Polymer rheology linear viscoelasticity

Marrucci G, Maffettone PL (1993) Liquid crystalline polymers. Pergamon, New York Mead DW (1994) Determination of molecular weight distributions of linear flexible polymers from linear viscoelastic material functions. J Rheol 38 1797-1827 Moldenaers P, Yanase H, Mewis J (1990) Effect of shear history on the theological behavior of lyotropic liquid crystals. Liq Cryst Polym 24(1990) 370-380 Muir MC, Porter RS (1989) Processing rheology of liquid taystal polymers a review. Mol Cryst Liq Cryst 169 83-95... 

This section is primarily concerned with the behaviour of simple homo-polymers. The development of viscoelastic theory was intimately linked with the study of polymeric species. This area of activity has led the way in the development of rheological models and experimental design and so is a very important area for the proto-rheologist to understand. So far in this chapter we have taken the approach of developing phase diagrams from a rheological perspective in order to understand linear viscoelastic... 

Contents Chain Configuration in Amorphous Polymer Systems. Material Properties of Viscoelastic Liquids. Molecular Models in Polymer Rheology. Experimental Results on Linear Viscoelastic Behavior. Molecular Entan-lement Theories of Linear iscoelastic Behavior. Entanglement in Cross-linked Systems. Non-linear Viscoelastic-Properties. 

The viscoelastic response of polymer melts, that is, Eq. 3.1-19 or 3.1-20, become nonlinear beyond a level of strain y0, specific to their macromolecular structure and the temperature used. Beyond this strain limit of linear viscoelastic response, if, if, and rj become functions of the applied strain. In other words, although the applied deformations are cyclic, large amplitudes take the macromolecular, coiled, and entangled structure far away from equilibrium. In the linear viscoelastic range, on the other hand, the frequency (and temperature) dependence of if, rf, and rj is indicative of the specific macromolecular structure, responding to only small perturbations away from equilibrium. Thus, these dynamic rheological properties, as well as the commonly used dynamic moduli... 

The linear viscoelastic models (LVE), which are widely used to describe the dynamic rheological response of polymer melts below the strain limit of the linear viscoelastic response of polymers. The results obtained are characteristic of and depend on the macromolecular structure. These are widely used as rheology-based structure characterization tools. 

Fatkullin NF, Kimmich R, Kroutieva M (2000) The twice-renormalised Rouse formalism of polymer dynamics Segment diffusion, terminal relaxation, and nuclear spin-lattice relaxation. J Exp Theor Phys 91(1) 150-166 Ferry JD (1980) Viscoelastic properties of polymers, 3rd edn. Wiley, London Ferry JD (1990) Some reflections on the early development of polymer dynamics Viscoelasticity, dielectric dispersion, and self-diffusion. Macromolecules 24 5237-5245 Ferry JD, Landel RF, Williams ML (1955) Extensions of the Rouse theory of viscoelastic properties to undilute linear polymers. J Appl Phys 26 359-362 Fikhman VD, Radushkevich BV, Vinogradov GV (1970) Reological properties of polymers under extension at constant deformation rate and at constant extension rate. In Vinogradov GV (ed) Uspekhi reologii polimerov (Advances in polymer rheology, in Russian). Khimija, Moscow, pp 9-23... 

It is not clear why this transition should occur at such a higher level of arm entanglement for polystyrene stars than for other star polymers. This observation is in direct conflict with the standard assumption that through a proper scaling of plateau modulus (Go) and monomeric friction coefficient (0 that rheological behavior should be dependent only on molecular topology and be independent of molecular chemical structure. This standard assumption was demonstrated to hold fairly well for the linear viscoelastic response of well-entangled monodisperse linear polyisoprene, polybutadiene, and polystyrene melts by McLeish and Milner [24]. 

Measurement of the linear viscoelastic properties is the basic rheological characterization of polymer melts. These properties may he evaluated in the time domain (mainly creep and relaxation experiments) or in the frequency domain in this case we will talk about mechanical spectroscopy, where the sample experiences a harmonic stimulus (either stress or strain). 

It consists in developing numerical and analytical methods to invert a linear viscoelastic material fimction to determine the molecular weight distribution. There are several reasons to pursue such an objective many commercial polymers are slightly or not at aU soluble in usual solvents, thus techniques like gel permeation chromatography or light scattering are inapplicable. Rheological characterization can be performed on-line and in real time and it is also a less cots-effective technique. 

Polymeric fluids are the most studied of all complex fluids. Their rich rheological behavior is deservedly the topic of numerous books and is much too vast a subject to be covered in detail here. We must therefore limit ourselves to an overview. The interested reader can obtain more thorough presentations in the following references a book by Ferry (1980), which concentrates on the linear viscoelasticity of polymeric fluids, a pair of books by Bird et al. (1987a,b), which cover polymer constitutive equations, molecular models, and elementary fluid mechanics, books by Tanner (1985), by Dealy and Wissbrun (1990), and by Baird and Dimitris (1995), which emphasize kinematics and polymer processing flows, a book by Macosko (1994) focusing on measurement methods and a book by Larson (1988) on polymer constitutive equations. Parts of this present chapter are condensed versions of material from Larson (1988). The static properties of flexible polymer molecules are discussed in Section 2.2.3 their chemistry is described in Flory (1953). 

Keywords Elastohydrodynamic interactions Glass transition Linear viscoelasticity Nonlinear rheology Polymer-colloid materials Shear-thinning Wall slip... 

The complex viscosity as a function of frequency, maximum strain and temperature is generally determined with one rheometer. Standard ASTM 4440-84/90 defines the measurement of rheological parameters of polymer samples using dynamic oscillation. This standard reiterates the importance of determining the linear viscoelastic region prior to performing dynamic frequency sweeps. 

The linear viscoelastic behavior of the pure polymer and blends has already been described quantitatively by using models of molecular dynamics based on the reptation concept [12]. To describe the rheological behavior of the copolymers in this study, we have selected and extended the analytical approach of Be-nallal et al. [13], who describe the relaxation function G(t) of Hnear homopolymer melts as the sum of four independent relaxation processes [Eq. (1)]. Each term describes the relaxation domains extending from the lowest frequencies (Gc(t)) to the highest frequencies (Ghf( )), and is well defined for homopolymers in Ref [13]. 

In summary, if G t), which is contained in Eqs. (4.30), (4.34)-(4.37), (4.49)-(4.51), (4.63) and (4.73), is known, all the linear viscoelastic quantities can be calculated. In other words, all the various viscoelastic properties of the polymer are related to each other through the relaxation modulus G t). This result is of course the consequence of the generalized Maxwell equation or equivalently Boltzmann s superposition principle. The experimental results of linear viscoelastic properties of various polymers support the phenomenological principle. Some viscoelastic properties play more important roles than the others in certain rheological processes related to... 

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