Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Heterophasic ethylene-propylene copolymers, also known as impact polypropylene (PP) copolymers (IPCs) or heterophasic copolymers (HECOs), are a unique group of polyolefins produced through the copolymerisation of ethylene and propylene, with the aim of improving the impact properties of the PP homopolymer at low temperatures. Therefore, this polymer comprises of a PP homopolymer matrix with a dispersed rubbery copolymer phase. Due to their unique properties, HECO polymers have become commercially important materials, with a wide range of applications. Therefore a fundamental understanding of the processes and chemistry that affects their final macroscopic properties needs to be expanded. The main focus of this investigation was to understand why specific organic peroxides influence or interact differently with the various phases of HECO polymers, in order to utilize their properties to obtain HECO polymers with optimal and desired properties. Two HECO polymers with different ethylene contents were fractionated into three fractions (30, 100 and 130 °C), using preparative temperature rising elution fractionation (P-TREF). Each individual TREF fraction was degraded with two different types of organic peroxides, and then characterised using four different analytical tools. The changes in the molecular structures of the different fractions were investigated by Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The changes in comonomer sequence distributions were investigated by carbon 13 nuclear magnetic resonance spectroscopy (13C-NMR). Moreover, the degradation of the different fractions was investigated by high temperature size exclusion chromatography (HT-SEC). The investigation showed that the HECO polymers with different ethylene contents were uniquely altered. It was evident that the ethylene content influenced the degradation behaviour of the HECO polymers. The ability of the peroxide to affect certain regions of the HECO polymer more than others is highly dependent upon its miscibility with certain regions of the HECO polymers. The “visbreaking” efficiency of a specific organic peroxide appears to be primarily dependent on the number of “peroxy” groups it contains in its molecular structure. Stellenbosch University https://scholar.sun.ac.za / AFRIKAANSE OPSOMMING: Heterofase etileen-propileen ko-polimere, ook bekend as impak PP ko-polimere (IPCS) of heterofase ko-polimere (HECO), is 'n unieke groep poliolefiene geproduseer deur die ko-polimerisasie van etileen en propileen, met die doel op die verbetering in die impak eienskappe van die PP homopolimeer by lae temperature. Hierdie polimeer bestaan dus uit 'n PP homopolimeer matriks met 'n verspreide rubberagtige ko-polimeer fase. As gevolg van hul unieke eienskappe, is HECO polimere van kommersiële belang, met 'n wye verskeidenheid van toepassings. 'n Fundamentele begrip van die prosesse en chemie wat die finale makroskopiese eienskappe beïnvloed moet dus uitgebrei word. Die hooffokus van hierdie ondersoek was om te verstaan waarom spesifieke organiese peroksiede verskillende invloede en interaksies met die verskillende fases van HECO polimere het, om sodoende van hul eienskappe gebruik te maak om HECO polimere te verkry met optimale en gewenste eienskappe. Twee HECO polimere met verskillende etileen inhoud was gefraksioneer in drie fraksies (30, 100 en 130 °C), met behulp van preparatiewe temperatuur styging eluering fraksionering (P-TREF). Elke individuele TREF fraksie was gedegradeer met twee verskillende tipes organiese peroksiede en daarna gekarakteriseer deur vier verskillende analitiese metodes. Die veranderinge in molekulêre strukture van die verskillende fraksies was geondersoek met behulp van Fourier transform infrarooi spektroskopie (FTIR) en differensiële skandering kalorimetrie (DSC). Die veranderinge in ko-monomeer volgorde distribusie was bestudeer deur middel van kern magnetiese resonans spektroskopie (KMR). Verder was die degradasie van die verskillende fraksies met behulp van hoë temperatuur grootte uitsluitingschromatografie (HT-SEC) bestudeer. Die ondersoek het getoon dat die HECO polimere met verskillende etileen inhoud uniek gedegradeer was. Dus is dit duidelik genoeg dat die etileen inhoud die degradasie gedrag van die HECO polimere beïnvloed het. Die vermoë van die peroksied om sekere areas van die HECO polimeer meer as ander te beïnvloed is hoogs afhanklik van die mengbaarheid met sekere areas van die HECO polimere. Die "visbreking" doeltreffendheid van 'n spesifieke organiese peroksiede is meestal afhanklik van die aantal "peroksie" groepe in die molekulêre struktuur.

L'atmosphère terrestre a subi, au cours de son histoire précoce, de très violents changements dans sa composition chimique. L'émergence des premiers êtres vivants photosynthétique a provoqué la mise en place et la modification des grands cycles biogéochimiques. L'usage des isotopes comme traceurs des processus physico-chimiques actifs pendant ces périodes s'est développé depuis les années 80. L'observation de compositions isotopiques anormales dans certaines molécules atmosphériques (ozone notamment), similaires à celles observées dans les météorites par Clayton (1973), pose question. De nombreuses hypothèses ont été proposées pour expliquer ce phénomène "anormal". L'objectif principal de cette thèse de doctorat est de développer, par l'expérimentation, l'étude d'un certain nombre de réactions en phase plasma du point de vue isotopique. Seront particulièrement étudiées des réactions appelées réactions à trois corps de formation de l'ozone, où la formation d'un complexe intermédiaire excité entre en jeu dans les mécanismes de génération de ces fractionnements isotopiques anormaux. / The Earth's atmosphere has undergone, during its early history, very violent changes in its chemical composition. The emergence of the first photosynthetic living beings has led to the establishment and modification of major biogeochemical cycles. The use of isotopes as tracers of active physico-chemical processes during these periods has been developed since the 1980s. The observation of abnormal isotopic compositions in certain atmospheric molecules (ozone in particular), similar to those observed in meteorites by Clayton (1973), raises questions. Many hypotheses have been proposed to explain this "abnormal" phenomenon. The main objective of this doctoral work is to develop, through experimentation, the study of plasma reactions from an isotopic point of view. In particular, ozone formation third-body reactions, where the formation of an excited intermediate complex is involved in the mechanisms of generating these abnormal isotopic fractionations, will be studied.

Cette thèse a pour but d’identifier et de préciser les processus biotiques et abiotiques qui contrôlent le comportement du Ca et plus spécifiquement le fractionnement des isotopes du Ca à l’interface géosphère-biosphère-hydrosphère en combinant différentes études expérimentales (hydroponiques et microcosmes). Les résultats obtenus lors des expérimentations hydroponiques ont permis d’identifier 3 niveaux de fractionnement des isotopes du Ca au sein des végétaux, ces 3 niveaux de fractionnement sont induits par des mécanismes physico-chimiques qui enrichissent les organes de végétaux en 40Ca.Les résultats des expérimentations hydroponiques montrent également que l’évolution de la composition isotopique du Ca de la solution nutritive et des plantes suit une loi de fractionnement des isotopes du Ca à l’équilibre (αplantes/solution nutritive = 0,99858). Les expérimentations abiotiques en microcosmes, quant à elles, indiquent que la dissolution de l’apatite par des acides organiques ou inorganiques n’influence pas la signature isotopique en Ca de la phase dissoute résultante. À l’inverse, lors des expérimentations biotiques en microcosmes, seule l’action combinée des racines de pins et des bactéries sur un substratum d’apatite enrichit la solution qui percole en 44Ca de 0,22‰. / The aim of this thesis is to identify and to specify biotic and abiotic processes affecting the Ca behavior and specifically the Ca isotope fractionation at the geosphere/biosphere/hydrosphere interface by combining different experimental studies (hydroponic and microcosm).Results of hydroponic experiments allow to identify three Ca isotopic fractionation levels, which are driven by physico-chemical mechanisms and enrich the plant organs in the light 40Ca isotope. Moreover, the evolution of Ca isotopic composition of nutrient solution and plants follow an equilibrium law (αplants/nutrient solution = 0.99858).Abiotic column experiments show no Ca isotopic fractonation during apatite disolution, whatever the nature of the acid (mineral or organic). At the opposite, during biotic microcosm experiments, only the combined action of roots of scots pines and bacteria on apatite substratum enrich the percolate solution in heavy 44Ca of 0.22‰.

The search for efficient and economical ways to beneficiate fine coal remains an active research area. Recent developments have shown that the reflux classifier can successfully be used on Australian coals, and based on that, a number of pilot plant investigations have been done in South Africa. While pilot scale units are usually used to test the applicability of a new technology on specific coals, a need exists to gather more fundamental data at a laboratory scale in order to save manpower, costs and time. This study has aimed at introducing a way to pre-test material prior to pilot plant trials in the design chain. The study shows that a laboratory water only reflux classifier can be used as a density fractionator, which accurately produces washability data for coal – this was also investigated by Callen et al. (2008). There is also a linear correlation between density cut-point and fluid velocity within the plates. Only when looking at the model proposed in Walton (2011:68), does it become clear that the relationship is indeed slightly curved. Many investigations from laboratory and pilot tests accept the linear relationship, and describe it as slightly curved due to the settling being in the intermediate settling regime (Iveson et al., 2014; Galvin & Lui, 2011). The separation procedures that produce two products – an overflow and underflow – compare well with fractionation results produced. Thus, fractionation results can generate washability data and predict batch separation operations. The laboratory reflux classifier setup is also dependent on particle size, where individual size ranges achieve e.p.m. values of 0.012 and 0.030, while the combined separation efficiency is 0.039. It was, however, found that the respective laboratory scale reflux classifier that was designed and built was not suitable for continuous operation. The vertical fluidisation section was not high enough to enable a steady fluidised bed. This was necessary for density separation within the bed and to produce a significant pressure differential. It is also recommended to obtain a PID controller. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

The search for efficient and economical ways to beneficiate fine coal remains an active research area. Recent developments have shown that the reflux classifier can successfully be used on Australian coals, and based on that, a number of pilot plant investigations have been done in South Africa. While pilot scale units are usually used to test the applicability of a new technology on specific coals, a need exists to gather more fundamental data at a laboratory scale in order to save manpower, costs and time. This study has aimed at introducing a way to pre-test material prior to pilot plant trials in the design chain. The study shows that a laboratory water only reflux classifier can be used as a density fractionator, which accurately produces washability data for coal – this was also investigated by Callen et al. (2008). There is also a linear correlation between density cut-point and fluid velocity within the plates. Only when looking at the model proposed in Walton (2011:68), does it become clear that the relationship is indeed slightly curved. Many investigations from laboratory and pilot tests accept the linear relationship, and describe it as slightly curved due to the settling being in the intermediate settling regime (Iveson et al., 2014; Galvin & Lui, 2011). The separation procedures that produce two products – an overflow and underflow – compare well with fractionation results produced. Thus, fractionation results can generate washability data and predict batch separation operations. The laboratory reflux classifier setup is also dependent on particle size, where individual size ranges achieve e.p.m. values of 0.012 and 0.030, while the combined separation efficiency is 0.039. It was, however, found that the respective laboratory scale reflux classifier that was designed and built was not suitable for continuous operation. The vertical fluidisation section was not high enough to enable a steady fluidised bed. This was necessary for density separation within the bed and to produce a significant pressure differential. It is also recommended to obtain a PID controller. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

Master of Science / Department of Geology / Sambhudas Chaudhuri / Rare earth element (REE) concentrations were measured in a source (reference) clay Ca-smectite standard and in the roots, stems, and leaves of a species of poplar plant (Populus eugenei). The poplar plant was grown in the clay standard under controlled laboratory conditions during a period of about three months. REEs were shown to fractionate in the clay mineral and plant materials with greater fractionation observed in plant materials. The REE data provide insight into the process of weathering of clay minerals such as a Ca-bearing smectite and provide insight into the degradation of and the composition of clay minerals in the plant environment. The degradation process is not followed by significant interlayer ion exchange effect on remaining clay minerals in the root environment. REEs were found to be transported into complex forms, potentially as REE-carboxylic anion pair complexes. The plant materials in this study were in general heavy REE (HREE) enriched relative to the source clay minerals due to the complexation effect. The REE anomalies observed in this study, in addition to the Ce and Eu anomalies, may be explained by the selective uptake by the plant by an enzyme effect rather than due to the influence of oxidation-reduction. The enzyme influence was more evident in the REE distribution when compared among the plant organs. These REE characteristics described for the plants may eventually be incorporated with data from numerous other studies and also used as a guide in the assessment of the contribution of plant materials to dissolved REE content in surface water and groundwater.

Thesis (PhD)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: Conventional, advanced and fractionation pretreatment technologies were employed to recover and/or enhance the efficacy of the main constituents present in lignocellulosic biomass. Bamboo and triticale bran are novel feedstocks and hence their response towards treatment is unknown. Thus, to assist with the characterisation of these feedstock, in terms of the amount of sugar released during acid and enzymatic hydrolysis, use were made of conventional pretreatment technologies. Pretreatment involved the use of either the conventional single-stage dilute-acid or the conventional acid-catalysed steam-explosion process at times, temperatures and acid concentration ranging between 5 to 40 min, 120 to 214°C, and 0.002 to 0.055 (H3O+) gmol/L, respectively. For additional comparison, results were also obtained from an established feedstock namely sugarcane bagasse, by subjecting it to the single-stage dilute-acid process, at similar pretreatment conditions employed during the treatment of the other feedstocks. Sugarcane bagasse and bamboo, upon pretreatment and enzymatic hydrolysis, both yielded a similar combined sugar recovery yield of 78.0% and 81.2%, respectively. Alternatively, only 55.3% (w/w) of the total sugar content in triticale bran could be recovered. Triticale bran consists predominantly of hemicellulose which, compared to cellulose, the main constituent in sugarcane bagasse and bamboo, is more susceptible to degradation. Thus, to enhance the combined sugar recovery yield, it is recommended that triticale bran be treated at less severe pretreatment conditions, in order to preserve the hemicellulose. To further enhance the amount of sugar (i.e. cellulose and hemicellulose) that can be recovered from sugarcane bagasse, the use of a two- rather than one-stage dilute acid process was proposed. The single-stage dilute acid process, despite being the subject of many research efforts, failed to recover more than 83% (w/w) of the total sugar content in sugarcane bagasse. Following an extensive literature study, it was concluded that sugarcane bagasse comprises a hemicellulose and cellulose fraction which dictates the use of different pretreatment conditions in order to ensure their effective recovery. The use of a more advance two-step dilute acid process was therefore proposed as it allows for multiple-sets of pretreatment conditions which accommodate the requirements set forth by each of the polysaccharides present in sugarcane bagasse. With the assistance of response surface methodology, a 4.8% (w/w) improvement over the single-stage method was calculated for the two-stage process, by assuming both pretreatment technologies operated at optimum pretreatment conditions. This improvement, which is similar to the 7.7% (w/w) obtained with substrates other than sugarcane bagasse, was accredited to the use of multiple-sets of pretreatment conditions. Both low and high severity pretreatment conditions were applied to maximise the recovery of hemicellulose and cellulose, respectively. In the case of bamboo however, little can be gained by using the two- in lieu of the one-stage method, as similar pretreatment conditions are required to maximise both hemicellulose and cellulose recovery. Alternatively, a three- rather than a two-stage process needs to be applied, when treating triticale bran, to accommodate for an additional set of pretreatment conditions required to recover arabinan, a third polysaccharide. In order to realise the full potential of sugarcane bagasse, use was made of a fractionation method, which in addition to the recovery of polysaccharide (i.e. cellulose and hemicellulose), also allowed for the recovery of the polyphenolic content (i.e. lignin) thereof. Limited by the complexity of the fractionation process, sugarcane bagasse was selected as the preferred substrate to be subjected to fractionation, mainly because of its availability in the South African (established sugar milling industry), and ease of treatment using both conventional (e.g. single-stage) and advanced (e.g. two-stage) pretreatment technologies. A novel fractionation technology, involving the use of the ionic liquid 1-butyl-3- mehylimidazolium methyl sulphate ([BMiM]MeSO4), was devised to separate the main constituents of sugarcane bagasse. Although other ionic liquid fractionation examples also exist in literature, processes used caused production of multi-component product streams with 34% (w/w) of the original lignin and hemicellulose being recovered in the same product stream. Tests conducted during the present study confirmed these results and further indicated that the production of multi-constituent product streams could not be avoided by using acetone, an acetone-water mixture or a sodium hydroxide solution as the solvent in a subsequent solvent extraction step. Hence, to avoid the production of multi-component product streams, a hemicellulose pre-extraction step, comprising the single-stage dilute acid process, was introduced to extract and recover 75% (w/w) of the hemicellulose content. The remaining solid was subjected to ionic liquid treatment whereafter it was effectively separated into cellulose and lignin enriched product streams through solvent extraction. Up to 73% (w/w) of the original lignin and cellulose content was recovered using optimum operating conditions (120 min; 125°C). Comparison of the novel ionic liquid ([BMiM]MeSO4) with 1-ethyl-3-methylimidazolium acetate, an established ionic liquid, identified the former to be the superior delignification solvent whereas the latter contributed more towards the digestibility of the residual solids. In conclusion, methods for the effective recovery of polysaccharides and polyphenol units from established (i.e. sugarcane bagasse) and novel (i.e. bamboo, triticale bran) lignocellulosic feedstocks have been demonstrated through the application of conventional (single-stage), advanced (two-stage) and fractionation pretreatment technologies. Economic improvement is promised through the application of these constituents as they may serve as precursor chemicals for the production of value-added products that may replace the fuel and chemicals currently derived from fossil carbon resources. / AFRIKAANSE OPSOMMING: Konvensionele, gevorderde en fraksionering voorafbehandeling tegnologieë is gebruik om die herwinning en gebruiksaamheid van die hoofbestanddele wat in lignosellulose biomassa aanwesig is, te verbeter. Bamboes en tritikale semels is nuwe rou materiale en dus is hul reaksie op behandeling onbekend. Ten einde die karaktereienskappe van hierdie rou materiale, in terme van die hoeveelheid suiker wat gedurende die suur- en suiker ensimatiese-hidrolise vrygestel word, te bepaal, is gebruik gemaak van konvensionele voorbehandeling tegnologieë. Voorbehandeling behels die gebruik van óf die konvensionele enkelstadium vedunde-suur óf die konvensionele suur-gekataliseerde stoomontploffingsproses; by tye, temperature en suurladings wat wissel tusen 5 en 40 minute, 120 tot 214°C, en 0.002 tot 0.055 (H3O+)gmol/L, onderskeidelik. Vir verdere vergelykings is resultate vanaf ’n gevestigde rou materiaal, naamlik suikerriet reste, verkry, deur dit te onderwerp aan ’n enkelstadium verdunde suur proses met dieselfde voorbehandeling toestande wat gegeld het gedurende die behandeling van die ander roumateriale. Tydens voorbehandeling en ensimaties-hidrolise het suikerriet reste en bamboes ’n gelyke gekombineerde terugwinnings opbrengs van 78.0% en 81.2% suiker, onderskeidelik, gelewer. Daar kon egter net 55.3% (w/w) van die totale suikerinhoud van tritikale semels herwin word. Tritikale semels bestaan hoofsaaklik uit hemisellulose, wat meer vatbaar is vir degradasie ten opsigte van sellulose, die hoof bestanddeel van suikerriet reste en bamboes. Om dus die gekombineerde suikerherwinnings-opbrengs te verbeter, word daar voorgestel dat tritikale semels aan minder strawwe toestande onderwerp word, om sodoende die hemisellulose te bewaar. Om verder die hoeveelheid suiker (d.w.s glukose en xilose) wat vanuit suikerriet reste herwin kan word, te verbeter, is die gebruik van ’n twee- in plaas van ’n eenstadium verdunde suur proses, voorgestel. Die enkelstadium verdunde suur proses het, ten spyte daarvan dat dit al die onderwerp van verskillende navorsing projekte was, nie daarin geslaag om meer as 83% (w/w) van die totale suikerinhoud vanuit die suikerriet reste te herwin nie. Na ’n uitgebreide literatuurstudie is daar tot die slotsom gekom dat suikerriet reste bestaan uit ’n hemisellulose deel en ’n sellulose deel wat die gebruik van verskillende voorbehandeling toestande noodsaak, om sodoende effektiewe herwinning daarvan te verseker. Die aanwending van ’n meer gevorderde twee-stap verdunde suur proses is dus voorgestel, aangesien dit van veelvoudige-stelle voorbehandelings toestande, soos vereis deur die polisakkariedes in suikerriet reste, gebruik maak. Deur die toepassing van reaksie oppervlakte metodologie, is ’n 4.2% verbetering op die enkel-stadium metode vir die twee-stadium proses behaal deur aan te neem dat beide van hierdie prosesse, by optimum kondisies vir maksimale suiker herwinning, uitgevoer is. Hierdie verbetering is soortgelyk aan die 7.7% (w/w) verbetering wat voorheen met andersoortige substrate (uitgesonder suikerriet reste) verkry is. Sodanige verhoging word toegeskryf aan die gebruik van veelvoudige stelle van voorbehandeling toestande, wat beide meer en minder strawwe toestande insluit, om sodoende die herwinning van xilose en glukose onderskeidelik te maksimeer. In die geval van bamboes, is die twee-stadium metode nie superieur tot die een-stadium metode nie, aangesien soortgelyke voorbehandeling-toestande benodig word om beide die herwinning van xilose en glukose te maksimeer. Alternatiewelik moet ’n drie-stadium in plaas van ’n twee-stadium proses gebruik word wanneer tritikale semels behandel word aangesien ’n bykomende stel voorbehandeling toestande benodig word om arabinan, ’n derde polisakkaried, te herwin. Om sodoende die volle potensiaal van suikerriet reste te ontgin, is gebruik gemaak van ʼn fraksioneringstegnologie. Waar konvensionele voorbehandeling metodes slegs fokus op die herwinning van polisakkariedes (naamlik sellulose en hemisellulose), kan die fraksioneringsproses ook die poli-fenoliese inhoud (naamlik lignien) in lignosellulose, herwin. Weens die ingewikkeldheid van die fraksioneringsproses, is suikerriet reste gekies as die mees geskikte substraat vir fraksionering, hoofsaaklik omdat dit veral in die Suid- Afrikaanse konteks, maklik beskikbaar is en omdat dit ook maklik is om met beide die konvensionele (bv. die enkel-stadium) en die gevorderde (bv. die twee-stadium) voorbehandeling proses behandel te word. ʼn Nuut ontwikkelde fraksionering tegnologie wat gebruik maak van die ioniese vloeistof 1-butiel-3-metielimidazolium metielsulfaat ([BMiM]MeSO4) is ontwikkel, om die hoofbestanddele in suikerriet reste van mekaar te skei. Literatuur bevat verskeie voorbeelde waar ioniese vloeistowe gebruik word vir fraksionering. Die doeltreffendheid van hierdie prosesse is egter deur die produksie van multi-komponent produkstrome, waartydens tot en met ekwivalente hoeveelhede hemisellulose en lignien in dieselfde produkstrome herwin is, beperk. Hierdie resultate is tydens die studie deur middel van toetse bevestig. Sodanige toetse het ook aangedui dat die produksie van multi-komponent produkstrome nie deur die gebruikmaking van asetoon, ʼn asetoon-water mengsel of ʼn natrium hidroksied oplosmiddel, wat deel maak van ʼn opvolgende oplossing-ekstraksie-stap, vermy kon word nie. Om gevolglik die vervaardiging van multi-komponent produkstrome te vermy, is ʼn hemisellulose vooraf-ekstraksie stap, bestaande uit die enkel-stap verdunde suur proses, gebruik, om sodoende 75% (w/w) van die hemisellulose inhoud in suikerriet reste, te herwin. Die oorblywende vastestof was onderwerp aan ioniese vloeistof behandeling waarna dit effektiewelik geskei is in onderskeidelik, sellulose en lignien verrykte produkstrome, verkry deur gebruikmaking van ʼn oplossing-ekstraksie-stap. Tot en met 73% (w/w) van die oorspronklike lignien en sellulose inhoud was herwin deur gebruik te maak van optimale behandelingskondisies (120 min, 125°C). ʼn Vergelyking tussen die nuut-geïdentifiseerde ioniese vloeistof ([BMiM]MeSO4) en 1-etiel-3-metielimidazolium asetaat, ʼn gevestigde ioniese vloeistof, het aangetoon dat eersgenoemde ʼn superieure delignifikasie oplosmiddel is terwyl laasgenoemde ʼn groter bydra tot die verteerbarheid van die oorblywende reste lewer. Ten slotte het hierdie studie, metodes vir die effektiewe herwinning van polisakkariedes en poli-fenoliese eenhede, vanaf gevestigde (bv. Suikerriet reste) en nuwe (bv. bamboes en tritikale semels) lignosellulose rou materiale, gedemonstreer, deur telkens van konvensionele (enkel-stadium), gevorderde (twee-stadium) en fraksionerings voorbehandeling tegnologieë gebruik te maak. Ekonomiese verbetering kan dus verwag word indien hierdie bestanddele as voorloper chemikalieë vir die produksie van waarde toegevoegde produkte aangewend word, aangesien sodanige produkte die plek kan inneem van brandstof en chemikalieë wat tans vanuit fossielbronne vervaardig word.

Mass dependent isotope fractionation of stable isotopes between meteorites and planetary materials has been used to assess processes that occurred during formation of Earth and its core. However, thus far little is known about the mass dependent isotope fractionation of Mo in the solar system, and at high temperatures in the Earth, in particular during mantle processes. Molybdenum is a refractory and moderately siderophile element. The processes that might have fractionated Mo in the early solar system include condensation and evaporation of dust grains, metal-silicate segregation, core crystallization, silicate and sulphide melting and aqueous alteration. In order to investigate the processes fractionating Mo isotopes, it is first necessary to assess how much fractionation takes place during mantle melting, estimate the isotopic composition of the bulk silicate Earth, and then make comparisons with primitive and differentiated meteorites. I present double spike Mo isotope data for forty-two mafic and seven ultramafic samples from diverse locations, and nineteen extra-terrestrial samples. The delta^98/95Mo values of all the terrestrial samples (normalized to NIST SRM 3134) exhibit a significant range from +0.53±0.21 to -0.56±0.09‰. The compositions of mid-ocean ridge basalts (MORBs) (+0.03±0.07‰, 2s.d.) and ultramafic rocks (+0.38±0.15‰, 2 s.d.) are relatively uniform and well resolved, providing evidence of fractionation associated with partial melting. In contrast intraplate and ocean island basalts (OIBs) display significant variability within a single locality from MORB-like to strongly negative (-0.56‰). The most extreme values measured are for nephelinites from the Cameroon Line and Trinidade, which also have anomalously high Ce/Pb and low Mo/Ce relative to normal oceanic basalts. The observed relationships between delta^98/95Mo and Ce/Pb, U/Pb and Mo/Ce provide evidence that sulphide plays a critical role in retaining Mo in the mantle and fractionating its isotopic composition in basaltic magmas. If residual sulphides are responsible the Mo isotopic composition, Mo budget of the bulk silicate Earth will be misrepresented by values estimated from basalts. On this basis a revised best estimate of the Mo content in the bulk silicate Earth (BSE) ranging between 251 to 268 ppb is derived, approximately 6 times higher than previously assumed, and similar to the levels of depletion in refractory siderophile elements such as W, Ni and Co. This significantly ameliorates the argument for Mo removal via late stage sulphide extraction to the core. The Mo isotopic composition of the BSE (0.35‰) is distinct from the delta^98/95Mo values found in primitive and iron meteorites. Although Mo isotopic fractionation varies between different phases within a single iron meteorite, and occurs during fractional crystallization in asteroidal cores, most iron meteorites have ddelta^98/95MoSRM3134 (-0.14 to -0.06‰) that are similar to ordinary and CI carbonaceous chondrite (-0.12 to -0.09‰). This range of delta^98/95Moo is not only significantly lighter than the BSE, but also enstatite chondrites, which have delta^98/95Mo values of 0.04 to 0.13‰. Several possible explanations are proposed. (A) Core-mantle differentiation fractionates Mo isotopes. The recently proposed Mo effect of sulphide liquid removal is likely to be minor because this should have generated a light Mo isotope composition for the BSE. However, isotopic fractionation associated with metal-silicate partitioning may be responsible for the heavy Mo in the BSE. (B) A distinct isotopic composition for the late material that contributed Mo to the BSE. Enstatite chondrites (or other putative groups of chondrites with a heavy Mo isotope composition) and sulphur-rich components form the cores of impacting bodies are the most likely candidates that could deliver heavy Mo to Earth. (C) The Mo isotopic composition of the Solar System is heterogeneous in a mass dependent fashion such that heavier Mo isotopes are enriched in the section of the disk from which Earth accreted. There are some difficulties behind each of these models and further work is needed to determine which is correct.

Thesis (MSc)-- Stellenbosch University, 2012. / ENGLISH ABSTRACT: Over the past two decades, field flow fractionation (FFF), as a polymer characterization technique, has become cutting edge technology. The demand for molar mass and size characterisation of complex polymer systems has increased, especially in cases where classical calibration techniques such as size exclusion chromatography (SEC) has shown several shortcomings. FFF is a technique resembling chromatography. It has several significant advantages over SEC, especially for the characterisation of ultrahigh molar mass (UHMM), branched and gel-containing polymers. In this study, polybutadienes, which often contain the abovementioned species, were analysed by SEC and asymmetric flow field flow fractionation (AF4). Both separation techniques were coupled to refractive index and multi-angle laser light scattering detection. Similarly, polyrotaxanes, which are polymers with complex and unique molecular architectures, were also investigated. Results showed that AF4 can explicitly be used as a superior tool over SEC. In the case of UHMM polybutadienes, much higher molar masses could be detected by AF4, due to the absence of shear degradation which is often encountered in SEC. Gel-containing species could be detected by AF4 as no filtering is required prior to injection. Abnormal retention behaviour, a phenomenon often encountered in UHMM branched polymers, was observed in SEC analysis of the polyrotaxanes materials. AF4 provided sufficient separation from low to high molar masses, without out any irregularities. / AFRIKAANSE OPSOMMING: Gedurende die afgelope twee dekades het veldvloeifraksionering (FFF) as ‘n polimeerkarakteriseringstegniek groot veld gewen. Die aanvraag na molekulêre massa en groottekarakterisering van komplekse polimeersisteme het toegeneem, veral in die gevalle waar klassieke kalibrasietegnieke soos grootte-uitsluitingschromatografie (SEC) etlike tekortkominge getoon het. FFF is ‘n tegniek soortgelyk aan chromatografie, en het voorheen bewys dat dit oor ‘n redelike aantal voordele bo SEC beskik, veral in die geval van ultrahoë molekulêre massa- (UHMM-), vertakte- en jelbevattende spesies. In die huidige studie is polibutadieenpolimere, wat dikwels bogenoemde spesies bevat, geanaliseer met behulp van SEC en onsimmetriese vloei-veldvloeifraksionering (AF4). Beide skeidingstegnieke is gekoppel aan ‘n brekingsindeks en multihoek-laserligverstrooiingsdetektors. Op dieselfde wyse is polirotaksane (polyrotaxanes) met komplekse molekulêre argitektuur bestudeer. Daar is bewys dat AF4 uitsluitlik gebruik kan word as ‘n meer geskikte tegniek bo SEC. Baie hoër molekulêre massas kon deur middel van AF4 vir UHMM polibutadieenpolimere raakgesien word as gevolg van die verminderde afbrekende degradasie wat dikwels voorkom met SEC. Jel-bevattende spesies is suksesvol geïdentifiseer met behulp van AF4 waartydens geen filtrering vir analise nodig was nie. Abnormale retensie was sigbaar tydens SEC analise van monsters van polirotaksane, wat dikwels voorkom in vertakte polimere. In teenstelling het AF4 bewys dat ‘n bevredigende skeiding van klein na groot molekulêre massas, sonder enige tekortkominge, moontlik is.

Thesis (DSc (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / Unstabilised polyolefins are susceptible to degradation when exposed to molecular oxygen, heat, irradiation as well as chemical and mechanical stimuli. Oxidation leads to changes in molecular properties such as molecular weight, molecular weight distribution, chemical composition, chemical composition distribution and crystallisability. Conventional analytical techniques are of limited use when studying the degradation of heterogeneous materials such as impact polypropylene copolymers (ICPP). These copolymers consist of a number of components of different monomer contents, isotacticity and crystallinity, ranging from amorphous EPR to highly crystalline polypropylene. The individual components are affected differently by degradation, leading to heterogeneity within the degradation of impact copolymers. Novel analytical approaches that acknowledge the heterogeneity in sample composition are needed to study the degradation behaviour of such heterogeneous materials. This study describes the combination of fractionation and hyphenated techniques with conventional analyses for extensive structural characterisation of complex impact copolymers as well as their degradation behaviour. Temperature rising elution fractionation (TREF) coupled to conventional techniques such as size exclusion chromatography (SEC), Fourier-Transform infrared spectroscopy (FTIR), Carbon-13 nuclear magnetic resonance (13C-NMR) and differential scanning calorimetry (DSC) indicated the ICPPs in question to consist of four main components, namely ethylene-propylene random copolymers (EPR), isotactic PP (iPP), as well as semi-crystalline ethylene-propylene copolymers (EPC) and lower isotacticity PP. The degradation of an ICPP was studied by a multi-component analysis procedure consisting of TREF coupled to SEC, 13C-NMR, as well as SEC-FTIR. Results obtained by this procedure indicated the change in crystallisability of the bulk sample observed by TREF, crystallisation analysis fractionation (CRYSTAF) and DSC to be the result of the preferential degradation of the iPP phase. Degradation of ICPPs initiates within this phase where chain scission and carbonyl group insertion leads to a change in the crystallisability of iPP chains. During TREF of degraded bulk ICPPs, the degraded iPP molecules elute at lower elution temperatures, depending on their degree of degradation. The other components of the copolymer were degraded to a lesser extent. Degradation products were also found to be heterogeneously distributed across the molecular weight distribution of each fraction, with a higher concentration appearing at the low molecular weight side. The multi-component analysis procedure was also used to study the difference in degradation behaviour between ICPPs of different comonomer content, isotacticity and crystallinity. The spatial heterogeneity of degradation within ICPPs was studied by Fourier-Transform infrared microspectroscopy (FTIR-μS). A heterogeneous distribution of degradation products was found across the depth of thicker sample specimens. These results were compared to those obtained by conventional layer-by-layer milling followed by SEC, FTIR and CRYSTAF. The principles of degradation within thick samples were similar to that observed for thin films, although additional contributions by sample morphology and oxygen diffusion were detected.