Crystallization in rubber

Well known examples of orientation induced crystallization are the stretching of rubber, fiber orientation in polyamides and polyesters, and the biaxial stretching of polycarbonate filuK. An example of thermal effects during induct crystallization in rubber is shown in Fig. 45, where the heat flow (Q) for successive steps of elongation and retraction is plotted as a function of time. 

The development of crystallization in rubber depends on the temperature and the degree of deformation. The optimum conditions for crystallization are obtained when the temperature and the deformation are such that the molecules have sufficient energy and mobility to associate in an ordered way, but not sufficient to dissociate under the influence of random thermal motion. In the undeformed state, there is in general a temperature, different for each polymer, at which crystallization takes place most rapidly. 

Stretching a polymer sample tends to orient chain segments and thereby facilitate crystallization. The incorporation of different polymer chains into small patches of crystallinity is equivalent to additional crosslinking and changes the modulus accordingly. Likewise, the presence of finely subdivided solid particles, such as carbon black in rubber, reinforces the polymer in a way that imitates the effect of crystallites. Spontaneous crystal formation and reinforcement... 

Zinc dithiocarbamates have been used for many years as antioxidants/antiabrasives in motor oils and as vulcanization accelerators in rubber. The crystal structure of bis[A, A-di- -propyldithio-carbamato]zinc shows identical coordination of the two zinc atoms by five sulfur donors in a trigonal-bipyramidal environment with a zinc-zinc distance of 3.786 A.5 5 The electrochemistry of a range of dialkylthiocarbamate zinc complexes was studied at platinum and mercury electrodes. An exchange reaction was observed with mercury of the electrode.556 Different structural types have been identified by variation of the nitrogen donor in the pyridine and N,N,N, N -tetra-methylenediamine adducts of bis[7V,7V-di- .vo-propyldithiocarbamato]zinc. The pyridine shows a 1 1 complex and the TMEDA gives an unusual bridging coordination mode.557 The anionic complexes of zinc tris( V, V-dialkyldithiocarbamates) can be synthesized and have been spectroscopically characterized.558... 

The stretching of amorphous but crystallizable materials can greatly increase the rate of crystallization in some cases. Natural rubber and polyethylene terephthalate are examples. The stretching of the polymer initially causes the crystallites to grow so that the chains in the crystallites are oriented parallel to the applied stress. Thus the growth of the crystallites... 

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. 

Attenuated total reflection (ATR) is the most common reflectance measurement modahty. ATR spectra cannot be compared to absorption spectra. While the same peaks are observed, their relative intensities differ considerably. The absorbances depend on the angle of incidence, not on sample thickness, since the radiation penetrates only a few micrometers into the sample. The major advantage of ATR spectroscopy is ease of use with a wide variety of solid samples. The spectra are readily obtainable with a minimum of preparation Samples are simply pressed against the dense ATR crystal. Plastics, rubbers, packaging materials, pastes, powders, solids, and dosage forms such as tablets can all be handled directly in a similar way. 

In rubber-plastic blends, clay reportedly disrupted the ordered crystallization of isotactic polypropylene (iPP) and had a key role in shaping the distribution of iPP and ethylene propylene rubber (EPR) phases larger filler contents brought about smaller, less coalesced and more homogeneous rubber domains [22]. Clays, by virtue of their selective residence in the continuous phase and not in the rubber domains, exhibited a significant effect on mechanical properties by controlling the size of rubber domains in the heterophasic matrix. This resulted in nanocomposites with increased stiffness, impact strength, and thermal stability. 

Polymer bonded explosives (PBXs) were developed to reduce the sensitivity of the newly-synthesized explosive crystals by embedding the explosive crystals in a rubber-like polymeric matrix. The first PBX composition was developed at the Los Alamos Scientific Laboratories in USA in 1952. The composition consisted of RDX crystals embedded in plasticized polystyrene. Since 1952, Lawrence Livermore Laboratories, the US Navy and many other organizations have developed a series of PBX formulations, some of which are listed in Table 1.2. 

Cl pigment blue 15, Cl No. 74160, is an alpha crystal that offers a red shade and the poorest stability of the copper phthalocyanines and as such is referred to as a crystallizing red-shade (CRS) blue. This grade is most often used in rubber and flexible PVC applications. Care must be exercised during the use of PB 15 since this crystal type has poor heat resistance at temperatures above 425°F (218°C) temperatures at which the pigment will likely revert to the more stable, green-shade beta crystal. 

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