense systems of complex molecules is demonstrated.Dedicated to the memory of Professor Tasos C. Papanastasiou     

Theory of dilute polymer solutions in viscoelastic fluid with a single relaxation time

Rheological equations of state of dilute polymer solutions in viscoelastic fluid with one relaxation time are derived by applying a structural approach. The system under consideration is simulated by the superposition of two interpenetrating interacting conitua. The hydrodynamic behaviour of single polymer chains is simulated using the subchain model representing a linear sequence of frictional centres, spherical Brownian particles chain-bonded by means of elastic forces. The oscillatory shearing flow of the solution is studied on the basis of the equations derived. The expressions for the complex viscosity and relaxation times are determined. It is shown that the availability of polymer additions brings about a strong smearing of the relaxation spectrum of the carrying medium.     

The effect of impurities on the viscoelastic response of polycarbonate reinforced with short glass fibers

Observations are reported in oscillatory torsion tests at room temperature on unfilled and fiber-reinforced polycarbonates melt-blended with impurities (acronitrile–butadiene–styrene, high-impact polystyrene, low-density polyethylene, poly(ethylene terephthalate) and Nylon 6,6). Constitutive equations are derived for the viscoelastic behavior of glassy polymers. With reference to the theory of cooperative relaxation, a polymer is treated as an ensemble of meso-regions with arbitrary shapes and sizes. The time-dependent response of the ensemble is attributed to rearrangement of meso-domains. The rearrangement events occur at random times, when meso-regions are excited by thermal fluctuations. Stress–strain relations are derived by using the laws of thermodynamics. The governing equations are determined by four adjustable parameters that are found by fitting the experimental data. Fair agreement is demonstrated between the observations and the results of numerical simulation. The study focuses on the effects of the concentration of impurities and glass fibers on material parameters.     

A modified tube dilatation theory for the relaxation of entangled linear polymer melts

In this paper, the “tube dilatation” or “tube Enlargement” concept introduced by Marrucci, is revisited in the case of broad entangled linear polymer melts. Using the tube fluctuation relaxation function of Doi and a linear mixing rule, the model implicitly contains both the features of double reptation and time modification by tube renewal. It has been shown that theoretical arguments of both double reptation with tube renewal and tube dilatation can be used to take into account the effect of polydispersity on the distribution of relaxation times. The model has been tested for some polymers with various N/Ne values. However, experiments indicate that the loss of only one entanglement does not systematically induce a change of the relaxation times through a constraint release and tube renewal process. The freeing of a critical volume, larger than the volume of a tube segment, is required to induce an efficient dilution effect on relaxation times.     

Transient shear flow properties of fiber-filled polyethylene melts

The growth and relaxation of shear and normal stresses have been investigated for glass and carbon fiber-filled polyethylene melts over a wide range of shear rates and temperatures by means of a cone-and-plate rheogoniometer. Flow parameters and flow curves characterizing the stress overshoot and relaxation phenomena of the fiber-filled systems were determined experimentally. The influence of fiber loading, fiber size and temperature on the transient flow parameters are discussed.Predictions by the Meister and Bogue constitutive equations were compared with the experimental data for the transient shear and normal stresses. These equations predict satisfactorily the non-linear transient shear flow of polymer melts and its fiber-filled systems.     

A non-linear viscoelastic model with structure-dependent relaxation times: I. Basic formulation

A non-linear constitutive equation for polymer melts and concentrated solutions is presented. Based on known results of network theories, the model contains a distinctive feature: that of letting the relaxation times depend upon the existing structure.The model extends the constitutive equation of linear viscoelasticity to the non-linear region in a well-defined way, with the uncertainty of just a single adjustable parameter.Predictions of the model for common cases of non-linear response are derived and discussed.     

An improved algorithm for calculating relaxation time spectra from material functions of polymers with monodisperse and bimodal molar mass distributions

Using the basic concept of Emri and Tschoegl, the algorithm for calculating relaxation time spectra has been improved such that excellent results are provided in the difficult case of polymers with narrow molar mass distributions. These spectra can be compared with those calculated by nonlinear regularization (Weese 1992), which we regard as a very exact method, and show equally good results with even less mathematical effort. Examples of dense relaxation time spectra (up to eight points per decade) are given for nearly monodisperse polystyrene melts and for mixtures of these up to four components. The relaxation time spectra describe the dynamic mechanical experimental data in each case with an overall error of less than 3%. The filtering method used to avoid physically senseless oscillations has been proven to resolve the characteristic peaks contributed by monodisperse polymers accurately.     

Investigation of the linear flow regime of commercial polymers by numerical conversion of MVM creep measurements

A new experimental and numerical method has been developed to characterize the terminal flow behavior of polydisperse, commercial grade polymer melts over a wide dynamic range of time/frequency scales. Experimentally, an MVM rheometer specifically designed for long time scale (t 10⁴ s) creep measurements is used to measure the creep compliance of three commercial polymers: two high density polyethylenes and one polystyrene. The long time scale MVM creep data are complemented in the short time scale regime by creep data from an industrial plate-plate rheometer. The time-dependent creep data is combined and converted to a discrete retardation spectra using a nonlinear regularization algorithm to address the ill-posed nature of the interconversion. The retardation spectrum is analytically converted to dynamic moduli and compared with independently measured dynamic moduli. In the overlapping frequency region, calculations and measurements show excellent agreement and the combined data span a much larger dynamic range than either independent data set. The calculated and measured dynamic moduli data are combined and a retardation spectrum with a vastly expanded dynamic range is generated. Combining long time scale MVM creep compliance data and dynamic moduli data exploits the intrinsic sensitivities of controlled strain and controlled stress rheological experiments and is a powerful means to greatly expand the experimentally accessible dynamic range of time/frequency. This approach is particularly useful for commercial polymers with broad molecular weight distributions and commensurately large distributions of relaxation times.     

Free vibration analysis of the axially moving Levy-type viscoelastic plate

In this paper, the viscoelastic theory is applied to the axially moving Levy-type plate with two simply supported and two free edges. On the basis of the elastic – viscoelastic equivalence, a linear mathematical model in the form of the equilibrium state equation of the moving plate is derived in the complex frequency domain. Numerical calculations of dynamic stability were conducted for a steel plate. The effects of transport speed and relaxation times modeled with two-parameter Kelvin–Voigt and three-parameter Zener rheological models on the dynamic behavior of the axially moving viscoelastic plate are analyzed.     

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.     

Comparison of linear viscoelastic constitutive equations for non-uniform polymer melts

Linear-viscoelastic properties of polydisperse and randomly-branched polymer melts were fit with several proposed relaxation functions by non-linear regression. Three polymer systems were investigated, including 1) crosslinked polyethylenes, 2) polydisperse linear poly(dimethylsiloxane)s, and 3) Marlex polyethylenes, which are polydisperse and probably contain long-chain branching. Four relaxation functions were evaluated, including the Rouse, reptation, stretched-exponential, and stretched-exponential-power-law (SEPL) relaxation functions. The SEPL best described each series of polymers, and therefore may be a general relaxation function for non-uniform polymer melts. The flow activation energy for crosslinked polyethylene may be coupled to a breadth-of-relaxation index, indicating that a coupling between a characteristic short relaxation time and longest relaxation time, as suggested by Ngai and Plazek (J. Polym. Sci. Polym. Phys. Ed. 1985, 23:2159–2180), may hold for some non-uniform polymers.     

Constitutive relationships for polymeric materials with power-law distributions of relaxation times

The linear relaxation modulus of polydisperse polymer melts and solutions can often be approximated by a power law,ct ^–m over some range of time,t. If, in addition, the nonlinear rheology is given by a separable integral equation, with a strain-dependent factor typical of those observed experimentally, then some commonly observed empirical rules and equations can be readily derived as approximations, namely the Cox-Merz relationship between complex viscosity and steady-state shear viscosity, Bersted's predictions of steady shear stress and first normal-stress difference from a truncated spectrum of linear relaxation times, and the observation of Koyama and coworkers that the ratio of the nonlinear to the linear time-dependent elongational viscosity is independent of strain rate, over a range of strain rates outside the linear regime.     

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.     

Stability and bifurcation analysis of a nonlinear transversally loaded rotating shaft

The dynamic stability and self-excited posteritical whirling of rotating transversally loaded shaft made of a standard material with elastic and viscous nonlinearities are analyzed in this paper using the theory of bifurcations as a mathematical tool. Partial differential equations of motion are derived under assumption that von Karman's nonlinearity is absent but geometric curvature nonlinearity is included. Galerkin's first-mode discretization procedure is then applied and the equations of motion are transformed to two third-order nonlinear equations that are analyzed using the theory of bifurcation. Condition for nontrivial equilibrium stability is determined and a bifurcating periodic solution of the second-order approximation is derived. The effects of dimensionless stress relaxation time and cubic elastic and viscous nonlinearities as well as the role of the transverse load are studied in the exemplary numerical calculations. A strongly stabilizing influence of the relaxation time is found that may eliminate self-excited vibration at all. Transition from super- to subcritical bifurcation is observed as a result of interaction between system nonlinearities and the transverse load.     

Orientation dynamics in commercial thermotropic liquid crystalline polymers in transient shear flows

In situ X-ray scattering measurements of molecular orientation under shear are reported for two commercial thermotropic liquid crystalline polymers (TLCPs), Vectra A950® and Vectra B950®. Transient shear flow protocols (reversals, step changes, and flow cessation) are used to investigate the underlying director dynamics. Synchrotron X-ray scattering in conjunction with a high-speed area detector provides sufficient time resolution to limit the total time spent in the melt during testing, whereas a redesigned X-ray capable shear cell provides a more robust platform for working with TLCP melts at high temperatures. The transient orientation response upon flow inception or flow reversal does not provide definitive signatures of either tumbling or shear alignment. However, the observation of clear transient responses to step increases or step decreases in shear rate contrasts with expectations and experience with shear-aligning nematics and suggests that these polymers are of the tumbling class. Finally, these two polymers show opposite trends in orientation following flow cessation, which appears to correlate with the evolution of dynamic modulus during relaxation. Specifically, Vectra B shows an increase in orientation upon flow cessation, an observation that can only be rationalized by the assumption of tumbling dynamics in shear. Together with prior observations of commercial LCP melts in channel flows, these results suggest that this class of materials, as a rule, exhibits director tumbling.     

Thermodynamics of relaxation processes in the glass transition region

Relaxation processes in the glass transition region, especially the recovery of the volume and the physical ageing of polymers, do not follow the common (linear) theory of relaxation. On the contrary, they show a development which depends on the previous history, may be non-monotonous and requires a relaxation time that may have negative values and a pole. These phenomena can be explained if the single relaxation time is replaced by a spectrum of relaxation times and the relaxation times are supposed to be subjected to a feedback via certain structure- and temperature-parameters (as, for instance, in the KAHR-theory).However, the feedback and a pole of the relaxation time arise already for a single internal degree of freedom by themselves, if, in the non-equilibrium thermodynamics, a dynamic and a static temperature are strictly differentiated. In the case of the relaxation of the diffusive translational motion of the molecules in the glass transition region the dynamic temperature is identical with the socalled fictive temperature introduced by Tool.With regard to the relaxation of the volume three different temperature regions must be distinguished: A fluid region at high temperatures where the relaxation is controlled by the free volume and complies with the linear theory at least approximately; a glass-like region at low temperatures where the relaxation is controlled by the thermal expansivity of the free volume and where, under certain conditions, the statements set up by Davies and Jones are valid; an intermediate region (the glass transition region) where the free volume as well as its coefficient of expansivity are decisive. In that region the effective relaxation time of the volume may have a pole and the dynamic temperature may approach its equilibrium value by discontinuous jumps or in a chaotic manner.Dedicated to Professor Dr. J. Meissner (ETH Zürich) on the occasion of his 60th birthday     

A model for the viscoelastic behavior of polymers at finite strains

Summary A constitutive model is derived for the isothermal nonlinear viscoelastic response in polymers, which do not possess the separability property. The model is based on the concept of transient networks, and treats a polymer as a system of nonlinear elastic springs (adaptive links), which break and emerge due to micro-Brownian motion of chains. The breakage and reformation rates for adaptive links are assumed to depend on some strain energy density. The viscoelastic behavior is described by an integral constitutive equation, where the relaxation functions satisfy partial differential equations with coefficients depending on the strain history. Adjustable parameters of the model are found by fitting experimental data for a number of polymers in tension at strains up to 400 per cent. To validate the constitutive relations, we consider loading with different strain rates, determine adjustable parameters at one rate of strains, and compare prediction of the model with observations at another rate of strains. Fair agreement between experimental data and results of numerical simulation is demonstrated when the rates of strains differ by more than a decade. Received 1 July 1997; accepted for publication 7 October 1997     

Characteristic-value analysis for plastic dynamic buckling of columns under elastoplastic compression waves

The characteristic-value analysis of plastic dynamic buckling is presented for columns under the action of elastoplastic compression wave caused by an axial-step load. Two critical conditions constituting a dynamic instability criterion are derived on the basis of transformation and conservation of energy. The governing equations, the boundary conditions and the continuity conditions derived by the use of the first critical condition are the same as those given by the adjacent-equilibrium criterion and are insufficient for determining two characteristic parameters involved in the governing equations. A supplementary restraint equation for buckling deformations at the plastic-wave front and the elastic-wave front is derived by the use of the second critical condition. Then, a couple of characteristic equations for two characteristic parameters are derived on the condition that the governing equations have non-trivial solutions satisfying the boundary conditions, the continuity conditions and the supplementary restraint equation. The critical-load parameters, dynamic characteristic parameter (exponent parameter of inertia term) and dynamic buckling modes are calculated from the solutions of the characteristic equations.