Polymeric materials, stress

Polymers, unlike metals, are subject to swelling rather than corrosion. Chloride-induced pitting corrosion, to which austenitic Cr-Ni steels are particularly susceptible, is unknown in polymeric materials. Stress corrosion cracking, however, is possible under conditions that cause the medium to attack the polymer chemically. Stress corrosion cracking can only occur at the same time that stresses resulting from manufacture, coating or lining, or the conditions of use are present. 

The various elastic and viscoelastic phenomena we discuss in this chapter will be developed in stages. We begin with the simplest the case of a sample that displays a purely elastic response when deformed by simple elongation. On the basis of Hooke s law, we expect that the force of deformation—the stress—and the distortion that results-the strain-will be directly proportional, at least for small deformations. In addition, the energy spent to produce the deformation is recoverable The material snaps back when the force is released. We are interested in the molecular origin of this property for polymeric materials but, before we can get to that, we need to define the variables more quantitatively. 

Plastics testing encompasses the entire range of polymeric material characterizations, from chemical stmcture to material response to environmental effects. Whether the analysis or property testing is for quaUty control of a specific lot of plastic or for the determination of the material s response to long-term stress, a variety of test techniques is available for the researcher. 

Initiation. Free-radical initiators are produced by several processes. The high temperatures and shearing stresses required for compounding, extmsion, and molding of polymeric materials can produce alkyl radicals by homolytic chain cleavage. Oxidatively sensitive substrates can react directly with oxygen, particularly at elevated temperatures, to yield radicals. 

APAOs has limited their utility in a number of applications. The broad MWD produces poor machining and spraying, and the low cohesive strength causes bond failures at temperatures well below the softening point when minimal stress is applied. To address these deficiencies, metallocene-polymerized materials have been developed [17,18]. These materials have much narrower MWDs than Ziegler-Natta polymerized materials and a more uniform comonomer distribution (see Table 3). Materials available commercially to date are better suited to compete with conventional EVA and EnBA polymers, against which their potential benefits have yet to be realized in practice. 

Polymeric materials exhibit mechanical properties which come somewhere between these two ideal cases and hence they are termed viscoelastic. In a viscoelastic material the stress is a function of strain and time and so may be described by an equation of the form... 

During fatigue the stress amplitude usually remains constant and brittle failure occurs as a result of crack growth from a sub-critical to a critical size. Clearly the rate at which these cracks grow is the determining factor in the life of the component. It has been shown quite conclusively for many polymeric materials that the rate at which cracks grow is related to the stress intensity factor by a relation of the form... 

Grayson MA, Wolf CJ (1979) In Stress mass spectrometry of polymeric materials a review, ACS Adv Chem Series no. 174, Koenig JL (ed), p 53-80... 

An important aspect concerning the surface indentation mechanism is the creep effect shown by polymeric materials i.e. the time dependent part of the plastic deformation of the polymer surface under the stress of the indenter14-16. The creep curves are characterized by a decreasing strain rate, which can be described by a time law of the form... 

When we consider the mechanical properties of polymeric materials, and in particular when we design methods of testing them, the parameters most generally considered are stress, strain, and Young s modulus. Stress is defined as the force applied per unit cross sectional area, and has the basic dimensions of N m in SI units. These units are alternatively combined into the derived unit of Pascals (abbreviated Pa). In practice they are extremely small, so that real materials need to be tested with a very large number of Pa... 

Fig. 4.3.3 (a) Shear flow of a Newtonian fluid defined as the ratio of the shear stress and trapped between the two plates (each with a shear rate, (b) A polymeric material is being large area of A). The shear stress (a) is defined stretched at both ends at a speed of v. The as F/A, while the shear rate (y) is the velocity material has an initial length of L0 and an gradient, dvx/dy. The shear viscosity (r s) is (instantaneous) cross-sectional area of A. 

Polyethylene and polystyrene are examples of plastics subject to environmental stress cracking. Crack resistance tests have shown that surfactants, alcohols, organic acids, vegetable and mineral oils, and ethers provide an active environment for stress cracking of polyethylene. Table 6 lists typical sterile devices and plastic materials used to fabricate them, while Tables 7-9 list the potential effects of sterilization processes on polymeric materials. The effect of gamma irradiation on elastomeric closures has been studied by the Parenteral Drug Association [15]. 

We now have the tools necessary to describe how a polymeric material will respond to applied stresses. The next step is to add a method to characterize individual polymers in terms of the ease by which they deform. Imagine that we impose a shear stress on two different materials for the same length of time. In the first material we observe a great deal of deformation in the second there is very little. What is the reason for this The answer lies in the fact that there are fundamental differences in the response of each of the materials to the imposed stress. We define these differences by taking the ratio of the applied stress to the strain rate and calling it the material s viscosity, q, which is defined in Eq. 6.3. 

It Is well known that mechanical properties of polymeric materials are greatly deteriorated by UV exposure (2-j)). The nature of this deterioration was determined using non-strained samples which were photooxidized at 37°C. Engineering stress-strain curves as a function of UV exposure are shown in Figure 1. The numbers next to each curve represent days of UV exposure. In terms of degradation, the points of interest are ... 

Dynamic oscillatory shear measurements of polymeric materials are generally performed by applying a time dependent strain of y(t) = y0sin(cot) and the resultant shear stress is a(t) = y0[G sin(a)t) + G"cos(cot)], with G and G" being the storage and loss modulus, respectively. 

ISO 844 2001 Rigid cellular plastics - Determination of compression properties ISO 3386-1 1986 Polymeric materials, cellular flexible - Determination of stress-strain characteristics in compression - Part 1 Low-density materials ISO 3386-2 1997 Flexible cellular polymeric materials - Determination of stress-strain characteristics in compression - Part 2 High-density materials ISO 5893 2002 Rubber and plastics test equipment - Tensile, flexural and compression types (constant rate of traverse) - Specification ISO 7743 2004 Rubber, vulcanized or thermoplastic - Determination of compression stress-strain properties... 

ISO 2440 1997 Flexible and rigid cellular polymeric materials - Accelerated ageing tests ISO 6914 2004 Rubber, vulcanized - Determination of ageing characteristics by measurement of stress at a given elongation... 

C. Galiotis and J. Parthenios, Stress/strain measurements in fibers and composites using Raman spectroscopy, in Vibrational Spectroscopy of Biological and Polymeric Materials, V.G. Gregoriou and M.S. Braiman (Eds), CRC Press, Boca Raton, 2006. 

The terms are arranged into sections dealing with basic definitions of stress and strain, deformations used experimentally, stresses observed experimentally, quantities relating stress and deformation, linear viscoelastic behaviour, and oscillatory deformations and stresses used experimentally for solids. The terms which have been selected are those met in the conventional mechanical characterization of polymeric materials. 

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