Elastomers orientation

NR and SBR blends including carbon black were subjected to large prestrain while storage and loss modulus were measured. The loss modulus was independent of pre-strain except at high carbon black loading of 50% where an increase was found at extension ratio of less than 2. The increase of loss modulus was interpreted as due to elastomer orientation and slip at the polymer-filler interface. Both events are non-linear, with orientation transient crystals formed, while interfadal rupture is an irreversible event for the original structure. 

Keywords Disorder Liquid crystal elastomer Orientational order Positional order Random field X-ray scattering... 

Figure Bl.19.35. Experimental nanoindentation eurves obtained with the AFM showing the loading and unloading behaviour of (a) an elastomer and highly oriented pyrolytie graphite and (b) a gold foil. (Taken from [183]. figure 4.)...

Acrylonitrile (AN), C H N, first became an important polymeric building block in the 1940s. Although it had been discovered in 1893 (1), its unique properties were not realized until the development of nitrile mbbers during World War II (see Elastomers, synthetic, nitrile rubber) and the discovery of solvents for the homopolymer with resultant fiber appHcations (see Fibers, acrylic) for textiles and carbon fibers. As a comonomer, acrylonitrile (qv) contributes hardness, rigidity, solvent and light resistance, gas impermeabiUty, and the abiUty to orient. These properties have led to many copolymer apphcation developments since 1950. 

The properties of elastomeric materials are also greatly iafluenced by the presence of strong interchain, ie, iatermolecular, forces which can result ia the formation of crystalline domains. Thus the elastomeric properties are those of an amorphous material having weak interchain iateractions and hence no crystallisation. At the other extreme of polymer properties are fiber-forming polymers, such as nylon, which when properly oriented lead to the formation of permanent, crystalline fibers. In between these two extremes is a whole range of polymers, from purely amorphous elastomers to partially crystalline plastics, such as polyethylene, polypropylene, polycarbonates, etc. 

However, conductive elastomers have only ca <10 of the conductivity of soHd metals. Also, the contact resistance of elastomers changes with time when they are compressed. Therefore, elastomers are not used where significant currents must be carried or when low or stable resistance is required. Typical apphcations, which require a high density of contacts and easy disassembly for servicing, include connection between Hquid crystal display panels (see Liquid crystals) and between printed circuit boards in watches. Another type of elastomeric contact has a nonconducting silicone mbber core around which is wrapped metalized contacts that are separated from each other by insulating areas (25). A newer material has closely spaced strings of small spherical metal particles in contact, or fine soHd wires, which are oriented in the elastomer so that electrical conduction occurs only in the Z direction (26). 

Resultant multiphase copolymers displayed properties ranging from soluble thermoplastic elastomers and engineering polymers to intractable thermosets, depending on the backbone composition and orientation, and especially the level of ODA incorpora-... 

Deloche, B., Samulski, E. T. Short-range nematic-like orientational order in strained elastomers a deuterium... 

Uniaxial deformations give prolate (needle-shaped) ellipsoids, and biaxial deformations give oblate (disc-shaped) ellipsoids [220,221], Prolate particles can be thought of as a conceptual bridge between the roughly spherical particles used to reinforce elastomers and the long fibers frequently used for this purpose in thermoplastics and thermosets. Similarly, oblate particles can be considered as analogues of the much-studied clay platelets used to reinforce a variety of materials [70-73], but with dimensions that are controllable. In the case of non-spherical particles, their orientations are also of considerable importance. One interest here is the anisotropic reinforcements such particles provide, and there have been simulations to better understand the mechanical properties of such composites [86,222],... 

IR dichroism has also been particularly helpful in this regard. Of predominant interest is the orientation factor S=( 1/2)(3—1) (see Chapter 8), which can be obtained experimentally from the ratio of absorbances of a chosen peak parallel and perpendicular to the direction in which an elastomer is stretched [5,249]. One representation of such results is the effect of network chain length on the reduced orientation factor [S]=S/(72—2 1), where X is the elongation. A comparison is made among typical theoretical results in which the affine model assumes the chain dimensions to change linearly with the imposed macroscopic strain, and the phantom model allows for junction fluctuations that make the relationship nonlinear. The experimental results were found to be close to the phantom relationship. Combined techniques, such as Fourier-transform infrared (FTIR) spectroscopy combined with rheometry (see Chapter 8), are also of increasing interest [250]. 

Figure 2. Scattering intensity versus azimuthal angle for a uniaxially oriented elastomer, X is 3, x is 0.2. Phantom network where , f is 3 A, f is 4 V, f is 10. Crosslink junctions fixed, X.

The synthesis and phase behavior of the model polydiethylsiloxane networks have also been studied. The networks were made by hydrosilylation of well-defined vinyl and allyl telechelic siloxanes obtained by kinetically controlled polymerization of cyclic trisiloxane.314 The effects of molecular weight between the cross-linkings on segment orientation in polydiethylsiloxane elastomers were studied.315... 

Both thermoplastics and thermosets can be used in four of the five major application areas plastics, elastomers, coatings, and adhesives. But, only thermoplastics can be used in making fibers. During the spinning and drawing process of fiber processing, it s necessary to orient the molecules. Only unbranched, linear polymers (not thermosets) are capable of orientation. 

Polymers have been valued since antiquity for their solid state properties. By this is meant their ability to undergo chain entanglement or co-linear orientation and microcrystalll-zatlon in the solid state. This underlies their use as structural materials, films, fibers, and elastomers. Such properties still constitute the driving force for most pol)nner-orlented research, especially with respect to the synthesis of heat-stable, radiation-stable, or highly flexible materials. 

Atomic force microscopy and attenuated total reflection infrared spectroscopy were used to study the changes occurring in the micromorphology of a single strut of flexible polyurethane foam. A mathematical model of the deformation and orientation in the rubbery phase, but which takes account of the harder domains, is presented which may be successfully used to predict the shapes of the stress-strain curves for solid polyurethane elastomers with different hard phase contents. It may also be used for low density polyethylene at different temperatures. Yield and rubber crosslink density are given as explanations of departure from ideal elastic behaviour. 17 refs. 

In shear yielding, oriented regions are formed at 45° angles to the stress. No void space is produced in shear yielding. Crazing often occurs prior to and in front of a crack tip. As noted earlier, the craze portion contains both fibrils and small voids that can be exploited after the stress is released or if the stress is maintained. Since many materials are somewhat elastic, most plastics are not ideal elastomers and additional microscopic voids occur each time a material is stressed. 

Elastomers exhibit this behavior due to their unique, crosslinked structure (cf. Section 1.3.2.2). It has been found that as the temperatme of an elastomer increases, so does the elastic modulus. The elastic modulus is simply a measme of the resistance to the uncoiling of randomly oriented chains in an elastomer sample under stress. Application of a stress eventually tends to untangle the chains and align them in the direction of the stress, but an increase in temperatme will increase the thermal motion of the chains and make it harder to induce orientation. This leads to a higher elastic modulus. Under a constant force, some chain orientation will take place, but an increase in temperatme will stimulate a reversion to a randomly coiled conformation and the elastomer will contract. 

Most elastomers are amorphous, but those with regular structures can crystallize when cooled to extremely low temperatures. Vulcanized soft rubber, which has a low cross-link density, when stretched crystallizes in a reversible process, and the oriented polymer has a high modulus (high stress for small strains, i.e., stiffness) and high tensile strength. 

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