La thèse s’inscrit dans le cadre d’un projet de recherche visant à élaborer une anode permettant le dégagement d’oxygène en milieu de cryolithe fondue à 960°C et dont l’utilisation supprimerait les émissions de dioxyde de carbone du procédé de production d’aluminium Hall-Héroult. Le type d’anode envisagée est un composite Cermet (CERamique – METal), généralement constitué d’une phase métallique à base de nickel, cuivre et fer et d’une ou plusieurs phase(s) oxyde(s) conductrice(s) du type NixFe3-xO4 et Ni1-xFexO. Deux types de cermet, biphasé et triphasé, ont été étudiés dans le cadre de ce projet. L’objectif principal a été de comprendre les mécanismes de dégradation de telles anodes durant les électrolyses. Les cermets ont été testés sous une densité de courant de 0,80 A/cm² pour différentes durées, puis analysés par microscopie optique et microscopie électronique à balayage couplée à une analyse dispersive en énergie. Les premières électrolyses, effectuées dans un électrolyte synthétique, sans aluminium métallique et sous atmosphère argon ont révélé à la fois une dégradation chimique et électrochimique. L’étude de la dégradation chimique a été réalisée grâce à des immersions dans l’électrolyte sans polarisation. Les résultats ont mis en évidence une dissolution de la phase spinelle, liée à un phénomène de substitution entre les ions Al3+ de l’électrolyte et Fe3+ du spinelle, entrainant la formation d’un aluminate du type NixFe3-x-yAlyO4. Lorsque x = 0 et y proche de 2, la phase spinelle est dissoute alors que lorsque x est proche de 1, la phase spinelle est stabilisée et sa dissolution ralentie. Les électrolyses menées jusqu’à la fin de vie des matériaux ont révélé l'attaque préférentielle de la phase métallique pour former des composés fluorés et oxydes. Grâce aux caractérisations micrographiques et aux calculs thermodynamiques (logiciel FactSage 7.1), un mécanisme de dégradation global des anodes a été proposé. La compréhension des mécanismes de dégradation chimique et électrochimique des matériaux a permis de proposer des voies d'amélioration concernant à la fois le matériau d'anode et la chimie du bain cryolithique. / The thesis is a part of a research project which develop an anode permitting the release of oxygen in molten cryolite medium at 960°C, in order to eliminate carbon dioxide emissions from the aluminium production process called Hall-Héroult process. The type of anode envisaged is a Cermet composite (CERamic - METal), generally consisting of a metallic phase based on nickel, copper and iron and one or more conductor oxide phase(s) such as NixFe3-xO4 and Ni1-xFexO type. Two types of cermet, two-phase and three-phase, have been studied in this project. The main objective was to understand the degradation mechanisms of such anodes during electrolysis. The cermets were tested at a current density of 0.80 A/cm² for different durations and analyzed by optical microscopy and scanning electron microscopy coupled with dispersive energy analysis. The first electrolyses, carried out in a synthetic electrolyte, without metallic aluminum and under argon atmosphere revealed both chemical and electrochemical degradations. Study of chemical degradation was carried out thanks to immersions in the electrolyte without polarization. The results showed a dissolution of the spinel phase, linked to a substitution phenomenon between the Al3+ ions from the electrolyte and Fe3+ from spinel, resulting in the formation of a NixFe3-x-yAlyO4 aluminate type. When x = 0 and y close to 2, the spinel phase is dissolved whereas when x is close to 1, the spinel phase is stabilized and its dissolution slowed down. Electrolyses conducted to the end of life of the materials revealed the preferential attack of the metal phase to form fluorinated compounds and oxides. Thanks to micrographic characterizations and thermodynamic calculations (FactSage 7.1 software), a global degradation mechanism of the anodes has been proposed. The understanding of the chemical and electrochemical degradation mechanisms of the materials made it possible to propose ways of improvement concerning both the anode material and the cryolithic bath chemistry.

Common methods for determining mineral absorption by the body are invasive and frequently utilize radioisotopes. In experiment one. rats were given a dose of radiolabeled ferrous sulfate. Relative absorption was estimated by changes in serum iron and by appearance of the radiotracer in the serum. There were no differences in relative absorption determined by the methods, although the low overall absorptions by the iron-replete rats may have decreased the sensitivity. In experiments two and three. iron and magnesium supplements were given orally to 12 women age 19-25. Each subject received iron and magnesium supplements once each week for 5 weeks. Blood samples were taken via venous catheter every 30 minutes for 2 hours and 30 minutes following dosing, and a urine sample was taken following the collection time period. Samples were analyzed for serum iron, serum magnesium, hematocrit, ferritin, urinary magnesium, and urinary creatinine. The increase in serum iron was evaluated from both the peak increase in serum iron and from the integrated increase in serum iron over the blood collection time. The data for each supplement were compared by analysis of variance. For the iron supplements. the taste-free iron supplement increased serum iron less than either the Ferrochel or the ferrous sulfate supplements. When the iron absorption was then compared to ferritin stores (low, medium, and high), the relative absorption of Ferrochel was higher in the low ferritin range (0-15 ng/ml) than in the upper ranges (P=.00l for peak and P=.0002 for area). Relative absorption from Ferrochel iron was also higher than the other supplements for subjects with low ferritin stores. Neither serum nor urinary magnesium values differed significantly among the three compounds examined. Serum magnesium values are stable in healthy individuals, and the urinary magnesium data were not evaluated over 24 h as in typical magnesium load tests. In summary, both the ferrous sulfate and Ferrochel supplements were absorbed more efficiently than the taste-free iron supplement. The Ferrochel was also absorbed more efficiently in individuals with low iron stores, demonstrating better regulation by the body than with the other supplements examined.

Includes bibliographical references (leaves 78-86) In the Herrmanns sub-catchment in the Mt. Lofty Ranges (near Mt. Torrens) soil sodicity was the dominant factor in causing clay to disperse in the eroded area along the foot slopes, wheras in non-eroded areas of the mid-slopes and on the stream banks, the dispersive power of sodicity was attenuated by the flocculative power of other soil properties.

xxi, 299 leaves : ill. ; 25 cm / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.1976) from the Dept. of Plant Physiology, University of Adelaide

Copies of author's previously published articles in pocket inside back cover. Bibliography: leaves 147-160. This thesis outlines the factors affecting soil strength and structural stability and their interrelationship in salt-affected soils. The objectives of this study are to investigate the influence of clay particles on soil densification and mellowing, the mellowing of compacted soils and soil aggregates as influenced by solution composition, the disaggregation of soils subjected to different sodicities and salinities and its relationship to soil strength and dispersible clay and the effect of organic matter and clay type on aggregation of salt-affected soils.

In this study / ferrocenyl and naphthalenyl substituted quinoxaline derivatives / 5,8- bis (2,3- dihydrothieno [3,4-b] [1,4] dioxin-5-yl)-2- (naphthalen-2-yl)- 3- ferrocenyl- 4a,8a-dihydroquinoxaline / 5,8- bis (2,3-dihydrothieno [3,4-b] [1,4]dioxin-5-yl) -2- (phenyl) -3-ferrocenylquinoxaline / 5,8-bis (2,3-dihydrothieno [3,4-b] [1,4]dioxin-5-yl) -2,3- di(naphthalen-2-yl)quinoxaline and trihexylthiophene and thiophene coupled benzimidazole derivatives / 4-(tert-butyl)-4,7-bis(4-hexylthiophen-2-yl)spiro[benzo[d]imidazole-2,1-cyclohexane] and 4-(tert-butyl)-4, 7-bis(thiophenyl)spiro[benzo[d]imidazole-2,1-cyclohexane] were used as photosensitizers to broaden the active area of diaryliodonium salts. Both quinoxaline and benzimidazole derivatives are expected to be efficient in cationic photopolymerization with a variety of vinyl and oxide monomers at room temperature upon long wavelength UV irradiation. Photopolymerization will be initiated by diphenyliodonium salts and monitored with Optical Pyrometry. Characterization will be completed with optical absorption, flourescence studies and photopolymerization under solar irradiation.

The first part of this thesis describes the efficient synthesis of several hypervalent iodine(III) compounds. Electron-rich diaryliodonium salts have been synthesized in a one-pot procedure, employing mCPBA as the oxidant. Both symmetric and unsymmetric diaryliodonium tosylates can be isolated in high yields. An in situ anion exchange also enables the synthesis of previously unobtainable diaryliodonium triflates. A large-scale protocol for the synthesis of a derivative of Koser’s reagent, that is an isolable intermediate in the diaryliodonium tosylate synthesis, is furthermore described. The large-scale synthesis is performed in neat TFE, which can be recovered and recycled. This is very desirable from an environmental point of view. One of the few described syntheses of enantiopure diaryliodonium salts is discussed. Three different enantiopure diaryliodonium salts bearing electron-rich substituents are synthesized in moderate to high yields. The synthesis of these three salts shows the challenge in the preparation of electron-rich substituted unsymmetric salts. The second part of the thesis describes the application of both symmetric and unsymmetric diaryliodonium salts in organic synthesis. A metal-free efficient and fast method for the synthesis of diaryl ethers from diaryliodonium salts has been developed. The substrate scope is wide as both the phenol and the diaryliodonium salt can be varied. Products such as halogenated ethers, ortho-substituted ethers and bulky ethers, that are difficult to obtain with metal-catalyzed procedures, are readily prepared. The mild protocol allows arylation of racemization-prone a-amino acid derivatives without loss of enantiomeric excess. A chemoselectivity investigation was conducted, in which unsymmetric diaryliodonium salts were employed in the arylation of three different nucleophiles in order to understand the different factors that influence which aryl moiety that is transferred to the nucleophile. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Accepted. Paper 5: Submitted. Paper 6: Manuscript.</p>

No description available.

In this work, electrolytes for secondary batteries and fuel cells were investigated. Ionic liquids (ILs), for use as battery electrolytes, were formed using quaternary ammonium salts (Quats) and aluminum chloride. The room temperature (RT) carbonate fuel cell was demonstrated by modifying a commercially available anion exchange membrane, utilizing positive quaternary ammonium fixed sites, to transport carbonate. The charge density on the nitrogen and the symmetry of the Quat were demonstrated to be the dominant factors in determining the IL melting point (MP). The introduction of a benzyl ring was found to lower the MP of the ILs by increasing the size of the Quat, while disrupting its symmetry. ILs formed from asymmetric quaternary ammonium salts having three distinct groups were found to have lower melting points than those formed using Quats with two groups. Replacement of an alkyl group with a rigid ether linkage can lower the IL melting point. Assymetric alkyl substituted Quats were found to form more electrochemically stable, less viscous ILs than their benzyl substituted counterparts. The increased electrochemical stability is due to the smaller butyl chain being a worse leaving group than the benzyl group. Similarly, the smaller size of the alkyl substituted Quats results in the lower viscosities. Lithium and sodium can be reversibly deposited from neutral ILs following the addition of an additive (such as SOCl2). The additive disrupts the strong coordination between Na+, or Li+, and AlCl4-. Chlorinated compounds, such as chloroform-D and carbon tetrachloride, were demonstrated to catalyze the reversible reduction of sodium. When neutralized with lithium and sodium, reversible Li-Na alloys were deposited. The Li-Na alloy appears to suppress dendrite formation and could potentially be used as a metal based anode in a rechargeable Li battery. A novel room temperature carbonate fuel cell was constructed. The alkaline environment could eliminate the need for water in the oxidation of methanol. Cells were operated on hydrogen, 1M methanol, and pure methanol fuels. CO2 was produced at the anode and O2 and CO2 were necessary at the cathode for operation, indicating that carbonate was the conducting ion.

Quaternary ammonium compounds (QACs) are widely used in commercial and consumer applications as disinfectants, fabric softeners, hair conditioners, and emulsifying agents. The massive production and utilization of QACs has led to their extensive discharge into the environment, raising concerns globally. Several studies have reported on potential risks and detrimental effects of QACs on the natural environment and public wastewater treatment plants. Biological treatment has been found to be an effective way to remove QACs and especially aerobic treatment processes can provide rapid biodegradation via a consortium of bacteria. Although extensive research has been conducted on the fate and effect of QACs, relatively little is known about their effect on aerobic biological treatment processes, especially on nitrification. Research was conducted on the fate and effect of alkyl benzyl dimethyl ammonium chloride (AB), a QAC widely used as disinfectant, in mixed aerobic and nitrifying cultures. The results of this study demonstrated that up to 50 mg/L AB was efficiently degraded in a mixed aerobic culture fed with dextrin and peptone, although trace residual AB levels were observed. Nitrification of the produced ammonia was complete at an AB concentration of 20 mg/L after an acclimation period, but was almost completely inhibited at 50 mg/L. Mixed aerobic cultures maintained only with AB as external nitrogen and carbon source achieved a high degree of AB degradation at both 20 and 50 mg/L. Ammonia oxidation by a nitrifying culture, enriched with ammonium chloride and sodium bicarbonate, was inhibited with increasing AB concentration and completely ceased at 15 mg/L AB. Degradation or utilization of AB was not observed for all tested AB concentrations between 2 to 20 mg/L. Based on these experimental results, and assuming non-competitive inhibition, a relatively low value of the AB inhibition coefficient was obtained, which indicates a relatively high susceptibility of the ammonia oxidizers to AB. The results of this study have significant implications for both engineered and natural systems relative to the fate and effect of QACs.