Rubber compounding polymers

H. Ismail, A.M.Norjulia, andZ. Ahmad, Theeffectsofuntreatedandtreatedkenafloading on the properties of kenaf fibre-filled natural rubber compounds. Polym. Plast. Technol. Eng. 49(5), 519-524(2010). 

The basic properties of polymers may be enhanced by physical as well as chemical means. An important example is the use of finely divided carbon black as a filler in rubber compounds. Polymers may be combined with stiffer filaments, such as glass or carbon fibres, to form a composite. We shall show later that some semicrystalline polymers may be treated as composites at a molecular level. 

Arroyo M, Lopez-Manchado M A and Herrero B (2003) Organo-montmorillonite as substitute of carbon black in natural rubber compounds, Polymer 44 2447-2453. 

M.A. Lopez Manchado, M. Arroyo. Short fibers as reinforcement of rubber compounds. Polym. Compos., 23 (4), 666-673,2002. 

Silicone Rubber. These polymers are based on chains of siUcon rather than carbon atoms, and owe thek temperature properties to thek unique stmcture. The most common types of siUcone mbbers are specifically and almost exclusively the polysdoxanes. The Si—O—Si bonds can rotate much more freely than the C—C bond, or even the C—O bond, so the siUcone chain is much more flexible and less affected by temperature (see Silicon COMPOUNDS, silicones). 

Manganese, copper, iron, cobalt and nickel ions can all initiate oxidation. Untinned copper wire can have a catastrophic effect on natural rubber compounds with which it comes into contact. Inert fillers for use in rubbers are usually tested for traces of such metal ions, particularly copper and manganese. The problem is perhaps less serious in saturated hydrocarbon polymers but still exists. 

The Auger depth profile obtained from a plasma polymerized acetylene film that was reacted with the same model rubber compound referred to earlier for 65 min is shown in Fig. 39 [45]. The sulfur profile is especially interesting, demonstrating a peak very near the surface, another peak just below the surface, and a third peak near the interface between the primer film and the substrate. Interestingly, the peak at the surface seems to be related to a peak in the zinc concentration while the peak just below the surface seems to be related to a peak in the cobalt concentration. These observations probably indicate the formation of zinc and cobalt complexes that are responsible for the insertion of polysulfidic pendant groups into the model rubber compound and the plasma polymer. Since zinc is located on the surface while cobalt is somewhat below the surface, it is likely that the cobalt complexes were formed first and zinc complexes were mostly formed in the later stages of the reaction, after the cobalt had been consumed. 

In general, the reaction mechanism of elastomeric polymers with vulcanisation reagents is slow. Therefore, it is natural to add special accelerators to rubber compounds to speed the reaction. Accelerators are usually organic compounds such as amines, aldehyde-amines, thiazoles, thiurams or dithio-carbamates, either on their own or in various combinations. 

Report 139 Rubber Analysis - Polymers, Compounds and Products, M.J. Forrest, Rapra Technology Ltd. 

The most prevalent approach to achieve long-lasting and nonstaining ozone protection of rubber compounds is to use an inherently ozone-resistant, saturated backbone polymer in blends with a diene rubber. The ozone-resistant polymer must be used in sufficient concentration (minimum 25 phr) and must also be sufficiently dispersed to form domains that effectively block the continuous propagation of an ozone-initiated crack through the diene rubber phase within the compound. Elastomers such as ethylene-propylene-diene terpolymers, halogenated butyl mbbers, or brominated isobutylene-co-para-methylstyrene elastomers have been proposed in combination with NR and/or butadiene rubber. 

FIGURE 26.56 Log Abrasion loss by a blade (solid lines) and log cut growth rate (dashed hnes) of noncrystallizing rubber compounds as function of log frictional and log tearing energy, respectively isomerized natural rubber (NR), 2 styrene-butadiene rubber (SBR), and 3 acrylate-butadiene rubber (ABR). (From Champ, D.H., Southern, E., and Thomas, A.G., Advances in Polymer Friction and Wear, Lieng Huang Lee (ed.), Plenum, New York/London, 1974, p. 134.)... 

Li, S., Lamminmaki, J., and Hanhi, K., Improvement of mechanical properties of rubber compounds using waste rubber/virgin rubber, Polym. Eng. Sci., 45, 1239, 2005. 

Ishiaku, U.S., Chong, C.S., and Ismail, H., Cure characteristics and vulcanizate properties of blends of a rubber compound and its recycled DE-VULC, Polym. Polym. Comp., 6, 399, 1998. 

Infrared spectroscopy is a major tool for polymer and rubber identification [11,12]. Infrared analysis usually suffices for identification of the plastic material provided absence of complications by interferences from heavy loadings of additives, such as pigments or fillers. As additives can impede the unambiguous assignment of a plastic, it is frequently necessary to separate the plastic from the additives. For example, heavily plasticised PVC may contain up to 60% of a plasticiser, which needs to be removed prior to attempted identification of the polymer. Also an ester plasticiser contained in a nitrile rubber may obscure identification of the polymer. Because typical rubber compounds only contain some 50% polymer direct FUR analysis rarely provides a definitive answer. It is usually necessary first... 

Analytical techniques used in troubleshooting and formulation experimentation available to the rubber compounder were reviewed [90]. Various textbooks deal with the analysis of rubber and rubber-like polymers [10,38,91]. Forrest [38] has illustrated the use of wet chemistry, spectroscopic, chromatographic, thermal, elemental and microscopy techniques in rubber analysis. 

Alternative approaches consist in heat extraction by means of thermal analysis, thermal volatilisation and (laser) desorption techniques, or pyrolysis. In most cases mass spectrometric detection modes are used. Early MS work has focused on thermal desorption of the additives from the bulk polymer, followed by electron impact ionisation (El) [98,100], Cl [100,107] and field ionisation (FI) [100]. These methods are limited in that the polymer additives must be both stable and volatile at the higher temperatures, which is not always the case since many additives are thermally labile. More recently, soft ionisation methods have been applied to the analysis of additives from bulk polymeric material. These ionisation methods include FAB [100] and LD [97,108], which may provide qualitative information with minimal sample pretreatment. A comparison with FAB [97] has shown that LD Fourier transform ion cyclotron resonance (LD-FTTCR) is superior for polymer additive identification by giving less molecular ion fragmentation. While PyGC-MS is a much-used tool for the analysis of rubber compounds (both for the characterisation of the polymer and additives), as shown in Section 2.2, its usefulness for the in situ in-polymer additive analysis is equally acknowledged. 

For the extraction of rubber and rubber compounds a wide variety of solvents (ethyl acetate, acetone, toluene, chloroform, carbon tetrachloride, hexane) have been used [149]. Soxtec extraction has also been used for HDPE/(Tinuvin 770, Chimassorb 944) [114] and has been compared to ultrasonic extraction, room temperature diffusion, dissolution/precipitation and reflux extraction. The relatively poor performance of the Soxtec extraction (50% after 4h in DCM) as compared with the reflux extraction (95% after 2-4 h in toluene at 60 °C) was described to the large difference in temperature between the boiling solvents. Soxtec was also used to extract oil finish from synthetic polymer yam (calibration set range of 0.18-0.33 %, standard error 0.015 %) as reference data for NIRS method development [150]. 

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