Viscoelastic properties time dependence

Thixotropy is the tendency of certain substances to flow under external stimuli (e.g., mild vibrations). A more general property is viscoelasticity, a time-dependent transition from elastic to viscous behavior, characterized by a relaxation time. When the transition is confined to small regions within the bulk of a solid, the substance is said to creep. A substance which creeps is one that stretches at a time-dependent rate when subjected to constant stress and temperature. The approximately constant stretching rates at intermediate times are used to characterize the creeping characteristics of the material. 

All polymer materials used in reinforced plastics display some viscoelastic or time-dependent properties. The origins of creep in composites stem from the behaviour of polymers under load together with local stress redistributions between fibre and matrix as a function of time. There is little creep at normal temperatures in the reinforcing fibres. The origin of the creep mechanisms is related to the nature and levels of internal bonding forces between the chains of the polymer, which are influenced by temperature and moisture. 

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. 

For a fiber immersed in water, the ratio of the slopes of the stress—strain curve in these three regions is about 100 1 10. Whereas the apparent modulus of the fiber in the preyield region is both time- and water-dependent, the equiUbrium modulus (1.4 GPa) is independent of water content and corresponds to the modulus of the crystalline phase (32). The time-, temperature-, and water-dependence can be attributed to the viscoelastic properties of the matrix phase. 

It has been also shown that when a thin polymer film is directly coated onto a substrate with a low modulus ( < 10 MPa), if the contact radius to layer thickness ratio is large (afh> 20), the surface layer will make a negligible contribution to the stiffness of the system and the layered solid system acts as a homogeneous half-space of substrate material while the surface and interfacial properties are governed by those of the layer [32,33]. The extension of the JKR theory to such layered bodies has two important implications. Firstly, hard and opaque materials can be coated on soft and clear substrates which deform more readily by small surface forces. Secondly, viscoelastic materials can be coated on soft elastic substrates, thereby reducing their time-dependent effects. 

The viscoelastic nature of the matrix in many fibre reinforced plastics causes their properties to be time and temperature dependent. Under a constant stress they exhibit creep which will be more pronounced as the temperature increases. However, since fibres exhibit negligible creep, the time dependence of the properties of fibre reinforced plastics is very much less than that for the unreinforced matrix. 

Mechanical properties of plastics are invariably time-dependent. Rheology of plastics involves plastics in all possible states from the molten state to the glassy or crystalline state (Chapter 6). The rheology of solid plastics within a range of small strains, within the range of linear viscoelasticity, has shown that mechanical behavior has often been successfully related to molecular structure. Studies in this area can have two objectives (1) mechanical characterization of... 

Time dependence Viscoelastic deformation is a transition type behavior that is characterized by the occurrence of both elastic strain and time-dependent flow. It is the time dependence of the mechanical properties of plastics that makes the behavior of these materials difficult to analyze by mathematical theory. 

When an engineering plastic is used with the structural foam process, the material produced exhibits behavior that is easily predictable over a large range of temperatures. Its stress-strain curve shows a significantly linearly elastic region like other Hookean materials, up to its proportional limit. However, since thermoplastics are viscoelastic in nature, their properties are dependent on time, temperature, and the strain rate. The ratio of stress and strain is linear at low strain levels of 1 to 2%, and standard elastic design... 

Viscoelasticity illustrates materials that exhibit both viscous and elastic characteristics. Viscous materials tike honey resist shear flow and strain linearly with time when a stress is applied. Elastic materials strain instantaneously when stretched and just as quickly return to their original state once the stress is removed. Viscoelastic materials have elements of both of these properties and, as such, exhibit time-dependent strain. Viscoelasticity is the result of the diffusion of atoms or molecules inside an amorphous material. Rubber is highly elastic, but yet a viscous material. This property can be defined by the term viscoelasticity. Viscoelasticity is a combination of two separate mechanisms occurring at the same time in mbber. A spring represents the elastic portion, and a dashpot represents the viscous component (Figure 28.7). 

The strength and extensibility of a noncrystallizable elastomer depend on its viscoelastic properties (28,29), even when the stress remains in equilibrium with the strain until macroscopic fracture occurs. In theory, such elastomers have a time- or rate-independent strength and ultimate elongation, but such threshold quantities apparently have not been measured, though rough estimates have been made (28,30). 

Actually, some fluids and solids have both elastic (solid) properties and viscous (fluid) properties. These are said to be viscoelastic and are most notably materials composed of high polymers. The complete description of the rheological properties of these materials may involve a function relating the stress and strain as well as derivatives or integrals of these with respect to time. Because the elastic properties of these materials (both fluids and solids) impart memory to the material (as described previously), which results in a tendency to recover to a preferred state upon the removal of the force (stress), they are often termed memory materials and exhibit time-dependent properties. 

For a Newtonian fluid, the shear stress is proportional to the shear rate, the constant of proportionality being the coefficient of viscosity. The viscosity is a property of the material and, at a given temperature and pressure, is constant. Non-Newtonian fluids exhibit departures from this type of behaviour. The relationship between the shear stress and the shear rate can be determined using a viscometer as described in Chapter 3. There are three main categories of departure from Newtonian behaviour behaviour that is independent of time but the fluid exhibits an apparent viscosity that varies as the shear rate is changed behaviour in which the apparent viscosity changes with time even if the shear rate is kept constant and a type of behaviour that is intermediate between purely liquid-like and purely solid-like. These are known as time-independent, time-dependent, and viscoelastic behaviour respectively. Many materials display a combination of these types of behaviour. 

The understanding of the temperature and conversion dependence of the crosslinking kinetics is one of the prerequisites for understanding the changes in viscosity and viscoelastic properties as a function of reaction time and reaction temperature ( ). Three main factors determine these relations the reaction kinetics determined by temperature and conversion, the changes in structure determined primarily by conversion and the changes in Tg determined primarily also by conversion. 

The time and temperature dependent properties of crosslinked polymers including epoxy resins (1-3) and rubber networks (4-7) have been studied in the past. Crosslinking has a strong effect on the glass transition temperature (Tg), on viscoelastic response, and on plastic deformation. Although experimental observations and empirical expressions have been made and proposed, respectively, progress has been slow in understanding the nonequilibrium mechanisms responsible for the time dependent behavior. 

The mechanical response of polypropylene foam was studied over a wide range of strain rates and the linear and non-linear viscoelastic behaviour was analysed. The material was tested in creep and dynamic mechanical experiments and a correlation between strain rate effects and viscoelastic properties of the foam was obtained using viscoelasticity theory and separating strain and time effects. A scheme for the prediction of the stress-strain curve at any strain rate was developed in which a strain rate-dependent scaling factor was introduced. An energy absorption diagram was constructed. 14 refs. 

Figure 5.60 (a) Maxwell spring and dashpot in series model of viscoelasticity and (b) constant stress conditions resnlting in time-dependent strain. From Z. Jastrzebski, The Nature and Properties of Engineering Materials, 2nd ed. Copyright 1976 by John Wiley Sons, Inc. This material is used by permission of John Wiley Sons, Inc. 

Dynamic mechanical analysis (DMA) or dynamic mechanical thermal analysis (DMTA) provides a method for determining elastic and loss moduli of polymers as a function of temperature, frequency or time, or both [1-13]. Viscoelasticity describes the time-dependent mechanical properties of polymers, which in limiting cases can behave as either elastic solids or viscous liquids (Fig. 23.2). Knowledge of the viscoelastic behavior of polymers and its relation to molecular structure is essential in the understanding of both processing and end-use properties. 

Figure 8.12 illustrates the effect of complex formation between protein and polysaccharide on the time-dependent surface shear viscosity at the oil-water interface for the system BSA + dextran sulfate (DS) at pH = 7 and ionic strength = 50 mM. The film adsorbed from the 10 wt % solution of pure protein has a surface viscosity of t]s > 200 mPa s after 24 h. As the polysaccharide is not itself surface-active, it exhibited no measurable surface viscosity (t]s < 1 niPa s). But, when 10 wt% DS was introduced into the aqueous phase below the 24-hour-old BSA film, the surface viscosity showed an increase (after a further 24 h) to a value around twice that for the original protein film. Hence, in this case, the new protein-polysaccharide interactions induced at the oil-water interface were sufficiently strong to influence considerably the viscoelastic properties of the adsorbed biopolymer layer. 

The mean times t and tw will be called the number-average and weight-average relaxation times of the terminal region, and tw/t can be regarded as a measure of the breadth of the terminal relaxation time distribution. It should be emphasized that these relationships are merely consequences of linear viscoelastic behavior and depend in no way on assumptions about molecular behavior. The observed relationships between properties such as rj0, J°, and G and molecular parameters provides the primary evidence for judging molecular theories of the long relaxation times in concentrated systems. 

Sakai, M., Fukaya, H., Nagasawa, M. Time dependent viscoelastic properties of concentrated polymer solutions. Trans. Soc. Rheol. 16,635-649 (1972). 

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