Structural characterisation of kaolinite : NaCl intercalate and its derivatives

Kaolinite:NaCl intercalates with basal layer dimensions of 0.95 and 1.25 nm have been prepared by direct reaction of saturated aqueous NaCl solution with well-crystallized source clay KGa-1. The intercalates and their thermal decomposition products have been studied by XRD, solid-state 23Na, 27Al, and 29Si MAS NMR, and FTIR. Intercalate yield is enhanced by dry grinding of kaolinite with NaCl prior to intercalation. The layered structure survives dehydroxylation of the kaolinite at 500°–600°C and persists to above 800°C with a resultant tetrahedral aluminosilicate framework. Excess NaCl can be readily removed by rinsing with water, producing an XRD ‘amorphous’ material. Upon heating at 900°C this material converts to a well-crystallized framework aluminosilicate closely related to low-camegieite, NaAlSiO4, some 350°C below its stability field. Reaction mechanisms are discussed and structural models proposed for each of these novel materials.

Kinetic study of goethite dehydration and the effect of aluminium substitution on the dehydrate

Goethite and Al-substituted goethite were synthesized and were characterized using XRD and XRF. The kinetic study of goethite dehydrate was investigated by TG and DTG at different heating rates (2, 5, 10, 15, 20 ◦C/min) and the effect of Al substitution for Fe on dehydrate was studied. The results showed that two types of absorbed water with the same Ed values of 3.4, 6.2 kJ/mol were confirmed on goethite and Alsubstituted goethite. Three types of hydroxyl units were proved, one being on the surface and the other two being in the structure of goethite. The substitution of Al for Fe in the structure of goethite decreases the desorption rate of hydroxyl, increases the dehydroxylation temperature, broadens the desorption peaks in DTG curves, and improves the Ed values from 19.4, 20.4, 26.1 kJ/mol to 21.6, 30, 33.6 kJ/mol when Al substitution comes to 9.1%.

The thermal decomposition of hydronium jarosite and ammoniojarosite

The thermal decomposition of hydronium jarosite and ammoniojarosite was studied using thermogravimetric analysis and mass spectrometry, in situ synchrotron X-ray diffraction and infrared emission spectroscopy. There was no evidence for the simultaneous loss of water and sulfur dioxide during the desulfonation stage as has previously been reported for hydronium jarosite. Conversely, all hydrogen atoms are lost during the dehydration and dehydroxylation stage from 270 to 400 °C and no water, hydroxyl groups or hydronium ions persist after 400 °C. The same can be said for ammoniojarosite. The first mass loss step during the decomposition of hydronium jarosite has been assigned to the loss of the hydronium ion via protonation of the surrounding hydroxyl groups to evolve two water molecules. For ammoniojarosite, this step corresponds to the protonation of a hydroxyl group by ammonium, so that ammonia and water are liberated simultaneously. Iron(II) sulfate was identified as a possible intermediate during the decomposition of ammoniojarosite (421–521 °C) due to a redox reaction between iron(III) and the liberated ammonia during decomposition. Iron(II) ions were also confirmed with the 1,10-phenanthroline test. Iron(III) sulfate and other commonly suggested intermediates for hydronium and ammoniojarosite decomposition are not major crystalline phases; if they are formed, then they most likely exist as an amorphous phase or a different low temperature phases than usual.

Organo-LDH synthesized via tricalcium aluminate hydration in the present of Na-dodecylbenzenesulfate aqueous solution and subsequent investigated by near-infrared and mid-infrared

Na-dodecylbenzenesulfate (SDBS), a natural anionic surfactant, has been successfully intercalated into a Ca based LDH host structure during tricalcium aluminate hydration in the presence of SDBS aqueous solution (CaAl-SDBS-LDH). The resulting product was characterized by powder X-ray diffraction (XRD), mid-infrared (MIR) spectroscopy combined with near-infrared (NIR) spectroscopy technique, thermal analysis (TG–DTA) and scan electron microscopy (SEM). The XRD results revealed that the interlayer distance of resultant product was expanded to 30.46 Å. MIR combined with NIR spectra offered an effective method to illustrate this intercalation. The NIR spectra (6000–5500 cm−1) displayed prominent bands to expound SDBS intercalated into hydration product of C3A. And the bands around 8300 cm−1 were assigned to the second overtone of the first fundamental of CH stretching vibrations of SDBS. In addition, thermal analysis showed that the dehydration and dehydroxylation took place at ca. 220 °C and 348 °C, respectively. The SEM results appeared approximately hexagonal platy crystallites morphology for CaAl-SDBS-LDH, with particle size smaller and thinner.

Thermal behavior of kaolinite–urea intercalation complex and molecular dynamics simulation for urea molecule orientation

The thermal behavior of kaolinite–urea intercalation complex was investigated by thermogravimetry–differential scanning calorimetry (TG–DSC), X-ray diffraction (XRD), and fourier transform infrared spectroscopy (FTIR). In addition, the interaction mode of urea molecules intercalated into the kaolinite gallery was studied by means of molecular dynamics simulation. Three main mass losses were observed at 136 °C, in the range of 210–270 °C, and at 500 °C in the TG–DSC curves, which were, respectively, attributed to (1) melting of the surface-adsorbed urea, (2) removal of the intercalated urea, and (3) dehydroxylation of the deintercalated kaolinite. The three DSC endothermic peaks at 218, 250, and 261 °C were related to the successive removals of intercalated urea with three different distribution structures. Based on the angle between the dipole moment vector of urea and the basal surface of kaolinite, the three urea models could be described as follows: (1) Type A, the dipole moment vector is nearly parallel to the basal surface of kaolinite; (2) Type B, the dipole moment vector points to the silica tetrahedron with the angle between it and the basal surface of kaolinite ranging from 20°to 40°; and (3) Type C, the dipole moment vector is nearly perpendicular to the basal surface of kaolinite. The three distribution structures of urea molecules were validated by the results of the molecular dynamics simulation. Furthermore, the thermal behavior of the kaolinite–urea intercalation complex investigated by TG–DSC was also supported by FTIR and XRD analyses.

Effect of heat-treatment on strength of clays

The main objective of this investigation was to understand the strength development of clays below fusion or vitrification temperatures of 900°C. The other objective was to establish threshold temperatures to produce a satisfactory construction material from clayey sediments from the Western Beaufort Sea for shore protection of artificial islands with minimum expense of thermal energy. Studies were, therefore, conducted using kaolinite, bentonite, and a clayey sediment from the Beaufort Sea. Unconfined-compressive-strength tests were conducted on clay samples heat treated from 110 to 700°C. Furthermore, to understand the factors responsible for strength-development-thermogravimetric studies and pore-size analysis, using mercury porosimetry, were also conducted. A gradual increase in strength was obtained with an increase in firing temperature. However, substantial and permanent increase in strength occurred only after dehydroxylation of all the clays studied; Clay samples heated to temperatures above dehydroxylation became resistant to disintegration upon immersion in water. Results indicate that the clayey sediments from Western Beaufort Sea have to be heat treated to about 600°C to produce granular material for use as a fill or shore-protection material for artificial islands.

Synthesis of acicular hydrogoethite (alpha-FeOOH center dot xH(2)O; 0.1 < x < 0.22) particles using morphology controlling cationic additives and magnetic properties of maghemite derived from hydrogoethite

A method for the preparation of acicular hydrogoethite (alpha -FeOOH.xH(2)O, 0.1 < x < 0.22) particles of 0.3-1 mm length has been optimized by air oxidation of Fe( II) hydroxide gel precipitated from aqueous (NH4)(2)Fe(SO4)(2) solutions containing 0.005-0.02 atom% of cationic Pt, Pd or Rh additives as morphology controlling agents. Hydrogoethite particles are evolved from the amorphous ferrous hydroxide gel by heterogeneous nucleation and growth. Preferential adsorption of additives on certain crystallographic planes thereby retarding the growth in the perpendicular direction, allows the particles to acquire acicular shapes with high aspect ratios of 8-15. Synthetic hydrogoethite showed a mass loss of about 14% at similar to 280 degreesC, revealing the presence of strongly coordinated water of hydration in the interior of the goethite crystallites. As evident from IR spectra, excess H2O molecules (0.1- 0.22 per formula unit) are located in the strands of channels formed in between the double ribbons of FeO6 octahedra running parallel to the c- axis. Hydrogoethite particles constituted of multicrystallites are formed with Pt as additive, whereas single crystallite particles are obtained with Pd (or Rh). For both dehydroxylation as well as H-2 reduction, a lower reaction temperature (similar to 220 degreesC) was observed for the former (Pt treated) compared to the latter (Pd or Rh) (similar to 260 degreesC). Acicular magnetite (Fe3O4) was prepared either by reducing hydrogoethite (magnetite route) or dehydroxylating hydrogoethite to hematite and then reducing it to magnetite (hematite- magnetite route). According to TEM studies, preferential dehydroxylation of hydrogoethite along < 010 > leads to microporous hematite. Maghemite (gamma -Fe2O3 (-) (delta), 0 < < 0.25) was obtained by reoxidation of magnetite. The micropores are retained during the topotactic transformation to magnetite and finally to maghemite, whereas cylindrical mesopores are formed due to rearrangement of the oxygen sublattice from hexagonal to cubic close packing during the conversion of hydrogoethite to magnetite and then to maghemite. Accordingly, three different types of maghemite particles are realized: strongly oriented multicrystalline particles, single crystalline acicular particles with micropores or crystallites having mesopores. Higher values of saturation magnetization ((s) = 74 emu g(-1)) and coercivity (H-c = 320 Oe) are obtained for single crystalline mesoporous particles. In the other cases, the smaller size of particles and larger distribution of micropores decreases sigma (s) considerably ( < 60 emu g(-1)) due to relaxation effects of spins on the surface atoms as revealed by Mossbauer spectroscopy.

Photoluminescence of Sr(2-x)Ln(x)CeO(4+x/2) (Ln = Eu, Sm or Yb) prepared by a wet chemical method

A wet chemical route is developed for the preparation of Sr2CeO4 denoted the carbonate-gel composite technique. This involves the coprecipitation of strontium as fine particles of carbonates within hydrated gels of ceria (CeO2.xH(2)O, 40dehydroxylation is followed by the reaction with SrCO3 to form Sr2CeO4 with complete phase purity. Doping of other rare-earths is carried out at the co-precipitation stage. The photoluminescence (PL) observed for Sr2CeO4 originates from the Ce4+-O2- charge-transfer (CT) transition resulting from the interaction of Ce4+ ion with the neighboring oxide ions. The effect of next-nearest-neighbor (NNN) environment on the Ce4+-O2- CT emission is studied by doping with Eu3+, Sm3+ or Yb3+ which in turn, have unique charge-transfer associated energy levels in the excited states in oxides. Efficient energy transfer occurs from Ce4+-O2- CT state to trivalent lanthanide ions (Ln(3+)) if the latter has CT excited states, leading to sensitizer-activator relation, through non-resonance process involving exchange interaction. Yb3+-substituted Sr2CeO4 does not show any line emission because the energy of Yb3+-O2- CT level is higher than that of the Ce4+-O2- CT level. Sr2-xEuxCeO4+x/2 shows white emission at xless than or equal to0.02 because of the dominant intensities of D-5(2)-F-7(0-3) transitions in blue-green region whereas the intensities of D-5(0)-F-7(0-3) transitions in orange-red regions dominate at concentrations xgreater than or equal to0.03 and give red emission. The appearance of all the emissions from D-5(2), D-5(1) and D-5(0) excited states to the F-7(0-3) ground multiplets of Eu3+ is explained on the basis of the shift from the hypersensitive electric-dipole to magnetic-dipole related transitions with the variation in site symmetry with increasing concentration of Eu3+. White emission of Sr2-x SmxCeO4+x/2 at xless than or equal to0.02 is due the co-existence of Ce4+-O2- CT emission and (4)G(4)(5/2)-H-6(J) Sm3+ transitions whereas only the Sm3+ red emission prevails for xgreater than or equal to0.03. The above unique changes in PL emission features are explained in terms of the changes in NNN environments of Ce4+. Quenching of Ce4+-O2- CT emission by other Ln(3+) is due to the ground state crossover arising out of the NNN interactions.

Characterization of silver-kaolinite (AgK): an adsorbent for long-lived I-129 species

Bentonite is a preferred buffer and backfill material for deep geological disposal of high-level nuclear waste (HLW). Bentonite does not retain anions by virtue of its negatively charged basal surface. Imparting anion retention ability to bentonite is important to enable the expansive clay to retain long-lived I-129 (iodine-129; half-life = 16 million years) species that may escape from the HLW geological repository. Silver-kaolinite (AgK) material is prepared as an additive to improve the iodide retention capacity of bentonite. The AgK is prepared by heating kaolinite-silver nitrate mix at 400 degrees C to study the kaolinite influence on the transition metal ion when reacting at its dehydroxylation temperature. Thermo gravimetric-Evolved Gas Detection analysis, X-ray diffraction analysis, X-ray photo electron spectroscopy and electron probe micro analysis indicated that silver occurs as AgO/Ag2O surface coating on thermally reacting kaolinite with silver nitrate at 400 degrees C.

Synthesis, Oxidation and Photophysics of Perfluoroborated Tetrakis(pyrophosphito)diplatinate (II) and Density Functional Theory (DFT) Study of Electrochemical CO2 Reduction by Mn Catalysts

In the first part of this thesis (Chapters I and II), the synthesis, characterization, reactivity and photophysics of per(difluoroborated) tetrakis(pyrophosphito)diplatinate(II) (Pt(POPBF₂)) are discussed. Pt(POP-BF₂) was obtained by reaction of [Pt₂(POP)₄]^4- with neat boron trifluoride diethyl etherate (BF₃·Et₂O). While Pt(POP-BF₂) and [Pt₂(POP)₄]^4- have similar structures and absorption spectra, they differ in significant ways. Firstly, as discussed in Chapter I, the former is less susceptible to oxidation, as evidenced by the reversibility of its oxidation by I2. Secondly, while the first excited triplet states (T₁) of both Pt(POP-BF₂) and [Pt₂(POP)₄]^4- exhibit long lifetimes (ca. 0.01 ms at room temperature) and substantial zero-field splitting (40 cm^-1), Pt(POP-BF₂) also has a remarkably long-lived (1.6 ns at room temperature) singlet excited state (S₁), indicating slow intersystem crossing (ISC). Fluorescence lifetime and quantum yield (QY) of Pt(POP-BF₂) were measured over a range of temperatures, providing insight into the slow ISC process. The remarkable spectroscopic and photophysical properties of Pt(POP-BF₂), both in solution and as a microcrystalline powder, form the theme of Chapter II.

In the second part of the thesis (Chapters III and IV), the electrochemical reduction of CO₂ to CO by [(L)Mn(CO)₃]^- catalysts is investigated using density functional theory (DFT). As discussed in Chapter III, the turnover frequency (TOF)-limiting step is the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^0/- (bpy = bipyridine) by trifluoroethanol (TFEH) to form [(bpy)Mn(CO)₄]^+/0. Because the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^- is faster, maximum TOF (TOF_max) is achieved at potentials sufficient to completely reduce [(bpy)Mn(CO)₃(CO₂H)]⁰ to [(bpy)Mn(CO)₃(CO₂H)]^-. Substitution of bipyridine with bipyrimidine reduces the overpotential needed, but at the expense of TOF_max. In Chapter IV, the decoration of the bipyrimidine ligand with a pendant alcohol is discussed as a strategy to increase CO₂ reduction activity. Our calculations predict that the pendant alcohol acts in concert with an external TFEH molecule, the latter acidifying the former, resulting in a ~ 80,000-fold improvement in the rate of TOF-limiting dehydroxylation of [(L)Mn(CO)₃(CO₂H)]^-.

An interesting strategy for the co-upgrading of light olefins and alkanes into heavier alkanes is the subject of Appendix B. The proposed scheme involves dimerization of the light olefin, operating in tandem with transfer hydrogenation between the olefin dimer and the light alkane. The work presented therein involved a Ta olefin dimerization catalyst and a silica-supported Ir transfer hydrogenation catalyst. Olefin dimer was formed under reaction conditions; however, this did not undergo transfer hydrogenation with the light alkane. A significant challenge is that the Ta catalyst selectively produces highly branched dimers, which are unable to undergo transfer hydrogenation.

THEORETICAL-STUDIES ON THE CYCLIZATION PROCESS OF A NEW ORGANOSULFUR REACTION

The cyclization process of a new organosulfur reaction was studied by the MNDO (UHF) method. The first reaction path was assumed to be via the organosulfur radical intermediate, the second via the ionic (cationic and anionic) intermediates. The dehydroxylation process was assumed to occur with the synergistic cyclization. The results obtained indicate that the potential energy barrier of the first reaction path was about 102 kcal mol(-1), and although the formation of the ionic intermediate is comparatively difficult, the potential energy barrier of the second path is comparable to the first. The sequential reaction path via the radical intermediate, i.e. first cyclization, then dehydroxylation, was investigated for comparison. The cyclization reaction was found to be the thermodynamically favored process, while the ensuing dehydroxylation process was found to have a potential energy barrier of about 62 kcal mol(-1).

The effect of heating temperature on the properties of vermiculites from Tanzania with respect to potential agronomic applications

This study was carried out to assess the properties of vermiculites from Tanzania with respect to the temperature used to expand them. Vermiculites from five locations in the Mozambique Belt of Tanzania were sampled and heated at 15, 200, 400, 600 and 800 °C in a muffle furnace. Palabora Europe Ltd provided one sample for comparison from their South Africa deposit which provides vermiculite used worldwide as a soil amendment. Water release characteristic, cation exchange capacity, pH, mass loss, and bulk density were among the properties assessed. All six vermiculites responded differently on heating, and had a significant variation in their agronomic properties. Water release characteristic varied with the degree of exfoliation and phase composition. Although vermiculites from Tanzania expanded on heating, their capacity to retain plant available water was relatively low as compared to vermiculite from Palabora. Disintegration on heating and the presence of a high amount of iron could be among the factors affecting their water release characteristic. Loss of hydroxyl water was higher in vermiculites than in hydrobiotites. Dehydroxylation enhanced the availability of exchangeable K⁺ and reduced significantly the cation exchange capacity of vermiculites. The optimum exchangeable K⁺ was obtained on heating at a temperature of 600 °C. The pH was unaffected by heating to a temperature of less than 600 °C. At higher temperature, the pH increased in some samples and was accompanied by substantial amounts of exchangeable Mg²⁺. Thus, it was concluded that initial characterization of vermiculites is essential prior to potential agricultural applications in order to optimize their agronomic potential. © 2008 Elsevier B.V. All rights reserved.

Contribuição para o conhecimento das propriedades pozolânicas da fracção fina resultante da produção de areia de origem granítica

O presente estudo diz respeito a um trabalho de pesquisa no âmbito de uma Tese de Mestrado incluída no segundo ciclo de estudos do curso de Engenharia Geotécnica e Geoambiente, realizado sobre as condições de desidroxilação para a obtenção de metacaulino com propriedades cimentíceas, a partir da fracção argilosa proveniente dos finos residuais da produção de areias de natureza granítica. O produto resultante da alteração e desintegração dos feldspatos constituintes dos granitos são ricos em caulinite. Na natureza e em particular no Norte de Portugal, existem significativos depósitos cauliníticos com características potenciadoras para a produção de metacaulino. O metacaulino utilizado neste estudo foi obtido de uma amostra de argila submetida a 750oC, por um período de tempo de 30 minutos, processo que permitiu a desidroxilação quase total da matéria-prima, transformando esta numa fase amorfa e irreversível, com propriedades pozolânicas. Os metacaulinos, também conhecidos por geopolímeros, são produtos de fácil produção utilizando uma matéria-prima abundante e proporcionam a obtenção de novos produtos que permitem a substituição parcial do cimento Portland normal na composição das pastas de betão, com vantagens significativas no comportamento mecânico e na resistência aos agentes atmosféricos. Neste estudo são apresentados os resultados dos ensaios de caracterização da matéria-prima, das condições de calcinação e do produto resultante da desidroxilação, nomeadamente a determinação da pozolanicidade e das características fundamentais para a aplicabilidade do produto. No âmbito da especialidade de Georrecursos, consideramos que este trabalho está perfeitamente adequado, já que, para além do estudo para o conhecimento das propriedades da matéria-prima, foi possível, através das alterações introduzidas com o tratamento térmico, obter um novo produto, cuja utilização terá importantes reflexos na sustentabilidade dos recursos naturais e sua utilização.

Contribuição para o conhecimento sobre o efeito da utilização de material pozolânico no fabrico de betão

O presente trabalho, realizado no âmbito da Tese de Mestrado, tem como principal objectivo estudar as características pozolânicas dos materiais da zona de Arganil para substituição parcial do cimento Portland com o objectivo de intensificar certas qualidades devido à diminuição da porosidade do betão. Estas qualidades são interessantes quando se procura maior durabilidade. Para tal, foram realizados diversos ensaios para a caracterização física, química e mineralógica dos produtos. Os metacaulinos utilizados foram obtidos de amostras de argila submetidas a calcinação (750oC, durante uma hora), processo que permitiu a desidroxilação quase total da matéria-prima, transformando esta numa fase amorfa e irreversível, com propriedades pozolânicas. São apresentados os resultados dos ensaios de caracterização da matéria-prima, das condições de calcinação e do produto resultante da desidroxilação, nomeadamente a determinação da pozolanicidade e superfície específica e das características fundamentais para a aplicabilidade do produto. Descreve ainda o emprego do metacaulino em betões de resistência convencional. Estudou-se a influência do emprego do metacaulino (15% de substituição de cimento, em massa) na resistência à flexão e à compressão (aos 28 dias) em argamassas e o emprego de metacaulino (10%, 15% e 20% de substituição de cimento, em massa) na resistência à compressão (3, 7 e 28 dias) no betão.

Reactions of steroidal epoxides with strong organic bases and an investigation into the syntheses of some labelled pregnane derivatives

Reactions of 5,6- and 4,5-epoxycholestane derivatives with strong bases were investigated. Epoxidation of 3a-acetoxycholest-5-ene also gave a new compound along with the anticipated epoxides. Interconversions of the latter were observed. Some possible mechanisms of its formation and rearrangements have been pIioposed. No reaction was observed with any of the 5,6- and 4,5-steroidal epoxides employed in the present study, using potassium tertiary butoxide under refluxing conditions. n-Butyllithium reacted only with 5,6-epoxycholestanes bearing a ketal moiety at the C3 carbon. Opening of the ketal group was observed with n-butyllithium in the case of a ~-epoxide. The reaction was also investigated in the absence of epoxide functionality. A possible mechanism for the opening of ketal group has been proposed. Lithium diethylamide (LDEA) was found effective in rearranging 5,6- and 4,5-epoxides to their ~orresponding allylic alcohols. These rearrangements presumably proceed via syn-eliminations, however the possibility of a corresponding anti-elimination has not been eliminated. A substituent effect of various functional groups (R = H, OH, OCH2CH20) at C3 has-been observed on product distribution in the LDEApromoted rearrangements of the corresponding epoxides. No reaction of these epoxides was observed with lithium diisopropylamide (LDA) • In the second part of the project, several attempts were made towards the sYRthesis of deoxycorticoste~one~17,2l,2l~d3' a compound desirable for the 2l-dehydroxylation studies of deoxycorticosterone. Several routes were investigated, and some deuterium labelled pregnane derivatives were prepared in this regard. Microbial 21-hydroxylation of progesteronel7,21,21,2l- d4 by ~ niger led to loss of deuterium from C21 of the product. An effort was made to hydroxylate progesterone microbially under neutral condtions.