Thesis (Ph. D.)--State University of New York. College of Environmental Science and Forestry, Syracuse, 1997. / eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--State University of New York. College of Environmental Science and Forestry, Syracuse, 1997. / eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--Ohio State University, 2003. / Document formatted into pages; contains xvi, 371 p.; also contains graphics. Includes bibliographical references. Abstract available online via OhioLINK's ETD Center; full text release delayed at author's request until 2005 May 5.

Thesis (Ph.D)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009. / Committee Chair: Marder, Seth; Committee Member: Bredas, Jean-Luc; Committee Member: Kroger, Nils; Committee Member: Perry, Joe; Committee Member: Sandhage, Ken. Part of the SMARTech Electronic Thesis and Dissertation Collection.

The techniques of X-ray photoelectron spectroscopy (XPS), secondary ionization mass spectroscopy, chemical abstraction analysis and microelectrophoresis were used to confirm the existence of iron films on cassiterite grains recovered from the tin concentrator of Renison Limited (Australia). All analyses indicated the level of surface iron contamination to be far in excess of that characteristic of the bulk mineral lattice. No evidence was found in XPS analyses to support the contention that this iron represented lattice iron that had accumulated on the surface due to migration through the lattice, as has been suggested to be the case for certain sulphide minerals. Instead, all of the experimental data supported the hypothesis that the surface film was the result of previous adsorption of hydrous ferric oxide sols onto the cassiterite surface in the plant environment but which had undergone fundamental structural changes when the sample was dried. Specifically, the presence of the iron film did not change significantly the electrokinetic properties of cassiterite, as is known to be the case for other insoluble oxide minerals in the presence of freshly precipitated hydrolyzed metal ionic species. To reconcile these observations, it was shown independently that drying, both thermally and under vacuum, caused the charge reversal phenomena related to hydrolyzed metal ion adsorption either to diminish or disappear. In the presence of styryl phosphonic acid, the iron contaminated cassiterite exhibited a microflotation response that corresponded remarkably with the actual flotation observed in the plant from which it was taken. A critical examination of the literature revealed that this behaviour was indicative of that reported for other cassiterites in both batch and plant flotation of ores. Most notably the mineral floated strongly between pH 4.0 and 7.5. However, after acid leaching, the pH of maximum recovery moved to more acidic values around pH 2.0 and the mineral floated much less strongly in the slightly acidic to alkaline range. This latter behaviour correlated with a large body of published data for which it was known that the cassiterite used was either a high purity sample, not exposed to solutions containing dissolved metal ionic species, or had been acid cleaned prior to test work. Conversely, results from fundamental studies, where this was known not to be the case, exhibited remarkable consistency with the data obtained for the untreated cassiterite sample. The principal influence of the iron species adsorbed onto the surface of cassiterite was shown to be flotation activation in the pH range where the adsorbed species were not extensively solubilized. In the acidic range below pH 4.0, solubilization of the surface iron entities occurred which caused a severe flotation depressant effect. This solubilization was promoted in the presence of sodium fluoride, a known complexing agent for iron in acidic solutions, and the phosphonic acid. In the latter case, evidence was found for the formation of a soluble iron phosphonate complex. Independent confirmation was also sought and obtained from light scattering photometry to verify the strong affinity of phosphonic acids for hydrous ferric oxide species. Other ionic entities, such as those of magnesium and calcium were found to interact far less strongly. On the basis of this research, it has proven possible to provide a rational interpretation of all previously existing data pertaining to cassiterite flotation with phosphonic acids, for which reasonable sample description and preparation information exist. Such a reconciliation has not previously been provided, either through studies on the effects of cassiterite mineral lattice impurities or other work with dissolved metal ionic species. Furthermore, a significant link has been established between the results of fundamental analyses and industrial related observations. In particular, commercially successful practices, such as fluoride pretreatment of ore slurries prior to cassiterite flotation, now can be interpreted successfully in terms of fundamental ion solution chemistry. The evidence is that such processes involve the solubilization under acidic conditions of adsorbed iron hydroxy sols from the surface of minerals prior to cassiterite flotation. A bulk rejection of the complexed metal ionic species is then made in the water split of the desliming circuit that precedes flotation. The solution chemical evidence obtained supporting such a mechanism is considerable and no finding, in this work or elsewhere, refutes it. / Applied Science, Faculty of / Mining Engineering, Keevil Institute of / Graduate

The synthesis and characterization of some phosphonic acids as well as the modification of indium tin oxide (ITO) substrates using these phosphonic acids are presented in this thesis. Phosphonic acids have been known to bind strongly to the surface of a number of metal oxides. ITO substrates were reported to be modified with a variety of surface modifiers. Herein the ITO substrates were modified with the chosen phosphonic acids with different functional groups in order to tune the work function and compare the work function changes with the functional group properties.

Made available in DSpace on 2014-10-09T12:46:38Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:05Z (GMT). No. of bitstreams: 1 08351.pdf: 5297394 bytes, checksum: 64bc1483562150f9c5eeb05214a169f5 (MD5) / Dissertacao (Mestrado Profissionalizante em Lasers em Odontologia) / IPEN/D-MPLO / Instituto de Pesquisas Energeticas e Nucleares, IPEN/CNEN-SP; Faculdade de Odontologia, Universidade de Sao Paulo

Made available in DSpace on 2014-10-09T12:46:38Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:05Z (GMT). No. of bitstreams: 1 08351.pdf: 5297394 bytes, checksum: 64bc1483562150f9c5eeb05214a169f5 (MD5) / Dissertacao (Mestrado Profissionalizante em Lasers em Odontologia) / IPEN/D-MPLO / Instituto de Pesquisas Energeticas e Nucleares, IPEN/CNEN-SP; Faculdade de Odontologia, Universidade de Sao Paulo

Phosphonic acids are known to bind strongly to a variety of metal oxide surfaces. Phosphonic acids were designed in order to impart specific properties to the surface of a range of metal oxides upon formation of a monolayer. A large number of novel phosphonic acids were synthesized and fully characterized. The binding of phosphonic acids to the surface of several metal oxides, such as indium tin oxide (ITO) and barium titanate, was studied in detail and determined to be a mixture of bidentate and tridentate binding modes. The modification of several key surface properties of ITO by phosphonic acid modification was also studied. The work function of ITO could be increased or decreased with respect to unmodified ITO by controlling the dipole of phosphonic acids bound to the surface. Additionally, the surface energy could be substantially lowered by attaching phosphonic acids with non-polar terminal functional groups to the ITO surface. The ability to control these surface properties resulted in organic light-emitting diodes (OLEDs) which showed superior lifetimes and stability with respect to OLEDs incorporating ITO without a phosphonic acid monolayer. In addition, the binding of phosphonic acids to a number of other oxides, such as zinc oxide and zeolites, was also studied.

Porous metal phosphonate framework materials were synthesised by solvothermal reaction of bis(α-aminomethylenephosphonic acid) ligands with divalent and trivalent metal cations. The syntheses and characterisation by NMR and, where possible, single crystal X-ray diffraction of seven bisphosphonic acid ligands, including N,N′-piperazinebis(methylenephosphonic acid) (H₄L), its racemic and enantiopure (R) 2-methyl (H₄L′ and R-H₄L′) and 2,5-dimethyl (H₄L′′) derivatives, and N,N′-4,4′-bipiperidinebis(methylenephosphonic acid) (H₄LL) are reported. Syntheses of the known phase Y₂(LH₂)₃·5H₂O and the new phases, STA-13(Y) (St Andrews microporous material No. 13) and Y₂(R-L′H₂)₃·4H₂O, from reactions of Y(AcO)₃ with H₄L, H₄L′ and R-H₄L′ respectively are reported. The as-prepared and dehydrated structures of each phase have been determined from either laboratory or synchrotron powder X-ray diffraction data. Reaction of Y(AcO)₃ and H₄L′′ is shown to form a phase with a different structure. The features determining which structure crystallises are discussed. Syntheses of other rare-earth forms of STA-13 (Sc³⁺, Gd³⁺–Yb³⁺) and the porosity of each phase to N₂ are reported. STA-13(Y) is the most porous form with loadings of ∼3 mmol g⁻¹ and ∼4 mmol g⁻¹ for N₂ and CO₂ respectively. MIL-91(Fe) was synthesised for the first time from reactions of Fe³⁺ cations with H₄L. Its structure was confirmed by Rietveld refinement, but it was not porous. The first syntheses of [Fe₄L₁.₅(AcO)₁.₅(OH,H₂O)₃]·0.5NH₄5.5H₂O (L= L or L′) are reported, from reactions of H₄L or H₄L′ in the presence of an excess of Fe³⁺ cations. The phase is related to a previously reported Co phase. The synthesis of divalent metal bisphosphonate STA-12(Mg) (Mg₂(H₂O)₂L·5.6H₂O) was reported for the first time and its structure determined from single crystal X-ray diffraction. The dehydration behaviour of this material was compared with the known forms of STA-12. STA-12(Mg) is porous to both N₂ (∼5.5 mmol g⁻¹) and CO₂ (~ 8.5 mmol g⁻¹). Reaction of H₄LL with Co²⁺ and Ni²⁺ gave two materials isoreticular with STA-12, labelled STA-16(Co) and STA-16(Ni). The structures of both materials were solved from synchrotron powder X-ray diffraction data. On dehydration, STA-16(Co) undergoes a reversible structural transition to an unknown structure. By contrast, STA-16(Ni) retains the same symmetry in the dehydrated form and its structure was determined from synchrotron powder X-ray diffraction data. Both materials are porous to N₂, with an uptake of up to 22.2 mmol g⁻¹, and CO₂ with maximum loading of 21.7 mmol g⁻¹. NLDFT analysis of N₂ adsorption data confirm the crystallographically determined pore radii. Syntheses of other frameworks with divalent cations and initial reactions of H₄LL with trivalent cations are also reported.