Mechanisms of antifatigue agents used in natural rubber

A large number of compounds containing quinonoid or hindered phenol functions were examined for their roles as antifatigue agents. Among the evaluated quinones and phenols expected to have macroalkyl radical scavenging ability, BQ, αTOC, γTOC and GM showed relatively good performance for fatigue resistance (although their performance was slightly less effective than the commercial aromatic amine antioxidants, IPPD and 6PPD). The compounds which were shown to have higher reactivity with alkyl radicals (via calculated reactivity indices) showed better fatigue resistance. This fact supports the suggestion that strong alkyl radical scavengers should be also effective antifatigue agents. Evidence produced based on calculation of reactivity indices suggests that the quinones examined react with alkyl radicals on the meta position of the quinone rings producing phenoxyl radicals. The phenoxyl radicals are expected either to disproportionate, to recombine with a further alkyl radical, or to abstract a hydrogen from another alkyl radical producing an olefine. The regeneration of quinones and formation of the corresponding phenols is expected to occur during the antifatigue activity. The phenol antioxidant, HBA is expected to produce a quinonoid compound and this is also expected to function in a similar way to other quinones. Another phenol, GM, which is also known to scavenge alkyl radicals showed good antifatigue performance. Tocopherols had effective antifatigue activity and are expected to have different antifatigue mechanisms from that of other quinones, hence αTOC was examined for its mechanisms during rubber fatiguing using HPLC analysis. Trimers of αTOC which were produced during vulcanisation are suggested to contribute to the fatigue activity observed. The evidence suggests that the trimers reproduce αTOC and a mechanism was proposed. Although antifatigue agents evaluated showed antifatigue activity, most of them had poor thermoxidative resistance, hence it was necessary to compensate for this by using a combination of antioxidants with the antifatigue agents. Reactive antioxidants which have the potential to graft on the polymer chains during reactive processing were used for this purpose. APMA was the most effective antioxidant among other evaluated reactive antioxidants. Although high ratio of grafting was achieved after optimisation of grafting conditions, it is suggested that this was achieved by long branches of APMA due to large extent of polymerisation. This is expected to cause maldistribution of APMA leading to reducing the effect of CB-D activity (while CB-A activity showed clear advantages for grafting). Further optimisation of grafting conditions is required in order to use APMA more effectively. Moreover, although synergistic effects between APMA and antifatigue agents were expected, none of the evaluated antifatigue agents, BQ, αTOC, γTOC and TMQ, showed significant synergism both in fatigue and thermoxidative resistance. They performed just as additives.

Functionalisation of polymers: reactive processing, structure and performance characteristics

The main aim of this work was to study the effect of two comonomers, trimethylolpropane trimethacrylate (TRIS) and divinylbenzene (DVB) on the nature and efficiency of grafting of two different monomers, glycidyl methacrylate (GMA) and maleic anhydride (MA) on polypropylene (P) and on natural rubber (NR) using reactive processing methods. Four different peroxides, benzoyl peroxide (BPO), dicumyl peroxide (DCP), 2,5-dimethyl-2,5-bis-(tert-butyl peroxy) hexane (t-101), and 1,1-di(tert-butylperoxy)-3,3,5-trimethyl cyclohexene (T-29B90) were examined as free radical initiators. An appropriate methodology was established and chemical composition and reactive processing parameters were examined and optimised. It was found that in the absence of the coagents DVB and TRIS, the grafting degree of GMA and MA increased with increasing peroxide concentration, but the level of grafting was low and the homopolymerisaton of GMA and the crosslinking of NR or chain scission of PP were identified as the main side reactions that competed with the desired grafting reaction in the polymers. At high concentrations of the peroxide T-101 (>0.02 mr) cross linking of NR and chain scission of PP became dominant and unacceptable. An attempt to add a reactive coagent, e.g. TRIS during grafting of GMA on natural rubber resulted in excessive crosslinking because of the very high reactivity of this comonomer with the C=C of the rubber. Therefore, the use of any multifunctional and highly reactive coagent such as TRIS, could not be applied in the grafting of GAM onto natural rubber. In the case of PP, however, the use of TRIS and DVB was shown to greatly enhance the grafting degree and reduce the chain scission with very little extent of monomer homopolymerisation taking place. The results showed that the grafting degree was increased with increasing GMA and MA concentrations. It was also found that T-101 was a suitable peroxide to initiate the grafting reaction of these monomers on NR and PP and the optimum temperature for this peroxide was =160°C. A very preliminary work was also conducted on the use of the functionalised-PP (f-PP) in the absence and presence of the two comonomers (f-PP-DVB or f-PP-TRIS) for the purpose of compatibilising PP-PBT blends through reactive blending. Examination of the morphology of the blends suggested that an effective compatibilisation has been achieved when using f-PP-DVB and f-PP-TRIS, however more work is required in this area.

Individual differences in work behaviour of blue-collar workers : a study of rubber tappers in Malaysia

This thesis examines individual differences in work behaviour of rubber tappers. The study examined sex, age, experience and race differences and their interactions with terrain on job performance, absenteeism, and job satisfaction of 1053 rubber tappers. Rubber tappers are unskilled blue-collar workers who essentially do the same type of work and are paid the same rates of pay. There are very few studies that have compared male and female blue-collar workers doing similar jobs in organisational settings. This study is one of the few investigations that examine sex differences in job performance of blue-collar workers doing same job using production data. Studies on age differences in work behaviour encounter numerous methodological difficulties such as high turnover, internal transfers and problems associated with age differences in educational levels. The participation of rubber tappers in this study is envisaged to overcome these difficulties because attrition rates of rubber tappers are low, and internal transfers are non existent. Further, the educational levels of rubber tappers are relatively similar across different age cohorts, as most rubber tappers have little or no education. Two measures of both job performance and absenteeism were derived from payroll records. The two job performance measures were total crop production and attendance. The two absenteeism measures were avoidable and unavoidable absence rates. Overall job satisfaction was determined using a 4-item scale. Significant sex, age, experience and race differences were obtained for job performance, absenteeism and job satisfaction. Significant interactive effects were also obtained for sex, age , experience, race and terrain for job performance and absenteeism. The results are discussed in relation to the abilities and motivation of rubber tappers. The implication of these findings for employee selection and human resource management in rubber estates is discussed.

Fatigue in rubber vulcanisates

A study has been made of the effect of single extensions and continuous fatigue on the structures of various natural rubber networks. The change in network structure of a conventional vulcanisate on a single extension manifests itself as permanent set. The change in network structure has been assessed by the use of the chemical probes, propan-2-thiol/piperidine, hexane-thiol/piperidine and triphenyl phosphine, which determine the polysulphide and disulphide crosslink densities and main chain modification respectively. The permanent set induced on a single extension of a conventional sulphur vulcanisate has been shown to result from the destruction and reformation of polysulphide crosslinks. The magnitude of the effect was dependent upon the degree of extension and showed a maximum at extensions corresponding to the onset of stress-induced crystallisation. The incorporation of a reinforcing filler, HAF-carbon black, magnified the effect. Vulcanisates that possessed only mono and disulphide crosslinks did not show any significant permanent set. The continuous changes in network structure during fatigue have also been determined, and the effects of carbon black and antioxidants on these changes and the fatigue life have been assessed. During fatigue the overall crosslink density increased slightly, which resulted from the destruction of polysulphide crosslinks. and their replacement by principally disulphide crosslinks. Antioxidants reduced the rate of destruction of polysulphide crosslinks and increased the fatigue life of the rubber network. The fatigue life of the network also depended upon the concentration of free chain ends. These chain ends were incorporated into the network by masticating rubber under nitrogen in the presence of bis (diisopropyl)thiophosphoryl disulphide, which improved the fatigue resistance by up to 9%.

Investigations into long-term productivity improvements in an automotive rubber concern

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The interaction between the implementation of an occupational health and safety management system and safety culture:a case study in the rubber industry

A prominent theme emerging in Occupational Health and Safety (OSH) is the development of management systems. A range of interventions, according to a prescribed route detailed by one of the management systems, can be introduced into an organisation with some expectation of improved OSH performance. This thesis attempts to identify the key influencing factors that may impact upon the process of introducing interventions, (according to B88800: 1996, Guide to Implementing Occupational Health and Safety Management Systems) into an organisation. To help identify these influencing factors a review of possible models from the sphere of Total Quality Management (TQM) was undertaken and the most suitable TQM model selected for development and use in aSH. By anchoring the aSH model's development in the reviewed literature a range ofeare, medium and low level influencing factors were identified. This model was developed in conjunction with the research data generated within the case study organisation (rubber manufacturer) and applied to the organisation. The key finding was that the implementation of an OSH intervention was dependant upon three broad vectors of influence. These are the Incentive to introduce change within an organisation which refers to the drivers or motivators for OSH. Secondly the Ability within the management team to actually implement the changes refers to aspects, amongst others, such as leadership, commitment and perceptions of OSH. Ability is in turn itself influenced by the environment within which change is being introduced. TItis aspect of Receptivity refers to the history of the plant and characteristics of the workforce. Aspects within Receptivity include workforce profile and organisational policies amongst others. It was found that the TQM model selected and developed for an OSH management system intervention did explain the core influencing factors and their impact upon OSH performance. It was found that within the organisation the results that may have been expected from implementation of BS8800:1996 were not realised. The OSH model highlighted that given the organisation's starting point, a poor appreciation of the human factors of OSH, gave little reward for implementation of an OSH management system. In addition it was found that general organisational culture can effectively suffocate any attempts to generate a proactive safety culture.