Rubbers rubber under stress

Finally, a few articles have appeared on chemiluminescence of polymers. This technique has been used to detect hydroxy radicals in wood oxidation,y-irradiation effects on polyethylene, oxidation of nitrile-butadiene rubber, rubber under stress,antioxidant efficiencies in polyethylene, reactions of peroxy radicals, stereoregularity in poly(propylene), colour development in epoxy resins and structural changes in thermally aged poly(phenylene sulfide). ... 

The ozone concentration in the atmosphere is only a few pphm. In certain chemical plants as in electrolytic mercury cell houses in the chloralkali industry, the ozone concentration is higher. Although the atmospheric ozone level is low, it reacts with rubber double bonds rapidly and causes cracking of rubber products. Especially when rubber is under stress (stretching and bending as in the case of flexible cell covers), the crack development is faster. Neoprene products resist thousands of parts per hundred million of ozone for hours without surface cracking. This nature of neoprene is quite suitable for cell house application in chlor-alkali industries. Natural rubber will crack within minutes when subjected to ozone concentration of only 50 pphm. 

Creep - The deformation in either vulcanized or un-vulcanized rubber under stress that occurs in time after the immediate deformation. 

In order to deal with the four non-crystalline forms in a unified way, we define a network chain in a crosslinked system, as the section of network between neighbouring crosslinks (Fig. 3.6). The shape of both a network chain in a rubber, and a molecule in a polymer melt, can be changed dramatically by stress, and both can respond elastically. However, when the polymer is cooled below Tg, the elastic strains are limited to a few per cent (unless a glassy polymer yields), so the molecular shape is effectively fixed. If the melt or rubber was under stress when cooled, the molecular shape in the glass is non-equilibrium. This molecular orientation may be deliberate, as in biaxially stretched polymethylmethacrylate used in aircraft windows, or a by-product of processing, as the oriented skin on a polystyrene injection moulding. Details are discussed in Chapter 5. 

Finally, as rubber ages, further slower creep may take place as covalent bonds in the chains are broken by degradation reactions, a process that can be hastened when the rubber is under stress. 

FIGURE 7.16 Joints for rubber under stress (a) equal modulus and (b) unequal modulus [11]. 

Natural rubber is composed of polymerized isoprene units. When rubber is under tension, ozone attacks the carbon-carbon double bond, breaking the bond. The broken bond leaves adjacent C = C bonds under additional stress, eventually breaking and placing shll more stress on surrounding C = C bonds. This "domino" effect can be discerned from the structural formulas in Fig. 9-4. The number of cracks and the depth of the cracks in rubber under tension are related to ambient concentrations of ozone. 

When diene rubbers are exposed to ozone under stressed conditions cracks develop which are perpendicular to the direction of stress. Whilst ozone must react with unstressed rubber no cracking occurs in such circumstances nor when such rubber is subsequently stressed after removal of the ozone environment. For many years such rubbers were protected by waxes which bloomed on to the surface of the rubber to form an impermeable film. This was satisfactory for static applications but where the rubber was operating under dynamic conditions the wax layer became broken and hence less effective. 

Stress factors Sustained stress, cyclic stress, compression set (in rubbers) under continuous loading... 

FIGURE 26.47 Two-dimensional stress pattern in a transparent rubber block under a line force under polarized bgbt. (From ScbaUamacb, A., Wear, 13, 13, 1969.)... 

According to the importance of the cross-links, various models have been used to develop a microscopic theory of rubber elasticity [78-83], These models mainly differ with respect to the space accessible for the junctions to fluctuate around their average positions. Maximum spatial freedom is warranted in the so-called phantom network model [78,79,83], Here, freely intersecting chains and forces acting only on pairs of junctions are assumed. Under stress the average positions of the junctions are affinely deformed without changing the extent of the spatial fluctuations. The width of their Gaussian distribution is predicted to be... 

Hence, the elastic modulus corresponds in principle to the force per square millimeter that is necessary to extend a rod by its own length. Materials with low elastic modulus experience a large extension at quite low stress (e.g., rubber, = 1 N/mm ). On the other hand, materials with high elastic modulus (e.g., polyoxymethylene, s 3500 N/mm ) are only slightly deformed under stress. Different kinds of elastic modulus are distinguished according to the nature of the stress applied. For tension, compression, and bending, one speaks of the intrinsic elastic modulus ( modulus). For shear stress (torsion), a torsion modulus (G modulus) can be similarly defined, whose relationship to the modulus is described in the literature. 

An important feature of filled elastomers is the stress softening whereby an elastomer exhibits lower tensile properties at extensions less than those previously applied. As a result of this effect, a hysteresis loop on the stress-strain curve is observed. This effect is irreversible it is not connected with relaxation processes but the internal structure changes during stress softening. The reinforcement results from the polymer-filler interaction which include both physical and chemical bonds. Thus, deforma-tional properties and strength of filled rubbers are closely connected with the polymer-particle interactions and the ability of these bonds to become reformed under stress. 

Processing Stability. As with elastomers or other rubber modified polymers, the presence of double bonds in the elastomeric phase increases sensitivity to thermal oxidation either during processing or end use. Antioxidants are generally added at the compounding step to ensure retention of physical properties. Physical effects can also have marked effects on mechanical properties due to orientation, molded-in stress, and the agglomeration of dispersed rubber particles under very severe conditions. Proper drying conditions are essential to prevent... 

Liquid nitrogen and its vapor are extremely cold and can rapidly freeze human tissue. Liquid nitrogen spills should be flushed with water to accelerate evaporation. When exposed to liqiud nitrogen, carbon steel, rubber, and plastic become embrittled and may fracture under stress. 

Typical examples of stress corrosion are crack formation in strained rubber vulcanizates under the influence of ozone, hair cracks in PE under stress in the presence of a surface active agent (see also 7.4.2), crack formation in PC, when exposed to e.g. CCI4, within a few seconds after the application of a small stress. 

The ozone sensitivity of natural rubber under mechanical stresses double bonds are broken an example is found in, e.g. laboratories where glass tubes are connected with rubber hoses at the connection where the rubber is subjected to stresses, in the long run little tears are formed. 

A critical requirement for obtaining engineering properties from a rubbery material is its existence in a network structure. Charles Goodyear s discovery of vulcanization changed natural rubber from a material that became sticky when hot and brittle when cold into a material that could be used over a wide range of conditions. Basically, he had found a way to chemically connect the individual polymer chains into a three-dimensional network. Chains that previously could flow past one another under stress now had only limited extensibility, which allowed for the support of considerable stress and retraction upon release of the stress. The terms vulcanization, rubber cure, and cross-linking all refer to the same general phenomenon. 

If the rubber is evenly dispersed throughout the polystyrene matrix, cracks which form under stress soon encounter a rubber particle during propagation through the material thus further progress of the crack is hindered by the energy absorbing properties of the rubber. 

From a rubber it is essentially demanded to elongate under stress, to withstand stress without breaking and to reversibly find back to its original shape after the stress ceases. An unfilled, cured polymer will rarely fulfill these requirements this is a fact, which is true for most rubber-like systems. The industrial development of elastomers therefore is strongly related to the production of active reinforcing fillers. 

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