Dissertationen zum Thema „Copper silicates“

Acid leaching of different natural chrysocolla samples under ambient conditions demonstrated that the chemical and chrystallographic inhomogenity significantly affects the rate and that it is virtually impossible to use the mineral as a model for the kinetics of hydrometallurgical processing of copper ores.Dissolution experiments, stability diagrams,and X-ray powder diffraction studies are undertaken and studied in this research and results are given.It is found that a complete solid solution series exists in Nature with most tungstenian wulfenites and molybdenum stolzites containing a range of compositions. The first occurrence of a molybdenum stolzite from Broken Hill, Australia, which also contains small amounts of chromium is noted.Raman microprobe spectroscopy has proven to be a very quick and effective non-destructive method for semi-quantitative analysis of the wulfenite-stolzite and powellite-scheelite solid-solution series and in detecting very small amounts of substituted chromate in wulfenite, stolzite and anglesite
Doctor of Philosophy (PhD)

Thesis (PhD) -- University of Western Sdyney, 2001.
"A thesis presented in accordance with the regulations governing the award of the degree of Doctor of Philosophy, University of Western Sydney" "November 2001" Bibliography: leaves 249 - 254.

Dans ce travail nous avons analyse de petits agregats metalliques en verre dans le but d'en determiner les proprietes structurales, leur lien avec la reponse optique et l'influence de l'ordre locale sur les proprietes de diffusion des metaux dans les verres alkalino-silicates. - verres silicates implantes cu : la structure des agregats de cu formes par implantation ionique dans la silice amorphe a ete etudiee au point de vue morphologique et locale. Les techniques de diffusion et diffraction de rayons x en incidence rasante ont ete utilisees et ont permis de determiner la taille des particules ainsi que leur phase cristalline. La technique de l'absorption des rayons x (xas) a ete utilisee pour determiner la structure locale des atomes de cu dans le verre ainsi que leur etat de valence. Les agregats metalliques ont ete observes et caracterises du point de vue structurale. Les agregats les plus petits montrent une reduction du parametre de maille ainsi que une augmentation du desordre statique. - l'etat de valence du cu dans les verres implantes. Les analyses des seuils d'absorption de rayons x ont montre que le cu peut etre loge dans le verre sous la forme de cu#+#1 ou cu#+#2 aussi que dans l'etat metallique. Nous avons trouve l'evidence que les ions metalliques a l'interieur du verre sont plus oxydes que ceux pres de la surface et proposons une explication pour ce phenomene. Verres soda-lime dopes par echange ionique : nous avons etudie des verres soda-lime dopes avec cu et ag par la methode de l'echange ionique prepares suivant differentes procedures. La structure atomique locale autour du metal a ete determine et ne depend pas des details de preparation de l'echantillon mais seulement du metal dopant. Agregation des metaux provoquee par bombardement ionique dans les verres la structure locale des atomes d'ag dans des verres traites par bombardement ionique a ete analysee et les phases structurales obtenues par differentes parametres de traitement ont ete determinees.

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Tese (Doutorado em Tecnologia Nuclear)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

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Dissertação (Mestrado em Tecnologia Nuclear)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Silicate melt inclusions are ubiquitous in quartz phenocrysts, yet there are few studies of such inclusions from porphyry copper systems. A melt inclusion forms when magma is trapped in a growing phenocryst. If a phenocryst is able to preserve the original parent magma, then accurate information can be obtained for ancient volcanic systems. In recent igneous systems, melt inclusions are commonly preserved as optically clear homogeneous glass representative of magma stored at depth before eruption. Melt inclusions are difficult to recognize in quartz phenocrysts from porphyry copper system because they are crystalline and hidden by exsolved magmatic volatiles. The inclusions range in size from less than 5 to over 150 μm. In order to evaluate the magmatic contribution to economic mineralization, we conducted three separate studies to determine whether or not crystallized melt inclusions preserve representative samples of magma. The first study modeled the phase relationships that occur during equilibrium crystallization and melting of haplogranite magma trapped in quartz. Results from the model are similar to observations made during the heating of crystallized melt inclusions from porphyry copper systems. It is necessary to re-melt the crystal and volatile phases before chemical analysis. Micro-explosions caused by heating resulted in the loss of important chemical components. Our second study evaluated several microthermometric heating procedures using synthetic melt inclusions trapped at conditions similar to those inferred for porphyry copper systems. A synthetic hydrous melt was saturated with saline hydrothermal solutions allowing both melt and aqueous fluids to be trapped in quartz. Based on microthermometric measurements from these coeval melt and aqueous fluid inclusions we were able to predict the known trapping temperature and pressure of formation. This technique can be applied to natural samples to constrain trapping pressures and temperatures. It was found that slower heating rates could be used to avoid overheating and that heating under a confining pressure greatly minimizes the decrepitation of inclusions. The third study examined the copper concentrations in melt inclusions from the Red Mountain, Arizona porphyry copper system. Older andesite magma contains pyroxene with melt inclusions of higher copper concentrations compared to melt inclusions in quartz from quartz latite. The higher water concentrations in crystallized melt inclusions in the quartz, and abundant aqueous fluid inclusions indicates that the exsolution of water from the magma occurred prior to the trapping of melt inclusions in quartz. The lower water concentrations and the absence of aqueous fluid inclusions indicates that the andesite never reached the stage of water exsolution. The results obtained here are consistent with models that suggest that copper is extracted from the melt by saline magmatic fluids, producing a metal-charged hydrothermal solution and leaving behind a metal-depleted melt and serves to identify the potential contribution of melt inclusion studies to constrain the origin of ore metals in porphyry copper deposits.
Ph. D.

Zinc-nickel ?-phase silicate and copper-nickel silicate corrosion resistant coatings have been prepared via electrochemical methods to improve currently available corrosion resistant materials in the oil and gas industry. A layered silicate, montmorillonite, has been incorporated into the coatings for increased corrosion protection. For the zinc nickel silicate coatings, optimal plating conditions were determined to be a working pH range of 9.3 -9.5 with a borate based electrolyte solution, resulting in more uniform deposits and better corrosion protection of the basis metal as compared to acidic conditions. Quality, strongly adhering deposits were obtained quickly with strong, even overall coverage of the metal substrate. The corrosion current of the zinc-nickel-silicate coating is Icorr = 3.33E-6 for a borate based bath as compared to a zinc-nickel bath without silicate incorporation (Icorr = 3.52E-5). Step potential and direct potential methods were examined, showing a morphological advantage to step potential deposition. The effect of borate addition was examined in relation to zinc, nickel and zinc-nickel alloy deposition. Borate was found to affect the onset of hydrogen evolution and was examined for absorption onto the electrode surface. For copper-nickel silicate coatings, optimal conditions were determined to be a citrate based electrolytic bath, with pH = 6. The solutions were stable over time and strong adhering, compact particle deposits were obtained. The corrosion current of the copper-nickel-silicate coatings is Icorr = 3.86E-6 (copper-nickel coatings without silicate, Icorr = 1.78E-4). The large decrease in the corrosion current as the silicate is incorporated into the coating demonstrates the increase in corrosion resistance of the coatings with the incorporation of silicates.

The TaSiO6 films, ~8Å thick, were formed by sputter deposition of Ta onto ultrathin SiO2 substrates at 300 K, followed by annealing to 600 K in 2 torr O2. X-ray photoelectron spectroscopy (XPS) measurements of the films yielded a Si(2p) binding energy at 102.1 eV and Ta(4f7/2) binding energy at 26.2 eV, indicative of Ta silicate formation. O(1s) spectra indicate that the film is substantially hydroxylated. Annealing the film to > 900 K in UHV resulted in silicate decomposition to SiO2 and Ta2O5. The Ta silicate film is stable in air at 300K. XPS data show that sputter-deposited Cu (300 K) displays conformal growth on Ta silicate surface (TaSiO6) but 3-D growth on the annealed and decomposed silicate surface. Initial Cu/silicate interaction involves Cu charge donation to Ta surface sites, with Cu(I) formation and Ta reduction. The results are similar to those previously reported for air-exposed TaSiN, and indicate that Si-modified Ta barriers should maintain Cu wettability under oxidizing conditions for Cu interconnect applications. XPS has been used to study the reaction of tert-butylimino tris(diethylamino) tantalum (TBTDET) with atomic hydrogen on SiO2 and organosilicate glass (OSG) substrates. The results on both substrates indicate that at 300K, TBTDET partially dissociates, forming Ta-O bonds with some precursor still attached. Subsequent bombardment with atomic hydrogen at 500K results in stoichiometric TaN formation, with a Ta(4f7/2) feature at binding energy 23.2 eV and N(1s) at 396.6 eV, leading to a TaN phase bonded to the substrate by Ta-O interactions. Subsequent depositions of the precursor on the reacted layer on SiO2 and OSG, followed by atomic hydrogen bombardment, result in increased TaN formation. These results indicate that TBTDET and atomic hydrogen may form the basis for a low temperature atomic layer deposition (ALD) process for the formation of ultraconformal TaNx or Ru/TaNx barriers. The interactions of sputter-deposited ruthenium with OSG at 300 K have been studied by XPS for Ru coverages from ~ 0.1 monolayer to several monolayers, using in-situ sample transfer between the deposition and analysis chambers. The results indicate Stranski-Krastanov (SK) type growth, with the completion of the first layer of Ru at an average thickness corresponding to 1 monolayer average coverage. Ru(0) is the only electronic state present. XPS core level spectra indicate weak chemical interactions between Ru and the substrate. A less pronounced tendency towards SK growth was observed for Ru deposition on parylene. Deposition of Ru on OSG followed by electroless deposition of Cu resulted in the formation of a shiny copper film that failed the Scotch® tape test. Results indicate failure mainly at the Ru/OSG interface.

The effects of corrosion inhibitors on water quality and the distribution system were studied. This dissertation investigates the effect of inhibitors on iron surface roughness, copper surface roughness, and copper release. Corrosion inhibitors included blended poly/ortho phosphate, sodium orthophosphate, zinc orthophosphate, and sodium silicate. These inhibitors were added to a blend of surface water, groundwater, and desalinated brackish water. Surface roughness of galvanized iron, unlined cast iron, lined cast iron, and polyvinyl chloride was measured using pipe coupons exposed for three months. Roughness of each pipe coupon was measured with an optical surface profiler before and after exposure to inhibitors. For most materials, inhibitor did not have a significant effect on surface roughness; instead, the most significant factor determining the final surface roughness was the initial surface roughness. Coupons with low initial surface roughness tended to have an increase in surface roughness during exposure, and vice versa, implying that surface roughness tended to regress towards an average or equilibrium value. For unlined cast iron, increased alkalinity and increased temperature tended to correspond with increases in surface roughness. Unlined cast iron coupons receiving phosphate inhibitors were more likely to have a significant change in surface roughness, suggesting that phosphate inhibitors affect stability of iron pipe scales. Similar roughness data collected with new copper coupons showed that elevated orthophosphate, alkalinity, and temperature were all factors associated with increased copper surface roughness. The greatest increases in surface roughness were observed with copper coupons receiving phosphate inhibitors. Smaller increases were observed with copper coupons receiving silicate inhibitor or no inhibitor. With phosphate inhibitors, elevated temperature and alkalinity were associated with larger increases in surface roughness and blue-green copper (II) scales.. Otherwise a compact, dull red copper (I) scale was observed. These data suggest that phosphate inhibitor addition corresponds with changes in surface morphology, and surface composition, including the oxidation state of copper solids. The effects of corrosion inhibitors on copper surface chemistry and cuprosolvency were investigated. Most copper scales had X-ray photoelectron spectroscopy binding energies consistent with a mixture of Cu2O, CuO, Cu(OH)2, and other copper (II) salts. Orthophosphate and silica were detected on copper surfaces exposed to each inhibitor. All phosphate and silicate inhibitors reduced copper release relative to the no inhibitor treatments, keeping total copper below the 1.3 mg/L MCLG for all water quality blends. All three kinds of phosphate inhibitors, when added at 1 mg/L as P, corresponded with a 60% reduction in copper release relative to the no inhibitor control. On average, this percent reduction was consistent across varying water quality conditions in all four phases. Similarly when silicate inhibitor was added at 6 mg/L as SiO2, this corresponded with a 25-40% reduction in copper release relative to the no inhibitor control. Hence, on average, for the given inhibitors and doses, phosphate inhibitors provided more predictable control of copper release across changing water quality conditions. A plot of cupric ion concentration versus orthophosphate concentration showed a decrease in copper release consistent with mechanistic control by either cupric phosphate solubility or a diffusion limiting phosphate film. Thermodynamic models were developed to identify feasible controlling solids. For the no inhibitor treatment, Cu(OH)2 provided the closest prediction of copper release. With phosphate inhibitors both Cu(OH)2 and Cu(PO4)·2H2O models provided plausible predictions. Similarly, with silicate inhibitor, the Cu(OH)2 and CuSiO3·H2O models provided plausible predictions.
Ph.D.
Department of Civil and Environmental Engineering
Engineering and Computer Science
Environmental Engineering PhD

It is important to optimize glass compositions for their specific purpose but also for the efficiency of the production process, the manufacturing of glass. This will be beneficial economically and environmentally. Today many processes and glass compositions are already optimized, but due to more strict legislation on toxic elements and substances there must be changes in many glass compositions. One of these elements is antimony; the oxide is used as fining agent to obtain a bubble free glass within a reasonable process time. One aim with this thesis is to obtain a deeper understanding of the fining mechanism in 20R2O-10MO-70SiO2 (R=Na and/or K, M = Ca and/or Ba, Mg, Sr) glasses in order to minimise the amount of Sb2O3. Another intention is to study the structure of 20R2O-10CaO-70SiO2 (R = Na, K) with Cu2+ as probe ion and thus get a deeper knowledge of the surrounding glass matrix.  The optical basicity scale is used to determine the acid/base character of the different glass compositions.   Fining efficiency results showed a remarkable increase of the number of remaining bubbles when the glass contains either approximately equal amounts of Na and K or Ca and Ba, Mg or Sr. The much higher number of bubbles in the potassium containing glasses compared to the sodium containing is explained by the increase in viscosity, the increase in optical basicity and thus lower oxygen activity. The differences in the fining efficiency when altering alkaline earth ions cannot be explained by the optical basicity values, it seems to be a more complicated situation.   This thesis also reports maximum in Vickers hardness and packing density as well as minimum in glass transition temperature for the mixed alkali glasses. The mixed alkaline earth glasses do not exhibit any clear nonlinear behaviour. Raman spectroscopy measurements showed a variation in the network connectivity which has a clear relation to the optical basicity of the different glass compositions. The combination of UV-Vis-NIR and X-ray absorption spectroscopy measurements showed that the coordination sphere for Cu(II) is a tetragonal distorted octahedron with two elongated Cu-O bonds along the z axis. There were no trends in the degree of tetragonal distortion, thus it was about the same for all the investigated glass compositions. Cu(I) is found to be coordinated by two oxygen ligands in mainly linear coordination sphere, evidenced from X-ray absorption spectroscopy.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES
The bacterial blight caused by Xanthomonas citri subsp. malvacearum (Xcm) is the most important bacterial disease of cotton in the Middle-West and Northeast Regions of Brazil. The variability of a population formed by 100 Xcm strains obtained from commercial fields in the states of Goiás, Mato Grosso, Mato Grosso do Sul and Bahia, Brazil, was analyzed based upon genetic and phenotypic characteristics. The enzymes amylase, lipase, cellulase and the polysaccharide levan were produced by all Xcm isolates while the caseinase was only produced by 20 strains. All strains induced hipersensitivity reaction in tomato leaves. The 100 strains were sensitive to copper oxychloride (1500 mg L-1), copper hidroxide (1614 mg L-1), oxytetracicline (600 mg L-1), oxytetracicline (90 mg L-1) + tribasic copper sulfate (1500 mg L-1) and oxytetracicline (76.6 mg L-1) + streptomycin sulfate (367.2 mg L-1), but resistant to kasugamycin (60 mg L-1). Among the eighteen tested antibiotics the strains presented variable reaction in relation to: nalidixic acid, amoxicillin, azithromycin, bacitracin, eritromicin, kanamycin, pefloxacin, tobramycin e vancomycin. Rep-PCR (REP, ERIC and BOX) showed the formation of five groups at 70% similarity level. Group I contained 98 strains, including the reference strain Xcm IBSBF1733, group II contained only two strains from Bahia and the other three groups included strains of Xanthomonas citri pv. anacardii, X. citri pv. mangiferaeindicae e X. axonopodis pv. spondiae used for comparison. This work also evaluated the effect of silicon (Si) on the bacterial blight of cotton control and the putative mechanisms involved in the resistance potentialized by this element were evaluated. Calcium silicate (CaSiO3) was incorporated into the soil at concentrations of 0.00, 0.25, 0.50, 1.50 and 3.00 g of SiO2 kg-1 soil 25 days before planting. Leaves of 33-day-old-plants were inoculated by infiltration with 0.5 mL suspension of Xcm (108 CFU ml-1). Components of resistance were evaluated every two days until 10 days after inoculation, at which point plant development and the accumulation of Si and Calcium (Ca) were also determined. H2O2 production and the activity of enzymes related to plant defenses were analyzed at 6, 12 and 24 hours after inoculation in plants +/-Si. In vitro inhibition of pathogen growth due to Si was also assessed. No significant difference was seen among the treatments regarding incubation period, disease incidence or inhibition of bacterial growth. However, with the application of 1.50 g of SiO2 kg-1 of soil, a reduction in severity (54.9%) was observed along with a reduction in the area under the disease progression curve (35.76%) and an increase in plant height (7.04%). There was no observable accumulation of Si in the cotton leaves. Levels of soluble proteins and H2O2 and activity of the enzymes SOD, APX, guaiacol peroxidase, PAL and b Glu were altered in the presence of Si (1.80 g SiO2 kg-1). Thus based on the genetic and phenotypic characteristics studied we conclude that the population of 100 Xcm strains presents low variability, and that the reduction of cotton bacterial blight severity mediated by Si is probably associated to the characteristic events of induced resistance observed.
A mancha-angular, causada por Xanthomonas citri subsp. malvacearum (Xcm), é a principal doença bacteriana do algodoeiro no Centro-Oeste e Nordeste do Brasil. A variabilidade de uma população de 100 isolados de Xcm, oriundos de plantas com sintomas típicos de mancha-angular em áreas produtoras de algodoeiro dos estados de Goiás, Mato Grosso, Mato Grosso do Sul e Bahia, Brasil, foi analisada com base em características fenotípicas e genéticas. As enzimas amilase, lipase e celulase e o polissacarídeo levana foram produzidos por todos os isolados de Xcm, enquanto a caseinase foi produzida apenas por 20 isolados. Todos os isolados induziram reação de hipersensibilidade em folhas de tomateiro. Os 100 isolados foram sensíveis a oxicloreto de cobre (1500 mg l-1), hidróxido de cobre (1614 mg l-1), oxitetraciclina (600 mg l-1), oxitetraciclina (90 mg l-1) + sulfato tribásico de cobre (1500 mg l-1) e oxitetraciclina (76,6 mg l-1) + sulfato de estreptomicina (367,2 mg l-1), e resistentes a casugamicina (60 mg l-1). Dentre os 18 antibióticos testados, os isolados bacterianos apresentaram reação variável a nove: ácido nalidíxico, amoxicilina, azitromicina, bacitracina, eritromicina, kanamicina, pefloxacina, tobramicina e vancomicina. Rep-PCR (REP, ERIC e BOX) revelou a formação de cinco grupos ao nível de 70% de similaridade, sendo o grupo I constituído de 98 isolados, incluindo o isolado referência de Xcm IBSBF1733, o grupo II, formado apenas por dois isolados oriundos da Bahia e os três outros grupos por isolados de X. citri pv. anacardii, X. citri pv. mangiferaeindicae e X. axonopodis pv. spondiae utilizados para comparação. Neste trabalho também foi avaliado o efeito do silício (Si) no controle da mancha-angular do algodoeiro, e os possíveis mecanismos envolvidos na resistência potencializada por este elemento. O silicato de cálcio (CaSiO3) foi incorporado ao solo nas doses de 0,00; 0,25; 0,50; 1,50 e 3,00 g de SiO2 kg-1 de solo 25 dias antes do plantio. Plantas com 33 dias tiveram as folhas inoculadas por infiltração com 0,5 mL de suspensão de Xcm (108 UFC ml-1). Os componentes da resistência foram avaliados a cada dois dias até 10 dias após a inoculação, quando o desenvolvimento da planta e o acúmulo de Si e Ca foram também determinados. Foram ainda analisadas a atividade de enzimas relacionadas à defesa vegetal e a produção de H2O2 às 6, 12 e 24 h após a inoculação em plantas +/-Si e a inibição in vitro do crescimento do patógeno. Não foi verificada diferença significativa entre os tratamentos quanto ao período de incubação, incidência da mancha-angular e inibição do crescimento da bactéria. Com a aplicação da dose 1,50 g SiO2 kg-1 de solo, observou-se redução da severidade (54,9%), da área abaixo da curva de progresso da doença (35,76%) e aumento na altura das plantas (7,04%). Não foi verificado acúmulo de Si nas folhas de algodoeiro. Níveis de proteínas solúveis e H2O2 e atividade das enzimas SOD, APX, POX, PAL e GLU foram alterados na presença do Si (1,80 g SiO2 kg-1). Com base nas características fenotípicas e genéticas analisadas, conclui-se que a população de 100 isolados de Xcm estudada apresenta baixa variabilidade e que a redução da severidade da mancha-angular do algodoeiro mediada por Si está provavelmente associada aos eventos característicos de indução de resistência observados.

During the pyrometallurgical extraction of copper, a significant part of the copper is lost with discard slag, which decreases profits, overall copper recovery, and efficiency of raw material usage. Smelting furnace slag usually has a copper content that is close to or higher than that of copper ores. The investigation of copper losses to slag is thus a task of practical significance, as the ore grades are depleting. Slag cleaning, e.g., a settling furnace, can reduce copper losses to slag as the mechanically suspended copper-containing droplets separate from slag under the action of gravity and can hence be recovered.  An industrial trial was conducted in an electric settling furnace with slag originating from an electric smelting furnace and processed in a zinc fuming furnace. The trial was conducted to increase the understanding of copper losses to slag and how the process parameters temperature and settling time influence the slag copper content. The obtained slag samples were also evaluated to gain better insights as to the settling mechanism and, if any, factors that hinder the copper phases from settling. Slag modification with CaO was also evaluated to investigate how the modification influences the settling of copper phases and, thus, the final slag copper content.  Samples collected during the industrial trial were the basis for the evaluation in the current work. The samples came from batches with varying temperatures, settling times, and CaO content collected at four different sample positions. Instrumental techniques, including XRF, FAAS, ICP-SFMS, and SEM-EDS, were used to analyze the chemical compositions of the samples and the appearance of copper and associated phases.  The results indicated that the copper content of outgoing slag increased with increasing temperature in the evaluated interval. The copper content was also concluded to be more strongly affected by the temperature compared to the settling time. Regulating the temperature to the lower temperature interval in the settling furnace could thus decrease the final slag copper content. During the slag characterization, it was found that suspended copper-containing phases were hindered from settling, due to the attachment to solid phases and gas bubbles in the slag. By controlling and minimizing the presence of the bottom buildup and thus solid phases in the slag, the copper content can be decreased. The results indicated that the CaO slag modification decreased the final slag copper content, and can thus be used as a modifier for increased settling.

A study was conducted to investigate and quantify the effects of corrosion inhibitors on metal release within a pilot distribution system while varying the source water. The pilot distribution system consisted of pre-existing facilities from Taylor et al (2005). Iron, copper, and lead release data were collected during four separate phases of operation. Each phase was characterized by the particular blend ratios used during the study. A blended source water represented a water that had been derived from a consistent proportion of three different source waters. These source waters included (1) surface water treated through enhanced coagulation/sedimentation/filtration, (2) conventionally treated groundwater, and (3) finished surface water treated using reverse osmosis membranes. The corrosion inhibitors used during the study were blended orthophosphate (BOP), orthophosphate (OP), zinc orthophosphate (ZOP), and sodium silicate (Si). This document was intended to cite the findings from the study associated with corrosion treatment using various doses of sodium silicate. The doses were maintained to 3, 6, and 12 mg/L as SiO2 above the blend-dependent background silica concentration. Sources of iron release within the pilot distribution system consisted of, in the following order of entry, (1) lined cast iron, (2) un-lined cast iron, and (3) galvanized steel. Iron release data from these materials was not collected for each individual iron source. Instead, iron release data represented the measurement of iron upon exposure to the pilot distribution system in general. There was little evidence to suggest that iron release was affected by sodium silicate. Statistical modeling of iron release suggested that iron release could be described by the water quality parameters of alkalinity, chlorides, and pH. The R2 statistic implied that the model could account for only 36% of the total variation within the iron release data set (i.e. R2 = 0.36). The model implies that increases in alkalinity and pH would be expected to decrease iron release on average, while an increase in chlorides would increase iron release. The surface composition of cast iron and galvanized steel coupons were analyzed using X-ray photoelectron spectroscopy (XPS). The surface analysis located binding energies consistent with Fe2O3, Fe3O4, and FeOOH for both cast iron and galvanized steel. Elemental scans detected the presence of silicon as amorphous silica; however, there was no significant difference between scans of coupons treated with sodium silicate and coupons simply exposed to the blended source water. The predominant form of zinc found on the galvanized steel coupons was ZnO. Thermodynamic modeling of the galvanized steel system suggested that zinc release was more appropriately described by Zn5(CO3)2(OH)6. The analysis of the copper release data set suggested that treatment with sodium silicate decreased copper release during the study. On average the low, medium, and high doses decreased copper release, when compared to the original blend source water prior to sodium silicate addition, by approximately 20%, 30%, and 50%, respectively. Statistical modeling found that alkalinity, chlorides, pH, and sodium silicate dose were significant variables (R2 = 0.68). The coefficients of the model implied that increases in pH and sodium silicate dose decreased copper release, while increases in alkalinity and chlorides increased copper release. XPS for copper coupons suggested that the scale composition consisted of Cu2O, CuO, and Cu(OH)2 for both the coupons treated with sodium silicate and those exposed to the blended source water. Analysis of the silicon elemental scan detected amorphous silica on 3/5 copper coupons exposed to sodium silicate. Silicon was not detected on any of the 8 control coupons. This suggested that sodium silicate inhibitor varied the surface composition of the copper scale. The XPS results seemed to be validated by the visual differences of the copper coupons exposed to sodium silicate. Copper coupons treated with sodium silicate developed a blue-green scale, while control coupons were reddish-brown. Thermodynamic modeling was unsuccessful in identifying a controlling solid that consisted of a silicate-based cupric solid. Lead release was generally decreased when treated with sodium silicate. Many of the observations were recorded below the detection limit (1 ppb as Pb) of the instrument used to measure the lead concentration of the samples during the study. The frequency of observations below the detection limit tended to increase as the dose of sodium silicate increased. An accurate quantification of the effect of sodium silicate was complicated by the observations recorded below detection limit. If the lead concentration of a sample was below detection limit, then the observation was recorded as 1 ppb. Statistical modeling suggested that temperature, alkalinity, chlorides, pH, and sodium silicate dose were important variables associated with lead release (R2 = 0.60). The exponents of the non-linear model implied that an increase in temperature, alkalinity, and chlorides increased lead release, while an increase in pH and sodium silicate dose were associated with a decrease in lead release. XPS surface characterization of lead coupons indicated the presence of PbO, PbO2, PbCO3, and Pb3(OH)2(CO3)2. XPS also found evidence of silicate scale formation. Thermodynamic modeling did not support the possibility of a silicate-based lead controlling solid. A solubility model assuming Pb3(OH)2(CO3)2 as the controlling solid was used to evaluate lead release data from samples in which lead coupons were incubated for long stagnation times. This thermodynamic model seemed to similarly describe the lead release of samples treated with sodium silicate and samples exposed to the blended source water. The pH of each sample was similar, thus sodium silicate, rather than the corresponding increase in pH, would appear to be responsible if a difference had been observed. During the overall study, the effects of BOP, OP, ZOP, and Si corrosion inhibitors were described by empirical models. Statistically, the model represented the expected value, or mean average, function. If these models are to be used to predict a dose for copper release, then the relationship between the expected value function and the 90th percentile must be approximated. The USEPA Lead and Copper Rule (LCR) regulates total copper release at an action level of 1.3 mg/L. This action level represents a 90th percentile rather than a mean average. Evaluation of the complete copper release data set suggested that the standard deviation was proportional to the mean average of a particular treatment. This relationship was estimated using a linear model. It was found that most of the copper data sub-sets (represented by a given phase, inhibitor, and dose) could be described by a normal distribution. The information obtained from the standard deviation analysis and the normality assumption validated the use of a z-score to relate the empirical models to the estimated 90th percentile observations. Since an analysis of the normality and variance (essentially contains the same information as the standard deviation) are required to assess the assumptions associated with an ANOVA, an ANOVA was performed to directly compare the effects of the inhibitors and corresponding doses. The findings suggested that phosphate-based inhibitors were consistently more effective than sodium silicate when comparing the same treatment levels (i.e. doses). Among the phosphate-based inhibitors, the effectiveness of each respective treatment level was inconsistent (i.e. there was no clear indication that any one phosphate-based inhibitor was more effective than the other). As the doses increased for each inhibitor, the results generally suggested that there was a corresponding tendency for copper release to decrease.
Ph.D.
Department of Civil and Environmental Engineering
Engineering and Computer Science
Electrical Engineering PhD

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Universidade Estadual de Feira de Santana
Neste trabalho, utilizamos cálculos de primeiros princípios baseados na Teoria do Funcional da Densidade (DFT - Density Functional Theory) para investigar a estabilidade energética e as propriedades magnéticas de compostos químicos. Foram estudados os complexos com metais de transição contendo radicais do tipo nitronilnitróxido [M(II)(Phtfac)2(NITpPy)2] [M = Co, Mn] e [M(II)(NITmPy)2(DMSO)2] [M = Cu, Ni, Co], bem como o silicato de cobre Na2Cu5(Si2O7)2. A partir do cálculo da energia total, determinamos a configuração de equilíbrio para os cinco complexos metálicos e os valores das constantes de acoplamento. Além disso, foram obtidas também as respectivas distribuições de densidade de magnetização, fundamentais para entender os mecanismos de acoplamento magnético nesse tipo de sistema. Para o silicato de cobre, cujos responsáveis pelas propriedades magnéticas são cadeias alternadas de trímeros e dímeros, calculamos a energia total das 32 configurações possíveis; determinamos o estado fundamental e as constantes de acoplamento magnético.
In this work we use first principles calculations based on density functional theory (DFT) to investigate the energy stability and the magnetic of chemical compounds. We studied the transition metal complexes with nitronyl nitroxide radical M(II)(P[htfac)2(NITpPy)2] [M = Co, Mn] and [M(NITmPy)2(DMSO)2] [M = Cu, Ni, Co], as well as the copper silicate Na2Cu5(Si2O7)2. By calculating the total energy, we determine the equilibrium configuration for the five metal complexes and the values of coupling constants. Moreover, we obtained their magnetization density distributions, fundamental for understanding the mechanisms of magnetic coupling in this type of system. For the copper silicate, whose magnetic properties are responsible for alternate chains of dimers and trimers, we calculate the total energy of the 32 possible configurations and determine the ground state and magnetic coupling constants.

Abstract Pollutant (such as metals and sulphate) contamination exists in the wastewaters of many industries, including mining operations, metal plating facilities, and tanneries. Adsorption is one of the most commonly used processes for the removal of pollutants from waters and wastewaters due to its high efficiency and simple operation. Activated carbon is the most frequently used adsorbent material, although its high cost inhibits its widespread use in wastewater treatment. Therefore, there is a need to develop other adsorbents from alternative inexpensive raw materials such as locally available industrial and mineral waste and by-products. The aim of this thesis was to study the possibility of using industrial waste materials such as carbon residue, metakaolin, blast-furnace slag and analcime as an inexpensive sorbent for iron, copper, nickel, arsenic, antimony and sulphate removal from aqueous solutions. To enhance their adsorption capacity, different chemical treatments (i.e. activation, modification, geopolymerisation) were performed. As a result, the level of removal of iron, copper and nickel by carbon residue and zinc chloride activated carbon residue was higher than that by the commercial activated carbon. Iron chloride modified carbon residue was the most effective sorbent material for sulphate removal when compared to the other studied chemically modified/activated carbon residues. Blast-furnace slag and metakaolin geopolymers as well as their raw materials, were examined for the simultaneous removal of nickel, arsenic and antimony from the spiked mine effluent. In the case of blast-furnace slag, geopolymerisation clearly increased the efficiency of nickel, arsenic and antimony removal to a beneficial level. The barium chloride modified blast-furnace-slag geopolymer was a very efficient sorbent material for sulphate removal and it could thus be a technically feasible sulphate sorbent for wastewater treatment (e.g. in the mining industry in applications in which very low sulphate levels are desired). Barium chloride modified acid washed analcime could also be a potential sorbent for sulphate removal
Tiivistelmä Teollisuuden jätevedet kuten kaivosvedet ja metalliteollisuuden prosessien jätevedet voivat sisältää monenlaisia haitallisia ja jopa myrkyllisiä aineita kuten metalleja ja sulfaattia. Adsorptiota käytetään yleisesti esimerkiksi metallien ja orgaanisten yhdisteiden poistossa vesiliuoksista, koska se on tehokas ja yksinkertainen menetelmä. Aktiivihiili on yleisimmin käytetty adsorbenttimateriaali vedenpuhdituksessa, mutta sen hinta joissain tapauksissa rajoittaa sen käyttöä. Tämän vuoksi on tarvetta kehittää vaihtoehtoisia adsorbenttimateriaaleja edullisista raaka-aineista. Viime vuosien aikana on raportoitu mm. teollisuus- ja mineraalijätteistä, joita voidaan hyödyntää vesien ja jätevesien puhdistuksessa. Tämän työn tavoitteena oli hyödyntää teollisuudesta muodostuvia jätemateriaaleja (hiilijäännös, metakaoliini, masuunikuona ja analsiimi) raudan, kuparin, nikkelin, arseenin, antimonin tai sulfaatin poistossa malli- ja jätevesistä. Materiaaleja käsiteltiin erilaisilla kemikaaleilla (aktivointi, modifiointi tai geopolymerointi), jotta niiden adsorptiotehokkuudet paranisivivat poistettavia aineita kohtaan. Tulokset osoittivat, että raudan, kuparin ja nikkelin poisto oli sekä käsittelemättömällä että sinkkikloridilla aktivoidulla hiilijäännöksellä korkeampi kuin kaupallisella aktiivihiilellä. Arseenin, nikkelin ja antimonin poistoa kaivosvedestä tutkittiin masuunikuona- ja metakaoliinigeopolymeereillä, joista masuunikuonageopolymeeri osoittautui tehokkaimmaksi metallien poistajaksi. Bariumkloridilla modifioitu masuunikuonageopolymeeri puolestaan poisti erittäin tehokkaasti sulfaattia kaivoksen jätevedestä. Rautakloridilla modifioitu hiilijäännös ja happopesty bariumkloridilla modifioitu analsiimi osoittatuivat myös lupaavaksi materiaaliksi sulfaatin poistossa

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Dissertação (Mestrado em Tecnologia Nuclear)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Acid leaching of different natural chrysocolla samples under ambient conditions demonstrated that the chemical and chrystallographic inhomogenity significantly affects the rate and that it is virtually impossible to use the mineral as a model for the kinetics of hydrometallurgical processing of copper ores.Dissolution experiments, stability diagrams,and X-ray powder diffraction studies are undertaken and studied in this research and results are given.It is found that a complete solid solution series exists in Nature with most tungstenian wulfenites and molybdenum stolzites containing a range of compositions. The first occurrence of a molybdenum stolzite from Broken Hill, Australia, which also contains small amounts of chromium is noted.Raman microprobe spectroscopy has proven to be a very quick and effective non-destructive method for semi-quantitative analysis of the wulfenite-stolzite and powellite-scheelite solid-solution series and in detecting very small amounts of substituted chromate in wulfenite, stolzite and anglesite

碩士
國立臺灣大學
高分子科學與工程學研究所
104
The hybrids of zinc oxide, copper (II) oxide, silver oxide nanoparticles on the nanoscale silicate platelets (NSP) are synthesized and characterized by UV-visible spectroscopy, X-ray powder diffraction, and TEM. We employ the exfoliated silicate platelets to support and stabilize the nanoparticles. The particles-on-platelet nanohybrids are successfully synthesized and the naked nanoparticles associated with the NSPs are formed without organics contamination. It is suggested that the NSPs are suitable for supporting nanoparticles owing to their high aspect–ratio and high surface ionic charges. We further investigate the bactericidal efficacy of ZnO/NSP and CuO/NSP as compared with the home-made Ag/NSP at the weight ratio of 15/85. The antimicrobial tests are performed on Escherichia coli and Staphylococcus aureus. Additionally, we synthesize the Ag/ZnO/NSP that ZnO is regarded as a promoter in the hybrids in antibacterial uses. Also, the differences of antibacterial activities between Ag/NSP and Ag/ZnO/NSP are investigated. And, it is found that CuO/NSP (15/85, w/w) show better antibacterial efficacy against S. aureus as compared with ZnO/NSP and Ag/NSP. And the Ag-contained nanohybrids (Ag/NSP and Ag/ZnO/NSP) are excellent antibacterial agents for E. coli. Among the Ag/ZnO/NSP, ZnO promote the antibacterial activity of Ag/NSP.

碩士
國立成功大學
化學系碩博士班
100
For the concept of green chemistry, the scientists put much effort to reduce environmental pollution and slow down the greenhouse effect. It would be an important issue to control the effluent amount of waste water and toxic gas for the purpose of environmental protection. Mesostructural materials of high-surface area, tunable pore size and large pore volume have obvious potentials for the applications in adsorption, catalysis, enzyme-stabilization, and optical devices. In this research, we prepared the mesoporous copper-silicate of high surface area (〉 450 m2g-1), well-dispersed of CuO, tunable mesopores (pore size  3.4 ~ 4.0 nm) and high thermal stability was obtained from heterogeneous nucleation and hydrothermal treatment for 1 day on a mixture of copper hydroxide and porous silica without adding any organic template. Adding proper amount of sodium fluoride can accelerate the silica dissolving rate and reduce the reaction time. The base sources in the alkaline solution can affect the aggregation extent of Cu(OH)2. Using different silica sources such as mesoporous silica, rice husk porous silica and fumed silica can also get the mesoporous copper-silicate. In brief, we provided a new synthesis method to prepare the mesoporous copper-silicate by hydrothermal treatment on the simple mixtures of Cu(OH)2 precipitation, NaF and silica source. This synthetic method can be successfully extended to use the industry slurry (Cu-CMP) and agricultural waste stuff (rice husk and straw) to prepare mesoporous copper-silicates with excellent porous properties. In application, the mesoporous copper silicate act as a high-performance absorbent to remove the toxic gas of PH3 as dopant in IC industry (the maximum removal percentage = 99%), and reduce the COD values and heavy metal ions in the industrial waste water to below the legal limited in effluent (about 45 ppm).

A preservative that could be used to treat wood on farms would greatly increase the utility of farm timber and the profitability of timber production. Current preservatives are for the most part too toxic for use outside specialised treatment plants, or too expensive, or ineffectual. Many experimental preservatives appear to have potential, but remain untested or undeveloped. To test wood preservatives and develop wood preservatives for use on farms, an array of wood rotting fungi was grown from fruiting bodies collected on rotting wood and living trees. This process resulted in some new knowledge about the identity and habits of Tasmanian fungi. Putative brown rots were tested for copper tolerance, and an Antrodia isolate was identified as being very tolerant. This isolate was therefore used to test preservatives that used metals as fungicides. Two vigorous white rots were also used. A preservative system using silicate as a fixative for boron was identified as being likely to have easily developed potential, so a study was undertaken to clarify the effects of different concentrations of silicate, (as waterglass), and different ratios of silicate/boron on the leaching of boron. It was found that a fungicidal dose of boron could be fixed with a much lower dose of silicate than had previously been tried, and that the concentrations of boron being used were wastefully high, resulting in more than 90% of the boron being leached out. The order of treatment was found to be very important to both the initial concentration of boron in the wood and the percentage lost, through effects of treatment solution osmolarity and the affinity of silicate for boron. These effects hadn’t been described by previous authors and are very important to the practical use of this preservative system. An upper limit of waterglass concentration was identified, above which alkaline damage to the wood negates the positive effects of the greater concentration of silicate, (resulting in increased leaching). Another preservative system identified as having undeveloped potential was a waterglass and aluminium system, which had previously only been tested against two wood rot isolates, neither of which had proven tolerance of any metal. This preservative, (modified with the addition of a naturally occurring polysaccharide), was therefore tested against one of the same species of fungus that had been used in previous tests, (Trametes versicolor), along with another vigorous white rot, (Omphalotus nidiformis), and the copper tolerant Antrodia. The previously tested white rot was effectively suppressed. The other white rot showed no signs of suffering aluminium toxicity and grew healthily on the treated wood, but was unable to cause decay. Presumably the wood was protected by the polysaccharide, blocking access to lignin, (the preferred food of white rots). The copper tolerant Antrodia appeared to be susceptible to aluminium toxicity because it was unable to colonise the treated wood until late in the test, and then was unable to cover the wood with its usual exploratory growth but rather was restricted to defined patches of dense mycelium. Antrodia presumably required a dense population of mycelium to produce enough oxalic acid to detoxify the aluminium. The polysaccharide appeared to feed rather than inhibit Antrodia. Three new preservatives were also conceived and tested. The first used copper that was buffered so it could be combined in solution with a silicate fixative. Preliminary studies on leaching behaviour showed that fixation of copper was inhibited by excess buffer, such that practically attainable concentrations of silicate couldn’t fix high concentrations of copper (1% w/v in the treatment solution). Leaching resistance was improved by addition of boric acid to the solution, (or secondary treatment with boric acid), and also by secondary treatment with extra fixative, or drying the treated wood at 100°C instead of at room temperature. The effect of the latter is probably due to thermal decomposition of buffer. In decay tests it was seen that even a weak formulation of copper-silicate completely protected wood from white rot. The same formulation wasn’t entirely effective against Antrodia on pine, but a formulation of similar strength completely protected alder, because Antrodia had a poor ability to attack even untreated alder. There is thus a possibility that copper-silicate without any additional fungicide might be an effective treatment for hardwood, which in any case covers the vast majority of standing timber on Australian farms. Further tests on the hardwoods in question, with other species of brown rot and also with soft rots, are thus warranted. A copper-silicate formulation that had the copper concentration reduced to 0.25% w/v, and a low concentration of boric acid added, proved to have high resistance to leaching and was completely impervious to Antrodia, (despite the strong resistance of this fungus towards copper). The other two new preservative concepts needed neither copper nor boron as fungicides, but depended on synergy and mutual precipitation of weaker natural fungicides, (entirely organic in one case). These preservatives successfully protected wood against vigorous white rots, and are predicted to be similarly successful against brown rots. In summary, three new preservatives have shown strong efficacy and have potential for treating timber on farms. In addition, the combination of waterglass and boric acid is a simple preservative that also appears practically useful, since it was demonstrated to be capable of fixing a fungicidal dose of boron, with a low dose of waterglass. The combination of waterglass and aluminium, on the other hand, is less reliable than previously supposed: one white rot showed no sign of aluminium toxicity when growing on the treated wood, and a brown rot that did show signs of toxicity was never the less able to detoxify the aluminium and attack the wood.

Several arsenate and silicate compounds with interesting structural features have been synthesized by the molten salt flux method. These new materials were characterized by single crystal and powder X-ray diffraction, infrared spectroscopy, magnetic susceptibility, and elemental analysis. The compounds generally have an open-framework structural network, although some also exhibit layer-like or quasi-low-dimensional features. In the arsenate family of compounds, two copper arsenates, BaCuAs$\sb2$O$\sb7$ and $\rm Na\sb7Cu\sb4(AsO\sb4)\sb5,$ as well as two isomorphous manganese arsenates, NaMn$\sb4$(AsO$\sb4)\sb3$ and KMn$\sb4$(AsO$\sb4)\sb3,$ were synthesized and characterized. In the silicate system, two isostructural copper silicate chlorides, $\rm Na\sb2Rb\sb2Cu\sb4Si\sb{12}O\sb{29}Cl\sb2$ and $\rm Na\sb2Cs\sb2Cu\sb4Si\sb{12}O\sb{29}Cl\sb2,$ were successfully identified. Our study of structure/property correlations should prove insightful toward a better understanding of the conducting mechanism in technologically important metallic/magnetic oxides and in the development of new materials with desired applications.

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Many isotope proxies have been applied to study the prosperous iron oxide copper gold (IOCG) province in the eastern Gawler Craton (E.G.C) and Au mineralised region of the cental Gawler Craton (C.G.C), in Southern Australia. Yet, copper isotope proxies- an indicator for low temperature fluid flow and sulfide mineralisation- have yet to be applied to the region. In this study, purification techniques using automatic column chromatography were demonstrated during separation of Cu from matrix elements. Cu isotopes – 65Cu & 63Cu – were used to understand the extent of mantle input and mantle metasomatism, potentially responsible for the Cu in IOCG mineralisation. Eleven samples were gathered. Three mafic enclaves and four intrusives from the Central Gawler Gold Province and four intrusives from the eastern Gawler IOCG province. Separation using automatic column chromatography proved challenging, with matrix elements abundant throughout the purified fractions (Co, Ti, Fe, Mg, Na), due to poor separation. Ti proved to a major interference during isotopic analysis using a Multicollector-ICP-MS, positively offsetting values. E.C.G samples showed the most positively fractionated δ65Cu values (+0.69 ± 0.024‰ to +1.422 ± 0.077‰). Enclaves from the C.G.C showed the most negatively fractionated δ65Cu values (-0.053 ± 0.023‰ to -0.897 ± 0.006‰), while intrusives from this region showed more positive δ65Cu values (+0.084±0.23‰ to +0.397±0.011‰). All samples showed a lack of hydrothermal alteration. Magmatic sulphide-containing E.G.C samples had the most positive δ65Cu values; which cannot be explained by current understanding of Cu isotope fractionation during sulfide saturation. This trend may instead be attributed to a heterogeneous sub-continental lithospheric mantle (SCLM) source. In contrast the negative δ65Cu values of mafic enclaves is possibly caused by assimilation of S-type granitic crust and/or possibly due to a heterogeneous SCLM source.
Thesis (B.Sc.(Hons)) -- University of Adelaide, School of Physical Sciences, 2019

The search for novel compounds with nanosize transition metal oxide frameworks is important for the study and understanding of materials with interesting and important magnetic and electronic properties. These low-dimensional structural features have become associated with unusual physical phenomena such as charge density waves, magnetic ordering, and superconductivity. Exploratory synthesis of copper(II) and copper(I/II) phosphates containing oligomers, chains and layers has been investigated through the use of low-melting eutectic fluxes. Additionally, magnetic property studies of many of these compounds have been undertaken and interesting ordering has been observed. Ultimately, these new compounds should lead to structural models for experimental and theoretical studies of electrons in a confined lattice. Several interesting and significant low-dimensional copper phosphates and silicates have been synthesized by employing low-melting eutectic fluxes for crystal growth. Characterization was carried out by single and powder X-ray diffraction, thermal analysis (DTA and TGA), infrared spectroscopy and magnetic measurements. Three compounds exhibiting low-dimensional features dependent on the versatility of Cu-O-P-O-Cu bonding have been found: $\rm Na\sb2CuP\sb2O\sb7,$ $\rm Ba\sb2Cu(PO\sb4)\sb2$ and $\rm BaCuPO\sb4Cl.$ Long-range antiferromagnetic ordering has been found despite the long Cu--Cu distances and lack of Cu-O-Cu interactions. $\rm Li\sb2Cu\sb3Si\sb4O\sb{12}$ and LiCu$\sb2$PO$\sb5$ have copper oxide trimers and layers with Cu-O-Cu bonds, respectively. The magnetic properties of the latter and $\beta$-NaCuPO$\sb4$ (a structurally known compound containing one dimensional (Cu$\sb2\rm O\sb8\!\sb\infty\sp{12{-}}$ chains) have been studied and show strong coupling. Finally, investigations into the mixed-valence copper(I/II) system has produced two welcome additions to a small family of electronically distinct copper compounds, Cu$\sb2$PO$\sb4$ and $\rm Na\sb{2.2}Cu\sb{3.8}P\sb2O\sb9Cl.$ These compounds both have fascinating low-dimensional features: an array of $\rm Cu\sp{I}O\sb2$ cross-linked by PO$\sb4$ tetrahedra and a chain of condensed copper oxide polyhedra, respectively. Our structure/property correlation studies should offer insight into the conducting mechanism of technologically important materials and in the development of new materials with desired properties.

Attractive particle interactions which lead to the hetero-aggregation or 'sliming' of silicate clay gangue and valuable sulphide mineral particles are encountered in a number of hydrometallurgical and flotation processes. Sliming leads to poor recovery of the valuable minerals and high recovery of the clay gangue minerals in flotation concentrates. In the present work, the hetero-aggregation mechanism of hydrophilic mica clay mineral sericite (or muscovite) and hydrophobic chalcocite was investigated by probing the particle interactions and the prevailing interfacial chemistry under dispersion conditions where the individual chalcocite and sericite particles displayed negative zeta potentials. The mitigation/suppression of the hetero-aggregation was examined via the prudent control of dispersion conditions and pulp chemistry (i.e., pH modification and solution speciation control) and the use of two, anionic, polymeric dispersants with different molecular weight and functionality (carboxylate-substituted polyacrylamide, Cyquest 3223 and sulphonate-substituted polymaleic acid, P80 co-polymers) as dispersants. The adsorption behaviour of both polymers onto both minerals under industrially relevant suspension conditions have been quantified in terms of the polymer adsorption density and the adsorbed layer characteristics. These interfacial layer properties which impact on the mineral particles' zeta potentials and interactions, and also underpin the dispersion efficacy of polymers were characterized, using interfacial and solution analytical methods and TM-AFM imaging analysis.

MENVSC
Department of Ecology and Resource Management
Mine tailings (MT) have been a global problem due to the environmental impacts the waste generates such as air, soil and water pollution. The detrimental impacts include a global problem such as acid mine drainage (AMD) which has been difficult to cleanup. Several studies have been conducted to find alternative measures in reducing or mitigating impacts such as AMD and air pollution. Several studies have revealed how alumino-silicate mineral waste can be used as raw material to produce construction materials. This study aimed at evaluating the potential of synthesizing a geopolymer material from Musina copper mine tailings. Tailings were characterized for their physicochemical and mineralogical compositions using standard laboratory techniques in order to evaluate suitability in geopolymerization. First section of the results presented physicochemical and mineralogical characterization of the Musina copper tailings together with the bioavailability of the chemical species. It was observed that the tailings are mainly composed of SiO2 and Al2O3 as the major oxides indicating that they are aluminosilicate material. Mineralogical analysis revealed dominance of quartz, epidote and chlorite as the major minerals. The bioavailability assessment showed that largely Cu and Ca are bioavailable and highly soluble in an aqueous solution while Al, Mg, Ni, Co, Cr and Fe have a high proportion in non-labile phase. Second section presented the preliminary results wherein the potential application of Musina copper tailings in geopolymerization was evaluated. The results showed that Musina copper tailings can be used to synthesize a geopolymer material. However, it was recommended that several parameters influencing geopolymerization need to be evaluated. The third section presented the evaluation of optimum parameters that influence the geopolymerization process, which include type of alkali activators, alkali activator concentration, curing temperature, liquid-solid (L/S) ratio and curing regime. It was observed that a mixture of NaOH:Na2SiO3.5H20 at a ratio of 70:30 yields a better geopolymer material. The concentration of 10 M NaOH:Na2SiO3.5H20 at a ratio of 70:30 was observed to be the best that yielded the UCS that is acceptable according to SANS1215 standards. When evaluating curing regime, it was found that the material cured using greenhouse has lower UCS as compared to the material cured using oven. The v effect of temperature showed that the UCS decreases with increasing curing temperature. An admixture of river sand and cement was introduced which resulted in a high UCS of 21.16 MPa when using an admixture of cement. The mineralogical composition of the geopolymer bricks showed formation of secondary minerals such as phlogopite, fluorapatite, diopside and actinolite. Batch leaching conducted on the geopolymer bricks detected high leaching of Na from the bricks. Based on the findings of the study of the raw MT potential to produce geopolymer bricks, it was concluded that the material can be used to produce bricks that are within the SANS 1215 requirements. The study further recommended that the study a focus on using cylindrical moulds, other alkali activators and a mechanical mixer. It was also recommended that the greenhouse be restructured to contain heat within the greenhouse during the evening so as to allow constant temperature within
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