Deformation viscoelastic properties

Definition of terms relating to the non-ultimate mechanical properties of polymers. " This document defines mechanical terms of significance prior to failure of polymers. It deals in particular with bulk polymers and concentrated polymer solutions and their respective viscoelastic properties. It contains the basic definitions of experimentally observed stress, strain, deformations, viscoelastic properties, and the corresponding quantities that are commonly met in conventional mechanical characterization of polymeric materials. Definitions from ISO and ASTM publications are adapted. Only isotropic polymeric materials are considered. 

The elastic and viscoelastic properties of materials are less familiar in chemistry than many other physical properties hence it is necessary to spend a fair amount of time describing the experiments and the observed response of the polymer. There are a large number of possible modes of deformation that might be considered We shall consider only elongation and shear. For each of these we consider the stress associated with a unit strain and the strain associated with a unit stress the former is called the modulus, the latter the compliance. Experiments can be time independent (equilibrium), time dependent (transient), or periodic (dynamic). Just to define and describe these basic combinations takes us into a fair amount of detail and affords some possibilities for confusion. Pay close attention to the definitions of terms and symbols. 

In principle, the relaxation spectrum H(r) describes the distribution of relaxation times which characterizes a sample. If such a distribution function can be determined from one type of deformation experiment, it can be used to evaluate the modulus or compliance in experiments involving other modes of deformation. In this sense it embodies the key features of the viscoelastic response of a spectrum. Methods for finding a function H(r) which is compatible with experimental results are discussed in Ferry s Viscoelastic Properties of Polymers. In Sec. 3.12 we shall see how a molecular model for viscoelasticity can be used as a source of information concerning the relaxation spectrum. 

In the molten state polymers are viscoelastic that is they exhibit properties that are a combination of viscous and elastic components. The viscoelastic properties of molten polymers are non-Newtonian, i.e., their measured properties change as a function of the rate at which they are probed. (We discussed the non-Newtonian behavior of molten polymers in Chapter 6.) Thus, if we wait long enough, a lump of molten polyethylene will spread out under its own weight, i.e., it behaves as a viscous liquid under conditions of slow flow. However, if we take the same lump of molten polymer and throw it against a solid surface it will bounce, i.e., it behaves as an elastic solid under conditions of high speed deformation. As a molten polymer cools, the thermal agitation of its molecules decreases, which reduces its free volume. The net result is an increase in its viscosity, while the elastic component of its behavior becomes more prominent. At some temperature it ceases to behave primarily as a viscous liquid and takes on the properties of a rubbery amorphous solid. There is no well defined demarcation between a polymer in its molten and rubbery amorphous states. 

The mechanical properties of materials, though not often studied in detail, can have a profound effect on solids processing. Clearly, tableting properties are influenced by the elastic and plastic deformation properties as well as the viscoelastic properties of a material. As we have pointed out, the powder flow properties are also affected, as well as the tendency of materials to set up on storage. Because of the importance of mechanical properties, it is important to be able to... 

The dynamic viscoelastic properties of acetylated wood have been determined and compared with other wood treatments in a number of studies. Both the specific dynamic Young s modulus (E /j) and tan S are lower in acetylated wood compared with unmodified wood (Akitsu etal., 1991, 1992, 1993a,b Korai and Suzuki, 1995 Chang etal., 2000). Acetylation also reduces mechanosorptive creep deformation of the modified wood (Norimoto etal., 1992 Yano etal, 1993). In a study of the dynamic mechanical properties of acetylated wood under conditions of varying humidity, it was concluded that the rate of diffusion of moisture into the wood samples was not affected by acetylation (Ebrahimzadeh, 1998). 

Analyses of the results obtained depend on the shape of the specimen, whether or not the distribution of mass in the specimen is accounted for and the assumed model used to represent the linear viscoelastic properties of the material. The following terms relate to analyses which generally assume small deformations, specimens of uniform cross-section, non-distributed mass and a Voigt-Kelvin solid. These are the conventional assumptions. 

The specific material properties of most import to the compaction operation are elastic deformation behavior, plastic deformation behavior, and viscoelastic properties. These are also referred to as mechanisms of deformation. As mentioned earlier, they are equally important during compression and decompression i.e., the application of the compressional load to form the tablet, and the removal of the compressional load to allow tablet ejection. Elastic recovery during this decompression stage can result in tablet capping and lamination. 

Any rubber test piece with or without added mass has a natural or resonant frequency of vibration determined by the dimensions and viscoelastic properties of the rubber, the total inertia of the system, and the mode of deformation. If constant force amplitude cycles are applied to the rubber and the frequency varied, the resulting deformation cycles will have a maximum value when the applied frequency equals the resonant frequency of the test piece system. 

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 easy to understand that these solutions must exhibit viscoelastic properties. Under shear flow the vesicles have to pass each other and, hence, they have to be deformed. On deformation, the distance of the lamellae is changed against the electrostatic forces between them and the lamellae leave their natural curvature. The macroscopic consequence is an elastic restoring force. If a small shear stress below the yield stress ery is applied, the vesicles cannot pass each other at all. The solution is only deformed elastically and behaves like Bingham s solid. This rheological behaviour is shown in Figure 3.35. which clearly reveals the yield stress value, beyond which the sample shows a quite low viscosity. 

Plasticizers and flexibilizers are incorporated into an adhesive formulation to provide it with flexibility and/or elongation. Plasticizers may also reduce the melt viscosity of hot melt adhesives or lower the elastic modulus of a solidified adhesive. Similar to diluents, plasticizers are nonvolatile solvents for the base resin, and by being incorporated into the formulation, they separate the polymer chains and enable their deformation to be more easily accomplished. Plasticizers generally affect the viscoelastic properties of the base resin whereas diluents simply reduce the viscosity of the system. Whereas diluents result in brittle, hard adhesive systems, plasticizers result in increased flexibility and lower modulus. The temperature at which polymers exhibit rubbery properties (i.e., the glass transition temperature) can also be modified by incorporating plasticizers. 

Linear viscoelasticity is the simplest type of viscoelastic behavior, in which viscoelastic properties are independent of the magnitude of applied stress or strain (Barnes et al., 1989 Gunasekaran and Ak, 2002). Linear viscoelasticity is usually exhibited by food materials at very small strains (Rao, 1992) that cause negligible damage to the food s structure the phenomenon must therefore be investigated experimentally using small deformation test methods. 

For a given material the viscoelastic properties - the relaxation behaviour for solid materials - can be determined by a number of different techniques. The results obtained by each technique are expressed in the form of a characteristic function. In tensile deformation these functions are ... 

Shape retention is a factor in almost all articles made from polymeric materials (cf. warping of plastic articles, deformation of films, etc.). In textiles the lack of shape retention is reflected in the sagging of curtains, the bagging of trousers, etc. Shape retention is determined by the viscoelastic properties of the polymer, especially under the influence of moisture plastic deformation and creep are highly undesirable, whereas resilience is favourable. 

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