Non-linear viscoelastic behavior of polymer melts interpreted by fractional viscoelastic model

Very recently, researchers dealing with constitutive law pertinent viscoelastic materials put forward the successful idea to introduce viscoelastic laws embedded with fractional calculus, relating the stress function to a real order derivative of the strain function. The latter consideration leads to represent both, relaxation and creep functions, through a power law function. In literature there are many papers in which the best fitting of the peculiar viscoelastic functions using a fractional model is performed. However there are not present studies about best fitting of relaxation function and/or creep function of materials that exhibit a non-linear viscoelastic behavior, as polymer melts, using a fractional model. In this paper the authors propose an advanced model for capturing the non-linear trend of the shear viscosity of polymer melts as function of the shear rate. Results obtained with the fractional model are compared with those obtained using a classical model which involves classical Maxwell elements. The comparison between experimental data and the theoretical model shows a good agreement, emphasizing that fractional model is proper for studying viscoelasticity, even if the material exhibits a non-linear behavior.     

Some applications of molecular rheology: Polymer formulation and molecular design

“Molecular rheology” is the missing link between the macromolecular structure of polymeric materials and their viscoelastic properties in the melt state. It complements the engineering or continuum mechanics aspects of rheology, which generally ignores the molecular details of the objects under study. The pioneering vision of the diffusion and relaxation processes of flexible macromolecular chains initiated by P.-G. de Gennes has lead to very effective and predictive models of viscoelasticity of polymer melts, which go far beyond academic interest.We present, in this paper, two very different examples of application of molecular rheology: molecular design of block copolymers corresponding to expected end-user properties (which are directly linked to linear viscoelastic properties) and formulation of blends of linear polymers in order to get strain-hardening effects in non-linear viscoelasticity usually obtained with long-chain branched (LCB) materials.     

Phenomenological nonlinear modelling of glassy polymers

Compared with the numerous works into the constitutive equations for the mechanical behaviour of metals, very little attention has been devoted to those of polymers. However, a model is required to describe both the complex shape of the stress–strain curves and strain rate sensitivity of glassy polymers. In this Note, a unified viscoelastic-viscoplastic model is presented in which the nonlinear pre-yield behaviour, the strain softening and the strain hardening are described by internal variables, in analogy with the models developed for metals. In order to check the predictive capability of the model, the numerical results are compared with the experimental data (monotone, creep and relaxation tests) of a typical amorphous glassy polymer. To cite this article: F. Zaïri et al., C. R. Mecanique 333 (2005).     

Unsteady non-linear convection in a second-order fluid

Linear and weakly non-linear analyses of convection in a second-order fluid is investigated. The Rivlin-Ericksen constitutive equation is considered to give viscoelastic correction to the momentum equation. The linear and non-linear analyses are, respectively, based on the normal mode technique and truncated representation of Fourier series. The linear theory reveals that the critical eigenvalue is independent of viscoelastic effects and the principle of exchange of stabilities holds. An autonomous system of differential equations representing cellular convection arising in the non-linear study is solved numerically. The non-linear analysis reveals that finite amplitudes have random behaviour. The effect of viscoelasticity on the non-linear solutions is analysed by considering different projections in the phase-space. Also, the transient behaviour concerning the variations of the Nusselt number with time has been investigated. The onset of chaotic motion is also discussed in this paper.     

Prediction of the creep behaviour of polyethylene and molybdenum from stress relaxation experiments

In many applications it is useful to be able to convert observed creep data of a material to corresponding stress relaxation data or vice versa. If the material exhibits non-linear viscoelasticity such a conversion can be rather difficult. In this paper two semi-empirical flow equations, the power law and the exponential law, are used to convert stress relaxation data into corresponding creep behaviour data. These two flow equations are often used to describe non-linear viscoelastic behaviour. The procedure adopted here is based on the assumption that the creep data during the experiment decrease due to an increase in the internal stress level, thus decreasing the effective stress for flow. The conversion method is applied to high density polyethylene and polycrystalline molybdenum at room temperature. In general predictions using the power law are in better agreement with the experimental results than predictions using the exponential formula. The concepts of secondary and ceasing creep are discussed in terms of build-up of internal stress during the creep process.     

On the response of physical systems governed by non-linear ordinary differential equations to step input

The response of physical systems governed by linear ordinary differential equations to step input is traditionally investigated using the classical theory of distributions. The response of non-linear systems is however beyond the reach of the classical theory. The reason is that the simplest non-linear operation—multiplication—is not defined for distributions. Yet the response of non-linear systems is of interest in many applications, and a framework capable of handling such problems is needed.We argue that a suitable framework is provided by Colombeau algebra that gives one the possibility to overcome the limitations of the classical theory of distributions, namely the possibility to simultaneously handle discontinuity, differentiation and non-linearity. Our thesis is documented by means of studying the response of two systems governed by non-linear ordinary differential equations subject to step input. In particular, we show that using the rules of calculus in Colombeau algebra it is possible to obtain an explicit and practically relevant characterisation of the behaviour of the considered systems at the point of the jump discontinuity.     

On the thermodynamics of fractional damping elements

Constitutive models of viscoelasticity in combination with fractional differential operators are successfully used by many authors to describe the mechanical properties of polymers. The topic of the present paper is the investigation of rheological models incorporating fractional damping elements from the point of view of thermodynamics. We take the Clausius Duhem inequality as admissibility criterion and investigate uniaxial and three-dimensional deformation processes at constant temperature. We specify sufficient conditions and show that rheological models, which consist of springs in combination with fractional dashpots, are compatible with the dissipation principle. As a new aspect of the subject, we present a systematic method for deriving the free energy functionals. With the help of two examples we demonstrate that the free energy of fractional systems can be derived as a generalisation of related discrete systems. To illustrate this method, we study in detail an isolated fractional dashpot (also known as a power-law model) and a fractional standard solid (Zener model). Finally, we propose a three-dimensional formulation of the fractional Zener model and specify the corresponding free energy functional. Received: July 3, 1996     

Rheological characterization in shear of a model dumbbell polymer concentrated solution

We investigate the linear and non-linear rheological behavior in shear of a concentrated solution of ??dumbbell?? polystyrene with long linear backbone and dense short brushes at both ends and compare it with corresponding linear polymers. This type of dumbbells has never been rheologically characterized before. In linear viscoelasticity, the dumbbell polymers show significant differences with conventional linear polymers. In particular, the reptation relaxation of the dumbbell is strongly slowed down. Furthermore, the addition of the side chains increases the friction so that the dumbbell lies above the ?? ₀ vs. number of entanglements relation of linear samples. Transient shear rheology experiments on weakly entangled solutions show a retardation of the chain stretch relaxation of the dumbbell by a factor 2.5 vs. a linear polymer with the same Rouse time. Additionally, a second peak in the transient viscosity is observed at high shear rates.     

计及热效应和湿分扩散的耦合黏弹性本构方程

高聚物在电子和航空等领域得到广泛运用,由于高聚物的亲水性,常常发生由于湿热引起的结构失效甚至材料的断裂.近年来,有实验显示,高聚物中的湿热效应及其力学反响是相互影响的,同时,考虑到高聚物的黏弹性,发展新的包含湿热效应的黏弹性本构方程来描述该问题是必要的.本文基于不可逆热力学的基本原理,运用连续介质力学的方法,通过引入内变量表示高聚物的黏性效应,基于 Helmholtz自由能导出一种热、湿分和黏弹性力学性质三场耦合的本构关系和系统控制方程,对实际的分析应用有较强的指导意义.     

Dynamic stiffness of chemically and physically ageing rubber vibration isolators in the audible frequency range

The constitutive equations of chemically and physically ageing rubber in the audible frequency range are modelled as a function of ageing temperature, ageing time, actual temperature, time and frequency. The constitutive equations are derived by assuming nearly incompressible material with elastic spherical response and viscoelastic deviatoric response, using Mittag-Leffler relaxation function of fractional derivative type, the main advantage being the minimum material parameters needed to successfully fit experimental data over a broad frequency range. The material is furthermore assumed essentially entropic and thermo-mechanically simple while using a modified William–Landel–Ferry shift function to take into account temperature dependence and physical ageing, with fractional free volume evolution modelled by a nonlinear, fractional differential equation with relaxation time identical to that of the stress response and related to the fractional free volume by Doolittle equation. Physical ageing is a reversible ageing process, including trapping and freeing of polymer chain ends, polymer chain reorganizations and free volume changes. In contrast, chemical ageing is an irreversible process, mainly attributed to oxygen reaction with polymer network either damaging the network by scission or reformation of new polymer links. The chemical ageing is modelled by inner variables that are determined by inner fractional evolution equations. Finally, the model parameters are fitted to measurements results of natural rubber over a broad audible frequency range, and various parameter studies are performed including comparison with results obtained by ordinary, non-fractional ageing evolution differential equations.     

A Fractional Model of Continuum Mechanics

Although there has been renewed interest in the use of fractional models in many application areas, in reality fractional analysis has a long and distinguished history and can be traced back to the likes of Leibniz (Letter to L’Hospital, 1695), Liouville (J. éc. Polytech. 13:71, 1832), and Riemann (Gesammelte Werke, p. 62, 1876). Recent publications (Podlubny in Math. Sci. Eng. 198, 1999; Sabatier et al. in Advances in fractional calculus: theoretical developments and applications in physics and engineering, Springer, Berlin, 2007; Das in Functional fractional calculus for system identification and controls, Springer, Berlin, 2007) demonstrate that fractional derivative models have found widespread applications in science and engineering. Late fundamental considerations have led to the introduction of fractional calculus in continuum mechanics in an attempt to develop non-local constitutive relations (Lazopoulos in Mech. Res. Commun. 33:753–757, 2006). Attempts have also been made to model microscopic forces using fractional derivatives (Vazquez in Nonlinear waves: classical and quantum aspects, pp. 129–133, 2004). Our approach in this paper differs from previous theoretical work, in that we develop a general framework directly from the classical continuum mechanics, by defining the laws of motion and the stresses using fractional derivatives. The timeliness and relevance of this work is justified by the surge in interest in applications of fractional order models to biological, physical and economic systems. The aim of the present paper is to lay the foundations for a new non-local model of continuum mechanics based on fractional order derivatives which we will refer to as the fractional model of continuum mechanics. Following the theoretical development, we apply this framework to two one-dimensional model problems: the deformation of an infinite bar subjected to a self-equilibrated load distribution, and the propagation of longitudinal waves in a thin finite bar.     

Dynamic stability and bifurcation analysis in fractional thermodynamics

In mechanics, viscoelasticity was the first field of applications in studying geomaterials. Further possibilities arise in spatial non-locality. Non-local materials were already studied in the 1960s by several authors as a part of continuum mechanics and are still in focus of interest because of the rising importance of materials with internal micro- and nano-structure. When material instability gained more interest, non-local behavior appeared in a different aspect. The problem was concerned to numerical analysis, because then instability zones exhibited singular properties for local constitutive equations. In dynamic stability analysis, mathematical aspects of non-locality were studied by using the theory of dynamic systems. There the basic set of equations describing the behavior of continua was transformed to an abstract dynamic system consisting of differential operators acting on the perturbation field variables. Such functions should satisfy homogeneous boundary conditions and act as indicators of stability of a selected state of the body under consideration. Dynamic systems approach results in conditions for cases, when the differential operators have critical eigenvalues of zero real parts (dynamic stability or instability conditions). When the critical eigenvalues have non-trivial eigenspace, the way of loss of stability is classified as a typical (or generic) bifurcation. Our experiences show that material non-locality and the generic nature of bifurcation at instability are connected, and the basic functions of the non-trivial eigenspace can be used to determine internal length quantities of non-local mechanics. Fractional calculus is already successfully used in thermo-elasticity. In the paper, non-locality is introduced via fractional strain into the constitutive relations of various conventional types. Then, by defining dynamic systems, stability and bifurcation are studied for states of thermo-mechanical solids. Stability conditions and genericity conditions are presented for constitutive relations under consideration.     

Structural analogies on systems of deformable bodies coupled with non-linear layers

The paper is addressed at phenomenological mapping and mathematical analogies of oscillatory regimes in systems of coupled deformable bodies. Systems consist of coupled deformable bodies like plates, beams, belts or membranes that are connected through visco-elastic non-linear layer, modeled by continuously distributed elements of Kelvin–Voigt type with nonlinearity of third order. Using the mathematical analogies the similarities of structural models in systems of plates, beams, belts or membranes are obvious. The structural models consist by a set of two coupled non-homogenous partial non-linear differential equations. The problems to solve are divided into space and time domains by the classical Bernoulli–Fourier method. In the time domains the systems of coupled ordinary non-linear differential equations are completely analog for different systems of deformable bodies and are solved by using the Krilov–Bogolyubov–Mitropolskiy asymptotic method. This paper presents the beauty of mathematical analytical calculus which could be the same even for physically different systems.The mathematical numerical calculus is a powerful and useful tool for making the final conclusions between many input and output values. The conclusions about nonlinear phenomena in multi-body systems dynamics have been revealed from the particular example of double plate׳s system stationary and non-stationary oscillatory regimes.     

Time domain modeling of damping using anelastic displacement fields and fractional calculus

A fractional derivative model of linear viscoelasticity based on the decomposition of the displacement field into an anelastic part and elastic part is developed. The evolution equation for the anelastic part is then a differential equation of fractional order in time. By using a fractional order evolution equation for the anelastic strain the present model becomes very flexible for describing the weak frequency dependence of damping characteristics. To illustrate the modeling capability, the model parameters are fit to available frequency domain data for a high damping polymer. By studying the relaxation modulus and the relaxation spectrum the material parameters of the present viscoelastic model are given physical meaning. The use of this viscoelastic model in structural modeling is discussed and the corresponding finite element equations are outlined, including the treatment of boundary conditions. The anelastic displacement field is mathematically coupled to the total displacement field through a convolution integral with a kernel of Mittag–Leffler function type. Finally a time step algorithm for solving the finite element equations are developed and some numerical examples are presented.     

Fractional order inductive phenomena based on the skin effect

The Maxwell equations play a fundamental role in the electromagnetic theory and lead to models useful in physics and engineering. This formalism involves integer-order differential calculus, but the electromagnetic diffusion points towards the adoption of a fractional calculus approach. This study addresses the skin effect and develops a new method for implementing fractional-order inductive elements. Two genetic algorithms are adopted, one for the system numerical evaluation and another for the parameter identification, both with good results.     

Ageing and rejuvenation in glassy amorphous polymers

Physical ageing of amorphous polymers well below their glass transition temperature leads to changes in almost all physical properties. Of particular interest is the increase in yield stress and post-yield strain softening that accompanies ageing of these materials. Moreover, at larger strain polymers seem to rejuvenate, i.e. aged and non-aged samples have identical stress-strain responses. Also, plastically deforming an aged sample seems to rejuvenate the polymer. In this work we use molecular dynamic simulations with a detailed force field suitable for macromolecular ensembles to simulate and understand the effects of ageing on the mechanical response of these materials. We show that within the timescales of these simulations it is possible to simulate both ageing and rejuvenation. The short range potentials play an important role in ageing and rejuvenation. A typical yield drop exhibited by glassy polymers is a manifestation of a sudden relaxation in the short range structure of an aged polymer. Moreover, the aged polymers are known to be brittle. We show that this is intimately related to its typical stress-strain response which allows it to carry arbitrarily large mean stresses ahead of a notch.