Polymer mechanical deformation

These observations were the basis for the proposal that polymers, like ionic crystals, exhibit shock-induced polarization due to mechanically induced defects which are forced into polar configurations with the large acceleration forces within the loading portion of the shock pulse. Such a process was termed a mechanically induced, bond-scission model [79G01] and is somewhat supported by independent observations of the propensity of polymers to be damaged by more conventional mechanical deformation processes. As in the ionic crystals, the mechanically induced, bond-scission model is an example of a catastrophic shock compression model. 

An uniaxial mechanical deformation provokes drastic changes in the identation pattern of drawn polymers. Some typical results illustrating the dependence of MH on draw ratio for plastically deformed PE are shown in Fig. 19 a. The quoted experiments 12) refer to a linear PE sample (Mw 80.000) prepared in the usual dumbbell form drawn at a rate of 0.5 cm/min at atmospheric pressure. Identations were performed longitudinally along the orientation axis. Before the neck (A = 1), the... 

If the ordered, crystalline regions are cross sections of bundles of chains and the chains go from one bundle to the next (although not necessarily in the same plane), this is the older fringe-micelle model. If the emerging chains repeatedly fold buck and reenter the same bundle in this or a different plane, this is the folded-chain model. In either case the mechanical deformation behavior of such complex structures is varied and difficult to unravel unambiguously on a molecular or microscopic scale. In many respects the behavior of crystalline polymers is like that of two-ph ise systems as predicted by the fringed-micelle- model illustrated in Figure 7, in which there is a distinct crystalline phase embedded in an amorphous phase (134). 

Amorphous adsorbents, 1 587-589 for gas separation, 1 631 properties and applications, l 587t Amorphous aluminum hydroxide, 23 76 Amorphous carbohydrates, material science of, 11 530-536 Amorphous carbon, 4 735 Amorphous cellulose, 5 372-373 Amorphous films, in OLEDs, 22 215 Amorphous germanium (a-Ge), 22 128 Amorphous glassy polymers, localized deformation mechanisms in, 20 350-351... 

While conductivities of nanocarbons dispersed in polymers fall short of those of metals, a variety of applications can be unlocked by turning an insulating matrix into a conductor, which requires only small volume fractions that can therefore keep the system viscosity at a level compatible with composite processing techniques. Of particular interest are novel functionalities of these conductive matrices that exploit the presence of a conductive network in them, such as structural health monitoring (SHM) based on changes in electrical resistance of the nanocarbon network as it is mechanically deformed [30]. 

Despite the similarities in brittle and ductile behavior to ceramics and metals, respectively, the elastic and permanent deformation mechanisms in polymers are quite different, owing to the difference in structure and size scale of the entities undergoing movement. Whereas plastic deformation (or lack thereof) could be described in terms of dislocations and slip planes in metals and ceramics, the polymer chains that must be deformed are of a much larger size scale. Before discussing polymer mechanical properties in this context, however, we must first describe a phenomenon that is somewhat unique to polymers—one that imparts some astounding properties to these materials. That property is viscoelasticity, and it can be described in terms of fundamental processes that we have already introduced. 

The potential applications of FT-IR to the determination of polymer structure are many. In a number of areas, the impact of FT-IR has been very significant including the structure of polymer blends, polymer surfaces and the structural changes induced by mechanical deformation. These topics will be discussed in detail below. 

Mechanical deformation induces orientation into the polymer samples and polarized infrared can be used to characterize this orientation either by direct measurement of the dichroic ratio 287,289) or by spectral subtraction 286), three dimensional sample tilting 68,286), or internal reflection spectroscopy 130). 

Dynamic mechanical tests measure the response of a material to a periodic force or its deformation by such a force. One obtains simultaneously an elastic modulus (shear, Young s, or bulk) and a mechanical damping. Polymeric materials are viscoelastic-i.e., they have some of the characteristics of both perfectly elastic solids and viscous liquids. When a polymer is deformed, some of the energy is stored as potential energy, and some is dissipated as heat. It is the latter which corresponds to mechanical damping. 

With 7 = 0.072 Nm-1 and 5 = 10 nm the effective pressure is of the order of P = 72 x 10s Pa. Such a high pressure can change the surface structure, cause mechanical deformation at the moving wetting line [250], and can lead to contact angle hysteresis [251-253], especially on soft polymer surfaces. 

The goal of this investigation of the mechanical properties of amorphous polymers (plastic deformation, micromechanisms of deformation, fracture) was to analyse the influence of secondary transition motions on these properties. 

For soft materials such as polymers and biomolecules, mechanical deformation of the sample caused by the tip is a point for serious concern. The consequences of the deformation are rather severe. First, it increases contact area and therefore reduces resolution. Second, the height profile of the surface can be underestimated. Third, the original structure of the sample can be destroyed irreversibly. Furthermore, the tip itself can be deformed when imaging hard samples [239]. 

When subjected to an applied stress, polymers may deform by either or both of two fundamentally different atomistic mechanisms. The lengths and angles of the chemical bonds connecting the atoms may distort, moving the atoms to new positions of greater internal energy. This is a small motion and occurs very quickly, requiring only 10 [-12] seconds [25],... 

In practice, many fabrication processes take place under non-isothermal, non-quiescent and high-pressure conditions. Mechanical deformation and pressure can enhance the crystallisation as well as the crystal morphology, by aligning the polymer chains. This leads to pressure-induced crystallisation and to flow-induced or stress-induced crystallisation, which in fact is the basis for fibre melt-spinning (see Sect. 19.4.1)... 

Plastic crystals present many challenges in terms of elucidating the mechanisms of rotational motion, conduction, diffusion, mechanical deformation, and the interrelationship between these mechanisms. Then there is the broader challenge of understanding the effect of doping or mixing these systems with additional components such as acids, inorganic salts, and polymers on these transport mechanisms. 

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