Devulcanisation of truck tyre tread vulcanisates in supercritical carbon dioxide using diphenyl disulphide and 2,2- dithiobis(benzothiazole)
- Authors: Mabuto, Briswell , Ogunlanja, A
- Date: 2019
- Subjects: Vulcanization , Polymeric composites Rubber Carbon dioxide -- Thermal properties Environmental chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/40702 , vital:36224
- Description: A lot of work has been done in the recycling industry in an effort to increase the amount of reclaimed rubber used in new tyre formulations. The major drawback has been inferior physical and mechanical properties of reclaimed/virgin rubber blends in comparison to the virgin rubber material. Deterioration in these properties has been identified to be a result of chain degradation during reclamation processes as well as presence of crosslinks in the final reclaim product. Devulcanisation techniques have gained precedence due to the relatively improved properties of devulcanised/virgin rubber blends. The concept of devulcanisation is to reverse vulcanisation, resulting in total or partial cleavage of crosslinks. In this way, chain degradation is minimised while crosslink scission is maximised, thereby resulting in good quality devulcanised rubber. However, due to the persistence of chain degradation and crosslinks during devulcanisation processes, a very limited number of reports have claimed success in achieving this goal. Therefore there is still the need to develop a devulcanisation method that ensures improved quality and productivity of devulcanised rubber. Typical truck tyre tread vulcanisates were used for optimisation of time, temperature, heating rate, pressure and amount of devulcanising agent while monitoring percentage devulcanisation in supercritical carbon dioxide medium. Optimisation of the devulcanisation conditions was done by employing a twolevel central composite design in the isothermal and non-isothermal heating stages. This was followed by a single factor analysis of devulcanisation conditions in the non-isothermal stage. The effect of the presence of carbon black was investigated by comparing the percentage devulcanisation of carbon black filled and unfilled samples. The results show that supercritical carbon dioxide is an effective medium of devulcanisation using diphenyl disulphide (DD) and 2,2-dithiobis(benzothiazole) (MBTS). The relatively higher degree of devulcanisation observed during the non-isothermal stage compared to the isothermal stage, led to a shift of focus to non-isothermal devulcanisation. Temperature and time were found to have a significant antagonistic effect on the percentage devulcanisation, while changes in pressure above critical point and mass of devulcanising agent showed no effect on percentage devulcanisation. The heating rate was determined by the set-point, of which 180 ℃ set-point temperature resulted in desirable degree of devulcanisation for both DD and MBTS. 76.18 ± 5.50 % devulcanisation in 5 minutes at 102 ℃ was observed for DD whilst 70.92 ± 4.10 % devulcanisation in 4 minutes at 97 ℃ was observed for MBTS. Changes in pressure above critical point and mass of devulcanising agent used in devulcanisation showed no significant effect in the percentage devulcanisation and so they were kept constant at 80 bars and 1.00 % v (of weight of rubber sample) devulcanisation agent, respectively. The presence of carbon black was found to have an effect on the degree of devulcanisation; 87.95 % and 81.33 % devulcanisation was observed for unfilled samples devulcanised using DD and MBTS respectively. Thermogravimetric analysis of the natural rubber/styrene butadiene rubber (NR/SBR respectively) relative composition of devulcanisates indicated uneven devulcanisation when using DD, whereas MBTS did not show any form of preference. DD showed preference for NR devulcanisation over SBR. Further analysis of the sol and gel fractions were performed using; Differential Scanning Calorimetry, Fourier Transform Infrared Spectroscopy, Gel Permeation Chromatography and Gas Chromatography coupled with Mass Spectroscopy. Application of the optimised conditions to devulcanise ground tyre rubber (GTR) resulted in relatively lower degrees of devulcanisation for both DD and MBTS; 41.22 ± 4.22 and 22.41 ± 1.97 respectively. The differences in the degree of devulcanisation of the laboratory prepared vulcanisates and the GTR was determined to be due to sample differences; i.e. sample constituents, particle dimensions and crosslink network (crosslink distribution in particular).
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- Date Issued: 2019
A comparison of the vulcanisation of Polyisoprene by a range of Thiuram Diulfides
- Authors: Van Rooyen, Jason Leigh
- Date: 2007
- Subjects: Vulcanization , Vulcanization accelerators
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10399 , http://hdl.handle.net/10948/733 , Vulcanization , Vulcanization accelerators
- Description: This study was initiated in an attempt to investigate dithiocarbamic acid accelerated sulfur vulcanisation. This was, however, found impossible due to the innate instability of dithiocarbamic acids. The focus of the study was then shifted toward thiuram disulfide accelerated sulfur vulcanisation, with emphasis being placed on a rate comparison. Three groups of accelerators were investigated, namely the aromatic, linear aliphatic and cyclic aliphatic thiuram disulfide adducts. The analysis methods that were employed were conventional rubber (cis-1,4-polyisoprene) techniques coupled to model (squalene) compound investigations. The data that was collected consisted of rheometrical torque vs. time data in the rubber system while the data obtained in the model compound study consisted of sulfur and accelerator concentration data as determined by means of high performance liquid chromatography (HPLC). The aromatic accelerators were synthesised in our labs by means of an addition reaction between the aromatic amine and CS2 in basic medium and subsequent oxidation with K3Fe(CN)6, all in a 1:1 molar ratio. The reaction yield was low due to the instability of the dithiocarbamate intermediates and a sluggish oxidation reaction. In the rate constant determination a first order mathematical approach was used for the rubber system as crosslinking is considered to roughly obey first order kinetics. The model compound data was also found to more accurately fit the first order rate law, with an initial slopes method also being applied to the system to determine secondary rate constants and relative rates for the system. The determination of vulcanisation rate constants in the cis-1,4-polyisoprene system was a success, while the rate data determined by means of the squalene model was more related to the rate of accelerator and sulfur consumption as opposed to the rate of crosslinking as is the case with the rubber rate data. The sulfur first order rate data mirrored the rate data derived from the rubber system more closely than the corresponding accelerator rate data, the relative rate data determined by means of initial slopes method, proved that the homolytic cleavage of thiuram disulfides and the subsequent formation of accelerator polysulfides were not limiting steps. This is seen in the similar relative rate data derived from both the raw sulfur and accelerator data in systems that exhibit vastly different vulcanisation rates. Squalene was deemed a suitable model for the cis-1,4-polyisoprene system, although one should consider the extent of charring and solution effects in the individual systems to account for possible incongruities that may be observed between the rubber and simulated system. The lack of agreement between the rubber and model compound rate constant data lies in the fact that the rate of crosslinking is not simplistically related to the rate at which accelerator and sulfur is consumed, this being especially true for the rate at which the accelerator is consumed. Thus the discussion over the acceleratory rates in the various accelerator systems was limited to observations made in the rubber system, with the model compound data was used exclusively to elucidate mechanistic processes. It was discovered that the groups of accelerators examined, namely linear, cyclic and aromatic thiuram disulfide adducts, produced vastly varied rate data. The aromatic thiuram disulfide adducts had only a slight acceleratory effect on the rate of vulcanisation as compared to the unaccelerated sulfur system. The morpholine adduct had a moderately larger rate of acceleration followed by tetramethyl and tetrethylthiuram disulfide, with N’N-dicyclopentamethylenethiuram disulfide having the fastest rate of acceleration.
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- Date Issued: 2007