Vulcanisation Studies

Other recent applications of ToF-SIMS without XPS include the examination of PS [6, 17-19], polyethylene (PE) [20], carbon fibre reinforced epoxy resins [21], polyalkyl methacrylates [22], alkylketene dimers [23], perfluorinated polymers [24], perflnorinated ethers [25], polyethylene glycol (PEG) oligomers [15, 25-29], rubber [30], ethylene-tetrafluoroethylene copolymer [30], Nylon-6 [31], PC [32,33], PDMS [34], polypyrrole coated PS [35], poly-p-phenylene vinylene [36], butyl rubber [37], poly(4-vinyl phenol)/poly(4-vinyl pyridine blends) [38], polypyrrole-silica gel composites [39], y-glycidoxypropyl trimethoxy silane [40], triblock copolymer poly(ethylene glycol)- 3 poly(phenylene ethylene)- 3 poly(ethylene glycol) [41], ethylene-terephthalate-hydroxybenzoate copolymer [42], PS-polyvinyl methyl ether, polycarbonate - PS blends [43] and PDMS-urethane [44], 

Both ToF-SlMS and XPS [45] have been applied to polytetrafluoroethylene (PTFE) [46,47], polybutadiene [48], rubbers [49,50], acrylics [51,52], PE [53-55], PU [56], PS [57], polyvinylcarbazole [58] polymalic acid [59], poly-P-hydroxy butyrate [60], poly-P hydroxyvalecate [60], y-glycidoxy propyl trimethoxy-silane [61], polypyrrole [62] and acrylonitrile-butadiene rubber [63]. 

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After these early studies an extensive FT-Raman study [77] was performed to bridge the gap between the low-molecular-weight ENBH model vulcanisation studies and the vulcanisation studies using high-molecular-weight EPDM. These studies will be presented in detail. First, a series of low-molecular-weight dialkenylsulfides will be discussed in order to determine the effect of sulfur vulcanisation on Raman spectra of olefins. Subsequently, the attachment of the sulfur crosslinks at the allylic positions, the conversion of ENB, the length of sulfur crosslinks and the network structure will be addressed for unfilled sulfur vulcanisates of amorphous EPDM. Some preliminary network structure/ properties relationships will also be presented. 

A. B. Sullivan, C. J. Harm, and G. H. Kuhls, "Vulcanisation Chemistry— Fate of Elemental Sulfur and Accelerator during Scorch Delay as Studied by Modem HPLC", Paper No. 9, presented at the MGS Tubber Division Meeting Toronto, Canada, May 21 —24, 1991, American Chemical Society, Washington, D.C., 1991. 

The earliest study describing vulcanised polymers of esters of acryUc acid was carried out in Germany by Rohm (2) before World War I. The first commercial acryUc elastomers were produced in the United States in the 1940s (3—5). They were homopolymers and copolymers of ethyl acrylate and other alkyl acrylates, with a preference for poly(ethyl acrylate) [9003-32-17, due to its superior balance of properties. The main drawback of these products was the vulcanisation. The fully saturated chemical stmcture of the polymeric backbone in fact is inactive toward the classical accelerators and curing systems. As a consequence they requited the use of aggressive and not versatile compounds such as strong bases, eg, sodium metasiUcate pentahydrate. To overcome this limitation, monomers containing a reactive moiety were incorporated in the polymer backbone by copolymerisation with the usual alkyl acrylates. 

In Ancient Egypt mummies were wrapped in cloth dipped in a solution of bitumen in oil of lavender which was known variously as Syrian Asphalt or Bitumen of Judea. On exposure to light the product hardened and became insoluble. It would appear that this process involved the action of chemical cross-linking, which in modem times became of great importance in the vulcanisation of rubber and the production of thermosetting plastics. It was also the study of this process that led Niepce to produce the first permanent photograph and to the development of lithography (see Chapter 14). 

Antioxidants may be assessed in a variety of ways. For screening and for fundamental studies the induction period and rate of oxidation of petroleum fractions with and without antioxidants present provide useful model systems. Since the effect of oxidation differs from polymer to polymer it is important to evaluate the efficacy of the antioxidant with respect to some property seriously affected by oxidation. Thus for polyethylene it is common to study changes in flow properties and in power factor in polypropylene, flow properties and tendency to embrittlement in natural rubber vulcanisates, changes in tensile strength and tear strength. 

In a study on the identification of organic additives in rubber vulcanisates using mass spectrometry, Lattimer et al. [22] used direct thermal desorption with three different ionisation methods El, Cl and FI. Also, rubber extracts were examinated directly by four ionisation methods (El, Cl, FD and FAB). The authors did not report a clear advantage for direct analysis as compared to analysis after extraction. Direct analysis was a little faster, but the extraction methods were considered to be more versatile. 

FAB has been used to analyse additives in (un) vulcanised elastomer systems [92,94] and FAB matrices have been developed which permit the direct analysis of mixtures of elastomer additives without chromatographic separation. The T-156 triblend vulcanised elastomer additives poly-TMDQ (AO), CTP (retarder), HPPD (antiozonant), and TMTD, OBTS, MBT and A,lV-diisopropyl-2-benzothiazylsulfenamide (accelerators) were studied in three matrix solutions (glycerol, oleic acid, and NPOE) [94]. The thiuram class of accelerators were least successful. Mixture analysis of complex rubber vulcanisates without chromatographic separation was demonstrated. The differentiation of matrix ions from sample ions was enhanced by use of high-resolution acquisition. 

These are unstable forms of elements which decay by the emission of radiation. A radioactive isotope of an element behaves chemically in the same way as the non-radioactive form, but its radiation may be detected and measured by a suitable instrument. In the rubber industry radioactive isotopes are used in beta ray thickness gauges, in studying the precise role of sulphur in vulcanisation, in the speedy determination of tread wear in tyres, etc. See Beta Rays. 

The reduction in stress which takes place in a test strip of rubber held at constant elongation. Stress relaxation measurements are used in the study of the ageing of rubber vulcanisates, the degradation of the network structure resulting in a reduction of the tension. 

STUDIES ON VULCANISATION SYSTEMS USED IN THE MANUFACTURE OF LATEX PRODUCTS... 

DNPT)) were studied using a gas evolution apparatus. The decomposition temperature of ADC decreased with both DNPT and 4,4-oxybis(benzenesulphonyl hydrazide) (OBSH) blending and this affected the structure and properties of the resulting foams. Using a tube mould for an extrudate to vulcanise the NR/EPDM extradate in a hot air oven was found to control the expansion and foam dimensions. The NR compositions affected the foam structure and properties. 16 refs. 

An investigation is reported of the dynamic mechanical response of aluminium silicate filled closed cell microcellular ethylene-octene copolymer (Engage) vulcanisates. The effect of blowing agent, frequency and temperature on dynamic mechanical properties is studied, and the strain-dependent dynamic mechanical properties of microcellular Engage are also investigated. 25 refs. INDIA... 

A study was made of relationships between compound rheological properties, microwave vulcanisation parameters and accelerators on the quality of extruded EPDM foam seals for the automotive industry. The influence of these factors on cell size and structure, density and mechanical properties was investigated. Correlations were found between the chemical composition of the compound, variations in processing parameters and the quality of the finished product. 12 refs. 

TG-DTA Characterisation of carbon black [149], flammability evaluation [64], polymer degradation studies [65], ageing studies [70-72], product control [77, 81], combustion performance [83], safety evaluation [83], antioxidation activity [68], pyrolysis of rubbers [82], thermal stability [67, 69, 76, 77], interfacial junctions in viscoelastic composites [78], weathering [72], vulcanisation [73], oxidative behaviour [79], materials evaluation [80], failure analyses [81],... 

Schonherr [43] has described the combination of decomposition in a thermogravimetry oven and FTIR spectroscopy for the identification of base polymers in elastomers, as exemplified for nitrile rubber, and has presented infrared spectra for decomposition products of various rubbers. The same author [36] studied use of the integrated TG-FTIR system for the identification of sixteen vulcanised rubbers in mechanical goods reporting the characteristic infrared spectra of the degradation products at temperatures ranging from 334 °C to 635 °C. 

A TG-DTA study of the thermochemical processes occurring at vulcanisation temperatures with N-oxydiethylene-2-benzthiazyl sulphenamide and N-cyclohexyl-2-benzthiazyl sulphenamide and their mixtures with sulphur showed the formation of high molecular weight polysulphides [73]. The influence of metallic oxides (Fe203, Sn02) on hot air ageing of one-pack room temperature vulcanised fluorosilicone rubber has been studied by means of TG-DTA [74, 75]. TG-DTA and TG were both applied to study the thermal characteristics of room temperature vulcanised silicone rubber [76]. 

Resols (phenol-formaldehyde resins) are commercially used for effective crosslinking of EPDM in the production of thermoplastic vulcanisates [8]. General studies on rubber crosslinking for different diene rubbers are presented here. 

The technology of sulfur vulcanisation of unsaturated elastomers has evolved since Goodyear s invention in 1839. Scientific studies into the chemistry of sulfur vulcanisation started to appear in the late 1950s (for reviews see References [14-18]). Two experimental approaches can be distinguished the analysis of rubber vulcanisates themselves and the so-called low-molecular-weight model studies. 

In general, most of the problems encountered in the study of the chemistry of the sulfur vulcanisation of elastomers are also encountered in the study of peroxide-curing. In comparison with sulfur vulcanisation only a limited number of spectroscopic studies on peroxide-curing have been published. 

Raman and IR spectroscopic studies dealing with the qualitative and/or quantitative determination of rubber compounding ingredients, i.e., the elastomer itself [22, 26-31], fillers [32, 33], vulcanisation chemicals and other additives [34-37], are not included here. The same applies to studies dealing with the crosslinking of elastomers by means of chemicals other than sulfur or peroxide [38-41], self-crosslinking of elastomers blends [42-44], crystallisation (strain-induced) [45-48] and oxidation/ageing [49-53]. 

The results of the optical spectroscopy studies into sulfur vulcanisation of polydiene rubbers correspond well with the results obtained via low molecular weight model olefin studies and solid state 13C NMR studies. From all these studies the mechanism for accelerated sulfur vulcanisation as shown in Figure 6.2 has emerged [14-18], which is... 

The mechanism of the accelerated sulfur vulcanisation of EPDM is probably similar to that of the highly unsaturated polydiene rubbers. The vulcanisation of EPDM has been studied with emphasis on the cure behaviour and mechanical and elastic properties of the crosslinked EPDM. Hardly any spectroscopic studies on the crosslinking chemistry of EPDM have been published, not only because of the problems discussed in Section 6.1.3 but also because of the low amount of unsaturation of EPDM relative to the sensitivity of the analytical techniques. For instance, high-temperature magic-angle spinning solid-state 13C NMR spectroscopy of crosslinked EPDM just allows the identification of the rubber type, but spectroscopic evidence for the presence of crosslinks is not found [72]. 

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