Viscoelastic behavior mechanisms

Popelar, C. F. and Liechti, K. M., A Distortion-Modified Free Volume Theory for Nonlinear Viscoelastic Behavior , Mechanics of Time-Dependent Materials, 7 89-141, 2003. 

We have relied heavily on the use of models in discussing the viscoelastic behavior of polymers in the transient and dynamic experiments of the last few sections. The models were mechanical, however, and while they provide a way for understanding the phenomena involved, they do not explicitly relate these phenomena to molecular characteristics. To establish this connection is the objective of this section. 

The typical viscoelastic response, as shown in Fig. 2.18, is the propagation of a shock due to the compression, followed by a relaxation to an equilibrium state. The relaxation response is a significant part of the total response. Relaxation times are typically in the 0.1 /is regime. At pressures over about 2 GPa, PMMA shows a change in relaxation time which may be indicative of mechanical failure. Anderson has recently extended this work to other polymers and found similar strong viscoelastic behavior [92A01]. 

In this approach the reviews concerned the rheology involving the linear viscoelastic behavior of plastics and how such behavior is affected by temperature. Next is to extend this knowledge to the complex behavior of crystalline plastics, and finally illustrate how experimental data were applied to a practical example of the long-time mechanical stability. 

There are several other comparable rheological experimental methods involving linear viscoelastic behavior. Among them are creep tests (constant stress), dynamic mechanical fatigue tests (forced periodic oscillation), and torsion pendulum tests (free oscillation). Viscoelastic data obtained from any of these techniques must be consistent data from the others. 

The Maxwell model is also called Maxwell fluid model. Briefly it is a mechanical model for simple linear viscoelastic behavior that consists of a spring of Young s modulus (E) in series with a dashpot of coefficient of viscosity (ji). It is an isostress model (with stress 5), the strain (f) being the sum of the individual strains in the spring and dashpot. This leads to a differential representation of linear viscoelasticity as d /dt = (l/E)d5/dt + (5/Jl)-This model is useful for the representation of stress relaxation and creep with Newtonian flow analysis. 

Contrary to the phase separation curve, the sol/gel transition is very sensitive to the temperature more cations are required to get a gel phase when the temperature increases and thus the extension of the gel phase decreases [8]. The sol/gel transition as determined above is well reproducible but overestimates the real amount of cation at the transition. Gelation is a transition from liquid to solid during which the polymeric systems suffers dramatic modifications on their macroscopic viscoelastic behavior. The whole phenomenon can be thus followed by the evolution of the mechanical properties through dynamic experiments. The behaviour of the complex shear modulus G (o)) reflects the distribution of the relaxation time of the growing clusters. At the gel point the broad distribution of... 

Real polymers are more complex than these simple mechanical models. Qualitatively, when a real polymer is forced to flow through a contraction or expansion in an extrusion screw, it will exhibit viscoelastic behaviour. The polymer molecules will be elongated if forced through a contraction, or they will retract when they flow into an expansion. The effect of viscoelastic behavior in a capillary rheometer is observed in the form of recirculation flow just before the polymer enters the... 

Rheological Properties Measurements. The viscoelastic behavior of the UHMWPE gel-like systems was studied using the Rheometric Mechanical Spectrometer (RMS 705). A cone and plate fixture (radius 1.25 cm cone angle 9.85 x 10" radian) was used for the dynamic frequency sweep, and the steady state shear rate sweep measurements. In order to minimize the error caused by gap thickness change during the temperature sweep, the parallel plates fixture (radius 1.25 cm gap 1.5 mm) was used for the dynamic temperature sweep measurements. 

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. 

Dynamic mechanical experiments yield both the elastic modulus of the material and its mechanical damping, or energy dissipation, characteristics. These properties can be determined as a function of frequency (time) and temperature. Application of the time-temperature equivalence principle [1-3] yields master curves like those in Fig. 23.2. The five regions described in the curve are typical of polymer viscoelastic behavior. 

Filler-filler interaction (Payne effect) - The introduction of reinforcing fillers into rubbery matrices strongly modifies the viscoelastic behavior of the materials. In dynamic mechanical measurements, with increasing strain amplitude, reinforced samples display a decrease of the storage shear modulus G. This phenomenon is commonly known as the Payne effect and is due to progressive destruction of the filler-filler interaction [46, 47]. The AG values calculated from the difference in the G values measured at 0.56% strain and at 100% strain in the unvulcanized state are used to quantify the Payne effect. 

There are several important things to note. The first is that elastic deformation is a reversible process, but plastic deformation and brittle fracture are not. More importantly, plastic deformation and viscoelastic behavior are kinetic phenomena time is important, and they can be affected by press speed. In reality, most materials exhibit both plastic and brittle behavior, but specific materials can be classified as primarily plastic or primarily brittle. For example, microcrystalUne cellulose defonns primarily by a plastic deformation mechanism calcium phosphate de-fonns primarily by a brittle fracture mechanism lactose is in the middle [8]. 

The Eyring analysis does not explicity take chain structures into account, so its molecular picture is not obviously applicable to polymer systems. It also does not appear to predict normal stress differences in shear flow. Consequently, the mechanism of shear-rate dependence and the physical interpretation of the characteristic time t0 are unclear, as are their relationships to molecular structure and to cooperative configurational relaxation as reflected by the linear viscoelastic behavior. At the present time it is uncertain whether the agreement with experiment is simply fortuitous, or whether it signifies some kind of underlying unity in the shear rate dependence of concentrated systems of identical particles, regardless of their structure and the mechanism of interaction. 

As shown in Chapter 10, molecular dynamics in polymers is characterized by localised and cooperative motions that are responsible for the existence of different relaxations (a, (3, y). These, in turn, are responsible for energy dissipation, mechanical damping, mechanical transitions and, more generally, of what is called a viscoelastic behavior - intermediary between an elastic solid and a viscous liquid (Ferry, 1961 McCrum et al., 1967). 

The number of PPE particles dispersed in the SAN matrix, i.e., the potential nucleation density for foam cells, is a result of the competing mechanisms of dispersion and coalescence. Dispersion dominates only at rather small contents of the dispersed blend phase, up to the so-called percolation limit which again depends on the particular blend system. The size of the dispersed phase is controlled by the processing history and physical characteristics of the two blend phases, such as the viscosity ratio, the interfacial tension and the viscoelastic behavior. While a continuous increase in nucleation density with PPE content is found below the percolation limit, the phase size and in turn the nucleation density reduces again at elevated contents. Experimentally, it was found that the particle size of immiscible blends, d, follows the relation d --6 I Cdispersed phase and C is a material constant depending on the blend system. Subsequently, the theoretical nucleation density, N , is given by... 

Summary In this chapter, a discussion of the viscoelastic properties of selected polymeric materials is performed. The basic concepts of viscoelasticity, dealing with the fact that polymers above glass-transition temperature exhibit high entropic elasticity, are described at beginner level. The analysis of stress-strain for some polymeric materials is shortly described. Dielectric and dynamic mechanical behavior of aliphatic, cyclic saturated and aromatic substituted poly(methacrylate)s is well explained. An interesting approach of the relaxational processes is presented under the experience of the authors in these polymeric systems. The viscoelastic behavior of poly(itaconate)s with mono- and disubstitutions and the effect of the substituents and the functional groups is extensively discussed. The behavior of viscoelastic behavior of different poly(thiocarbonate)s is also analyzed. 

Mechanical and viscoelastic behaviour of materials can be determined by different kind of instrumental techniques. Broadband viscoelastic spectroscopy (BVS) and resonant ultrasound spectroscopy (RUS) are more commonly used to test viscoelastic behavior because they can be used above and below room temperatures and are more specific to testing viscoelasticity. These two instruments employ a damping mechanism at various frequencies and time ranges with no appeal to time-temperature superposition. Using BVS and RUS to study the mechanical properties of materials is important to understanding how a material exhibiting viscoelasticity will perform. 

Models of mechanical behavior of tissues have been difficult to develop primarily because of the time dependence of the viscoelasticity. Analysis of viscoelastic behavior of even simple polymers at strains greater than a few percent is not accurate. In addition, most tissues undergo strains larger than a few percent, which makes the analysis require an understanding of the elongation behavior. In this chapter we focus on using modeling techniques to analyze the physical basis for determination of the tensile behavior of ECMs found in connective tissue. 

Figure 8.1. Diagram showing Maxwell mechanical model of viscoelastic behavior of connective tissues. In this model an elastic element (spring) with a stiffness Em is in series with a viscous element (dashpot) with viscosity T m. This model is used to represent time dependent relaxation of stress in a specimen bold of fixed length.

In an earlier section, we have shown that the viscoelastic behavior of homogeneous block copolymers can be treated by the modified Rouse-Bueche-Zimm model. In addition, the Time-Temperature Superposition Principle has also been found to be valid for these systems. However, if the block copolymer shows microphase separation, these conclusions no longer apply. The basic tenet of the Time-Temperature Superposition Principle is valid only if all of the relaxation mechanisms are affected by temperature in the same manner. Materials obeying this Principle are said to be thermorheologically simple. In other words, relaxation times at one temperature are related to the corresponding relaxation times at a reference temperature by a constant ratio (the shift factor). For... 

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