Thesis (Ph. D.)--University of Massachusetts Amherst, 2009. / Includes bibliographical references (p. 55-57). Print copy also available.

Thesis (Ph.D. Materials and Process Engineering)--University of Waikato, 2006. / Includes bibliographical references.

Aaueous polymer two phase systems containing dextran T500, PEG 8000, and buffer are widely used to separate and analyse cells and other biological material based on the way they partition between the two phases and their interface. The behaviour of human erythrocytes in such two phase systems was studied in order to characterize some of the physico-chemical interactions important in determining cell partition. Two aspects were studied: the role of electrostatic and affinity ligand effects in determining the relative affinity of the cell for the two phases, and the relationship of this relative affinity to the cell partition. The potential difference produced by the unequal affinity of the buffer cations and anions for each phase was related to the salt partition by a thermodynamic model, which agreed with experimental results obtained in single and mixed salt systems. A thermodynamic theory for the effects of an affinity ligand on the cell surface free energy difference between the phases was derived, and found to agree quantitatively with experimental results using the affinity ligand PEG-palmitate. The change in cell surface free energy difference as a function of potential and ligand concentration was determined by contact angle measurements. This change was very small, based either on previous estimates of the surface charge density, or on the amount of PEG-palmitate bound to the cell surface as determined by adsorption experiments. This was attributed to partial exclusion of the phases from the cell glycocalyx. Cell partition into the upper PEG rich phase increased as this phase was made more positive with respect to the lower phase, or as the amount of an affinity ligand, PEG-palmitate, in the system was increased. Contact angle measurements were used to determine the energy of erythrocyte attachment to the interface between the two phases. The dependence of the cell partition on this parameter showed that thermal energies are far too small to partition cells in these systems. The cell partition was unaffected by the density difference between the phases. This and other results led to the hypothesis that droplet coalescence is the primary process by which large particles (>1 µm dia.) such as cells are distributed between the interface and one of the phases. / Science, Faculty of / Chemistry, Department of / Graduate

L’injection de CO2 dans un réservoir géologique n’a rien d’un processus anodin : les impacts sur la roche hôte peuvent menacer l’intégrité du stockage suite à des modifications des propriétés pétrophysiques. Nous proposons ainsi d’envisager l’utilisation des isotopes stables du chlore comme indicateurs des processus physicochimiques générés par une injection de CO2. L’ion chlorure Cl- est en effet un élément conservatif et ubiquiste dans les eaux des réservoirs, et le rapport δ37Cl est connu pour être modifié par divers processus (diffusion, filtration ionique, précipitation de sel, changements de phase). La méthodologie adoptée a consisté à investiguer les effets de ces différents processus sur le signal isotopique du Cl en conditions P-T d’un réservoir de stockage. Des expériences en autoclaves ont montré que le Cl était solubilisé dans le CO2sc, mais en quantités suffisamment faibles pour ne pas impacter le signal isotopique dans les saumures si fractionnement isotopique il y a. Des expériences de migration d’une saumure réactive par advection (banc de percolation ICARE1, Université de Montpellier) et par diffusion (cellule développée à IFPEN) ont également été réalisées. Aucune évolution de δ37Cl n’a été mesurée au cours de la percolation (transport advectif conservatif) et les effets de la diffusion restent à évaluer et à mettre en relation avec les évolutions de porosité et perméabilité des roches. Les expériences de séchage et de précipitation de sel en milieu poreux ont montré que les concentrations en Cl et les valeurs de δ37Cl permettaient de caractériser les processus de transport en jeu. Ces résultats expérimentaux ont permis d’identifier des processus capables de modifier les abondances isotopiques de Cl et indiquent l’intérêt des isotopes pour le monitoring de site de stockage de CO2 / CO2 injection in a reservoir leads to physicochemical processes which can have harmful consequences on the reservoir integrity due to porosity and permeability alteration. In this work, we propose to test the possibility that stable chlorine isotopes could be used as a geochemical tool to assess these effects. Indeed, chloride is a conservative and a major component of reservoir brines, and it is already known that several processes can modify the ratio of its two stable isotopes δ37Cl (diffusion, ionic filtration, salt precipitation or phase change). To test this possibility, several types of experiments were performed to investigate the effects generated by a CO2 injection on Cl-isotopes. Autoclave experiments have shown that Cl can be solubilized in CO2SC, but the amounts would be too low to modify the isotopic signal of brines in case of any fractionation process. Reactive brine migration experiments by advection (ICARE1 percolation apparatus in Montpellier University) and diffusion (diffusion cell developed at IFPEN) were also conducted. No δ37Cl was observed during percolation (conservative advective transport) and the effects of diffusion remain to be investigated with regard to the evolution of rock porosity and permeability. Drying and salt precipitation experiments on porous media have shown that Cl concentrations and δ37Cl values can give information about transport processes during water evaporation. These experimental results allowed us to identify the processes capable of modifying the δ37Cl signal, and that Cl-isotopes can be of use for the monitoring of CO2 storage site

Lignin is the most abundant natural aromatic polymer on the earth. In this work, lignin properties were studied in order to explore its use as a low cost carbon precursor for graphene production. Initial studies focused on kinetics of lignin pyrolysis using ‘Kissinger method’ and ‘ASTM E 1641’ using thermogravimetry. The values obtained for kinetic parameters varied for the two methods and activation energy increased with increase in lignin purity. Lignin was solvent fractionated, using three organic solvents to extract the high molecular weight fraction suitable for the production of highly ordered graphene nano platelets. Acetone and Methanol were successful in sequential fractionation. Finally, polycrystalline graphene was produced using Protobind 1000 and lignosulfonate lignins by carbonization. The acid purified graphene had relatively less catalytic material remaining, and nitric acid purification was successful compared to HCl purification. However, HNO3 purification introduced minor structural damages to the sample.

Thesis (doctoral)--Lund University, 1998. / Added t.p. with thesis statement inserted.

Thesis (doctoral)--Lund University, 1998. / Added t.p. with thesis statement inserted.

Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Linear low density polyethylene (LLDPE), one of the fastest growing types of polyethylene, is made from the copolymerisation of ethylene and higher 1-olefin comonomers. 1-octene is the comonomer of choice as it gives mechanically better LLDPEs as compared to other 1-olefins. Recently, a shortage of 1-octene has been observed in the global market. Considering the fact that ethylene/1-heptene (EH) copolymers may have properties that are very similar to those of ethylene/1-octene (EO), replacing 1-octene with 1-heptene as the comonomer in the manufacture of commercial linear low density polyethylene (LLDPE) is a viable option. In order to do so, evaluation of microstructural and mechanical properties of both types of resins and their comparison were carried out first. Several LLDPE resins were synthesised using Ziegler-Natta (ZN) and metallocene type catalysts. The LLDPE resins were made using varying amounts of the comonomer to obtain copolymers of different compositions. Ten of the ZN-LLDPE resins became the core focus of the present study. Carbon-13 nuclear magnetic resonance spectroscopy (13C NMR) showed the differences in the compositions of both the EH and EOresins. Crystallisation analysis fractionation (CRYSTAF), differential scanning calorimetry (DSC) and high temperature high performance liquid chromatography (HT-HPLC) revealed the presence of at least two fractions within the EH and EO copolymers which varied in quantity and chemical composition as the comonomer content was increased. The fractions were identified as being the copolymer (of ethylene and the comonomer) and polyethylene. Comparisons of the EH and EO CRYSTAF and HPLC data showed similarities in the microstructures of the resins. Preparative-temperature rising elution fractionation (prep-TREF) was used to obtain several fractions from each resin for quantification and analyses. DSC, HT-HPLC, CRYSTAF, and 13CNMR revealed close similarities in the fractions of EH and EO copolymers with comparable comonomer contents. It also was revealed that TREF fractionations are influenced by the bulk resin comonomer content. EH and EO copolymers demonstrated high similarities in tensile strength and Young’s modulus at comonomer contents of < 3 mol %. Minor differences in the mentioned properties at comonomer content of > 3 mol % were attributed to the slightly better ability of 1-octene at reducing crystallinity as compared to 1-heptene as well as small differences in the comonomer contents of the test samples. The results of the study suggest that 1-heptene can be used in the place of 1-octene in the commercial manufacture of LLDPE. / AFRIKAANSE OPSOMMING: Lineêre lae digtheid poliëtileen (LLDPE), een van die vinnigste groeiende poliëtileen tipes, word produseer deur die ko-polimerisasie van etileen en ‘n hoër 1-olefien ko-monomeer. 1-okteen is die ko-monomeer wat die meeste gebruik word aangesien dit LLDPE met die beste meganiese eienskappe produseer. Daar is egter ‘n tekort aan 1-okteen in die globale mark. Aangesien etileen/1-hepteen (EH) kopolimere moontlik soortgelyke eienskappe het as etileen/1-okteen (EO), kan 1-okteen moontlik vervang word deur 1-hepteen as ‘n komonomeer in die produksie van LLDPE. Om dit te doen is die meganiese en mikrostrukturele eienskappe van beide polimere geëvalueer. Verskeie LLDPE polimere is gesintetiseer met behulp van Ziegler-Natta (ZN) en metalloseen kataliste. Die komonomeer inhoud is gevarieer om LLDPE polimere te produseer met verskillende komposisie. Tien van die gesintetiseerde ZN-LLDPE polimere is gekies en is die kernfokus van die huidige studie. 13-Koolstof kern magnetiese resonans spektroskopie (13C KMR) het die variasie in ko-monomeer inhoud bevestig van beide die EH en EO polimere. Kristallisasie analise fraksioneering (CRYSTAF), differensiële skandeer kalorimetrie (DSC) en 'n hoë temperatuur hoë verrigting vloeistof chromatografie (HT-HPLC) het die teenwoordigheid van ten minste twee fraksies binne die EH en EO ko-polimeer bevestig wat ‘n variasie in hoeveelheid en chemise samestelling getoon het met ‘n toename van die ko-monomeer inhoud in die ko-polimeer. CRYSTAF en HT-HPLC data het getoon dat hierdie fraksies in EH en EO ooreenkomstige mikrostrukturele gedrag getoon het. Preparatiewe temperatuur styging elueering fraksioneering (prep-TREF) is gebruik om die polimere te fraksioneer om sodoende kwantitief die poliëtileen fraksies te verky en te analiseer. Verdere analise van die fraksies deur DSC, HT-HPLC, CRYSTAF en 13C KMR het getoon dat die fraksies, bekom van die EH en EO kopolimere met vergelykbare ko-monomeer inhoud, baie dieselfde eienskappe toon. Die analises het ook getoon dat die TREF fraksionering beinvloed word deur die ko-monomeer inhoud van die oorspronklike ko-polimeer.

No description available.

In light of recent studies that show oxygen isotope fractionation in carbonate minerals to be a function of HCO3 2-; and CO3 2- concentrations, the oxygen isotope fractionation and exchange between water and components of the carbonic acid system (HCO3 2-, CO3 2-, and CO2(aq)) were investigated at 15, 25, and 40 (degrees)C. To investigate oxygen isotope exchange between HCO3 2-, CO3 -2, and H2O, NaHCO3 solutions were prepared and the pH was adjusted over a range of 2 to 12 by the addition of small amounts of HCl or NaOH. After thermal, chemical, and isotopic equilibrium was attained, BaCl2 was added to the NaHCO3 solutions. This resulted in immediate BaCO3 precipitation; thus, recording the isotopic composition of the dissolved inorganic carbon. Data from experiments at 15, 25, and 40 (degrees)C (1 atm) show that the oxygen isotope fractionation between HCO3 2-; and H2O as a function of temperature is governed by the equation: 1000 ;HCO3--H2O = 2.66 + 0.05(106T-2) + 1.18 + 0.52. where is the fractionation factor and T is in kelvins. The temperature dependence of oxygen isotope fractionation between CO32 and H2O is 1000 CO32--H2O = 2.28 + 0.03(106T-2) - 1.50 + 0.29. The oxygen isotope fractionation between CO2(aq) and H2O was investigated by acid stripping CO2(aq) from low pH solutions; these data yield the following equation: 1000 CO2(aq)-H2O = 2.52 + 0.03(106T-2) + 12.12 + 0.33. The kinetics of oxygen isotope exchange were also investigated. The half-times for exchange between HCO3- and H2O were 3.6, 1.4, and 0.25 h at 15, 25, and 40 (degrees)C, respectively. The half-times for exchange between CO2 and H2O were 1200, 170, and 41 h at 15, 25, and 40 (degrees) C, respectively. These results show that the 18O of the total dissolved inorganic carbon species can vary as much as 17 at a constant temperature. This could result in temperature independent variations in the 18O of precipitated carbonate minerals, especially in systems that are not chemically buffered.