Thesis (PhD)--Stellenbosch University, 2000. / ENGLISH ABSTRACT: Please refer to fulltext for abstract / AFRIKAANSE OPSOMMING: Sien asb volteks vir opsomming

This dissertation reports on the study of black molybdenum, a new cermet consisting of small Mo particles embedded in MoO₂. As with most two-phase materials, the optical properties of black molybdenum are significantly different from those of either constituent, and can be adjusted within wide limits through modifications of composition and microstructure due to variations of the fabrication process parameters. The subject of this work is to understand the exact relationships, to allow reproducible production of films with chosen optical properties. Theoretical interpretation of the optical properties of two-phase materials has in the past been hampered by insufficient microstructural characterization. Recent theoretical work by others has lifted the requirements of detailed microstructural knowledge, leaving only two required parameters for characterization of cermet reflectance: the optical properties of the constituent phases and their volume fractions in the cermet. Better characterization is obtained when structural considerations, such as film topology, surface texture and the presence of a possible amorphous phase, are taken into account. We adopted this approach to the study of black molybdenum, and accomplished satisfactory agreement between theoretical and observed reflectances. Black molybdenum films were prepared using two separate chemical vapor deposition (CVD) techniques, involving deposition from either Mo(CO)₆ or MoO₂Cl₂. We found the influence of composition through a comparison of films with different Mo:MoO₂ ratios, while the influence of structure on film reflectance was determined by comparing films from these two deposition techniques. During this investigation we produced black molybdenum films which display a spectrally selective profile--low visible reflectance combined with high infrared reflectance, and which may be applied to photothermal solar energy conversion. The versatility of CVD in adjusting film composition and structure resulted in another film of interest in photothermal conversion--black tungsten, a tungsten-tungsten oxide composite material. The black molybdenum and black tungsten systems studied here establish the utility of CVD for the production of high temperature thin film optical devices.

The electronic structures and bonding interactions in the syn and anti isomers of Mo₂S₄(edt)₂²⁻ (edt = ethanedithiolato, (SCH₂CH₂S)²⁻) were examined and compared through Fenske-Hall and extended Huckel molecular orbital calculations. The electronic structures of a hypothetical closed isomer and the fragment MoS₃(edt)³⁻ were calculated as well. A molybdenum-molybdenum bonding interaction accounts for the diamagnetism of the complexes and is important in determining the relative stabilities of the isomers (syn > closed > anti). The structure of the syn isomer of (P(C₆H₅)₄)₂W₂S₄(edt)₂ was determined by X-ray crystallography. The compound crystallizes in the space group P2₁/n with a = 16.126(7)A, b = 25.03(1)A, c = 13.021(6)A, β = 101.73(4)°, and Z = 4. The calculated and observed densities are 1.755 and 1.757 g cm⁻³. Full-matrix least squares refinement of the 7414 data with Fₒ² > 3σ(Fₒ²) gave R = 0.039 and R(w) = 0.046. Each tungsten atom is ligated by five sulfur atoms in approximate tetragonal-pyramidal geometry. The W-W distance is 2.862(1)A, indicating a metal-metal bond. The average W-S(terminal) distance is 2.144(2)A, the average W-S(bridging) is 2.328(2)A, and the average W-S(edt) distance is 2.404(2)A. A variety of sulfur compounds, including hydrogen sulfide, aromatic and aliphatic thiols, cysteine, and bisulfite reduced MoO(TTP)OR, oxoalkoxotetratolylporphinatomolybdenum(V) (R = H, CH₃, C₂H₅, C₅H₁₁, MoO(TTP)), to the corresponding Mo(IV) species, MoO(TTP). The kinetics of the redox reaction between MoO(TTP)OC₂H₅ and RSH (R = C₂H₅, C₆H₅) were monitored at ambient temperature. The rate law d(Mo(IV))/dt = k₂(Mo(V))(RSH), with k₂ = 8.0 x 10⁻¹³ M⁻¹sec⁻¹ for C₂H₅SH and k₂ = 8.2 M⁻¹sec⁻¹ for C₆H₅SH describes the kinetic data. Sulfur compounds also reduced MoO₂(TTP). The kinetics of the redox reaction of the novel compound MoO(TTP)HSO₃ were monitored in chloroform solution at ambient temperature. The rate law d(Mo(IV))/dt = k₂(Mo(V))² with k₂ = 3.4 x 10² M⁻¹sec⁻¹ describes the kinetic data. Oxidation of MoO(TTP) to Mo(V) occurs in the presence of air. Oxidation catalysis by oxomolybdenum porphyrins was demonstrated for the substrates C₂H₅SH, C₆H₅SH, and HSO₃⁻. Mechanisms for these reactions are proposed.

No description available.

Wheat (Triticum aestivum L.) is occasionally exposed to low temperature during flowering and huge economic losses can occur especially in some key production countries such as Australia. Although it is generally predicted that there will be a rise in global temperature there are still predicted to be risks associated with low temperature for temperate crops. Post head emergence frost damage remains a major constraint to increasing wheat production. Five Iraqi varieties (Abu-Ghariab, Fatah, Sham6, IPA95 and IPA99) were screened for their frost hardiness (LT50). Abu-Ghariab was chosen for further investigations along with the European cv. Claire because the acclimated frost hardiness level in these two varieties (LT50 -8.07 and -8.01°C for Claire and Abu-Ghariab respectively) was found to be significantly lower than the other varieties in this study. Several techniques were employed including REC%, IR thermography and molecular analysis of cold acclimation in order to characterise the frost resistance of those two varieties. REC% revealed that both Claire and Abu-Ghariab could tolerate some freezing when the spikes were just visible (ZCK 51-60) with an acclimation shift of the LT50 of -1.6 and -2.11°C respectively but this was not apparent at later growth stages. Based on molecular analysis, cold acclimation was shown to be activated at ZCK 51-60 in both varieties. Cbf14 was expressed after 8 hours exposure to acclimatising temperatures (4°C) and then declined to a low, but still up-regulated level in both varieties and this led to expression of the COR15a protein. These molecular changes correlated with the frost tolerance recorded at ZCK 51-60. It was concluded that the possibility existed to up-regulate cold acclimation after spike emergence if there was enough environmental stimulus. Molybdenum (Mo) was demonstrated to work synergistically with low temperature in increasing the expression of Cbf14 and COR15a. The European wheat cv. Claire showed a higher capacity (-8.14°C) to be acclimated than Iraqi wheat (-7.40°C) under the effect of both Mo and acclimation temperatures. Mo alone increased the expression of Cbf14 in both varieties but did not increase the frost tolerance. Observations of ice nucleation using an infrared thermography (IR) revealed that supercooling is highly likely in spikes and some spikes avoided frost damage even when the temperature fell to -12°C. It was observed that the proportion of frozen spikes was 22.8% while the remainder supercooled. Spraying plants with distilled water was not effective in facilitating ice nucleation in wheat spikes. Observations also revealed that spikes that did freeze started freezing at temperatures of -4 to -5 °C close to temperature of the putative constitutive frost hardiness of un-acclimated wheat and it is suggested that this may reflect that many laboratory freezing experiments may not actually freeze until -5°C. The anthesis stage of wheat was found to be the most vulnerable stage and it needs to be given more attention in terms of research to up-regulate cold acclimation. Frost damage to wheat during flowering continues to be a serious problem in certain production areas and therefore continued effort in characterising and finding suitable solutions to this are imperative.

O presente trabalho objetivou avaliar a capacidade de um sal mineral rico em molibdênio (Mo) em prevenir a intoxicação cúprica acumulativa (ICA), analisando variáveis clínicas, sangüíneas e os teores de cobre (Cu) e Mo hepático. Foram utilizados 25 ovinos da raça Ilede-France, aleatoriamente distribuídos em cinco grupos de cinco animais de cada, sendo que o grupo 1 recebia dieta contendo 80% volumoso e 20% concentrado, os grupos 2 e 3 recebiam 50% volumoso e 50% concentrado, e os grupos 4 e 5 recebiam a mesma dieta dos grupos 2 e 3 com a adição diária de 150 mg de sulfato de Cu até o término do experimento (150 d). Os grupos 1, 3 e 5 recebiam sal mineral contendo 300 ppm de Mo. Foram realizadas três biópsias hepáticas para determinação da concentração de Cu, Mo e Zn neste órgão e três ensaios de retenção aparente de Cu e Mo (0 d, 75 d, 150 d). Quinzenalmente, foi realizado exame clínico e coleta de amostras de sangue e urina. Três ovinos do grupo 4 e um do grupo 5 manifestaram ICA. Não existiu diferença entre a freqüência de mortalidade entre os grupos (P = 0,56). Os teores de Cu hepático nos ovinos com ICA (2450 ppm) foram superiores aos que não intoxicaram (1518 ppm). Quanto maior a ingestão de Mo na dieta menor foi o acúmulo de Cu hepático ao término do experimento (r = -0,72). Ovinos com ICA aumentaram a concentração de Zn hepático nas fases finais da intoxicação. A presença de altas atividades de GGT (>56,5 U/L) e de AST (>120 U/L) indicaram de maneira efetiva a presença de destacado acúmulo de Cu nos tecidos hepáticos (1000 ppm). / The aim of this project is to evaluate the capacity of a molybdenum-rich mineral salt in the prevention of cumulative cooper poisoning (CCP) in sheep, through clinical and blood exams and hepatic copper and molybdenum concentrations. Twenty five Ile-de-France sheep were randomly distributed into five groups of five animals each, where group 1 received a 80% forrage and 20% concentrate diet, groups 2 and 3 received a 50% forrage and 50% concentrate diet, and groups 4 and 5 received the same diet as groups 2 and 3 with a daily supplementation of 150mg of copper sulphate until the end of the experiment (150 d). Groups 1, 3 and 5 received a mineral salt with 300 ppm of molybdenum. For three times during the experiment (day zero, 45th and 105th day) a liver biopsy was carried out to evaluate the degree of copper accumulation in this organ. Clinical examination was followed every two weeks, as far as blood and urine samples were withdrawn. Three sheep from group 4 and one sheep from group 5 presented clinical picture of CCP. There was no difference in the frequency of mortality between groups 4 and 5 (P = 0.56). The liver copper concentration was higher in sheep with CCP (2450 ppm) compared to sheep that not presented CCP (1518 ppm). The higher the ingestion of molybdenum in the diet the lower the liver copper concentration at the end of the experiment (r = -0.72). Sheep with CCP had higher liver zinc concentration. The presence of high activity of GGT (> 56.5 U/L) and AST (>120 U/L) indicated effectively the high accumulation of copper in liver (> 1000 ppm).

O tratamento de rejeitos de determinados processos industriais vem ganhando importância, seja pelo impacto negativo do simples descarte no meio ambiente, seja pelo valor econômico de materiais e substâncias que podem ser eventualmente recuperados e reciclados. O rápido empobrecimento de reservas minerais primárias e o aumento de demanda de energia são problemas que merecem atenção especial. Neste contexto, a recuperação de metais existentes nos rejeitos de alguns processos de fabricação assume papel de maior importância. A recuperação do molibdênio presente em soluções nitro-sulfúricas, na forma de rejeitos líquidos do processo de fabricação de lâmpadas incandescentes e fluorescentes, não constitui exceção no que diz respeito à importância da reciclagem. Este rejeito, proveniente da dissolução dos mandris de conformação dos filamentos de tungstênio das lâmpadas, apresenta valores que podem ser recuperados e até reciclados no próprio processo. É o caso dos ácidos nítrico e sulfúrico. Já o molibdênio, presente em concentrações em torno de 40 a 90 g.L-1, pode ser recuperado e utilizado na fabricação de aços especiais, pigmentos, lubrificantes, adubo, etc. Neste trabalho foram desenvolvidos dois processos de recuperação deste rejeito. No primeiro, o rejeito é diluído e por cromatografia de troca iônica o molibdênio é recuperado. Os ácidos efluentes são destilados para a retirada da água. No segundo processo, o rejeito passa por uma destilação e ao mesmo tempo o molibdênio é precipitado. Em ambos os processos, os ácidos recuperados podem voltar à fábrica de lâmpadas para a dissolução dos mandris do filamento de tungstênio e o molibdênio encontra outras diferentes aplicações, além de possuir um valor significativo no mercado. / The waste treatment of certain industrial processes is becoming more important, either by the economic impact of simple disposal in the environment, or by the economic value of materials and substances that can eventually be recovered and recycled. The rapid depletion of mineral reserves and increasing primary energy demand are problems that deserve special attention. In this context, the recovery of metals present in waste of some manufacturing processes assumes a great importance. The recovery of molybdenum present in nitro-sulfur solutions in the form of liquid waste in the manufacturing process of incandescent and fluorescent lamps, is no exception with regard to the importance of recycling. The tailing from the dissolution of the molybdenum mandrel wires used in the conformation of the tungsten filament of electric lamps, has values that can be recovered and recycled to the process itself. Is the case of sulfuric and nitric acids. Molybdenum, present in concentrations around 40 to 90 g.L-1, can be recovered and used in the manufacture of special stainless steel, pigments, lubricants, fertilizer, etc.. In this work two processes for the recovery of this waste were proposed. At the first one, the waste is diluted and molybdenum is recovered by ion-exchange chromatography. The effluent acid from this process was distilled to extract water used in the dilution step. In the second case, the waste goes through a distillation while the molybdenum is precipitated. In both cases, the acids are recovered back to the lamp factory for the dissolution of the molybdenum mandrel wires and molybdenum finds other different applications, as well as having significant value in the market.

Thesis (MTech (Horticulture Science))--Cape Peninsula University of Technology, 2009 / The study used common bean (P. vulgaris L. variety Provider) in a spilt-split-plot design involving 2 levels of Rhizobium inoculation (with and without rhizobia), 3 levels of lime (0, 2 and 3 t.ha-1) and 3 levels of molybdenum (0, 6 and 12 g.kg-1 of seeds) in a glasshouse experiment. The glasshouse experiment was then verified in the field during 2008 and 2009 cropping seasons. The aim was to assess the effects of Rhizobium inoculation, molybdenum and lime supply on: i) yield and yield components of the P. vulgaris L. ii) Changes in soil pH and the concentrations of selected plant-available nutrients in the rhizosphere, iii) photosynthesis and chlorophyll formation in P. vulgaris L. and (iv) plant growth and N2-fixation in P. vulgaris L. The results showed that Rhizobium inoculation had significant effects in increasing yield components and ultimately the final seed yield. Rhizobial inoculation also significantly increased the levels of chlorophyll content in leaves, improved all photosynthetic parameters, increased dry matter yield of different organs and decreased 15N values in all organs assessed. As a result, % nitrogen derived from atmosphere (%Ndfa) in all organs as well as the amount of N derived from fixation was improved. In the field, the whole plant level of N-fixation of P. vulgaris L. from Rhizobium inoculation accounted for approximately 33 kg N.ha-1. Furthermore, soil pH and the concentration of mineral nutrients (P, K, Ca, Mg, Na, Fe, Cu, Zn and Mn) in the rhizosphere were significantly increased with Rhizobium inoculation when compared with the control.

O Brasil planeja construir uma planta de produção do 99Mo por fissão do 235U, devido à crescente utilização deste radioisótopo no setor de medicina nuclear. Neste trabalho buscou-se estimar as características físico-químicas e radiológicas dos rejeitos radioativos que serão gerados em tal instalação, além de fornecer subsídios teóricos a serem utilizados na definição do gerenciamento desses rejeitos. Estabelecidos dois cenários de produção para este projeto e utilizando-se o código Scale®, foram calculados os inventários radioisotópicos dos fluxos de rejeitos. Considerando-se o processamento químico dos alvos de urânio, foi possível caracterizar os rejeitos a partir de suas características químicas e radiológicas. Utilizando-se o software MicroShield®, determinou-se então as concentrações de atividade desses rejeitos em até 3 meses de produção. Este trabalho ainda apresenta o cálculo das taxas de dose variando-se tanto a espessura da blindagem, a ser utilizada numa embalagem para transporte in-site, quanto a quantidade de rejeito líquido retido em tal embalagem. Os radionuclídeos responsáveis pela maior parcela da dose de radiação foram identificados de forma a facilitar a determinação do método mais apropriado para o gerenciamento dos rejeitos após sua separação e antes de seu armazenamento. Os resultados aqui apresentados constituem uma compilação inicial do que é esperado em termos de rejeitos radioativos líquidos numa planta produtora de 99Mo e podem auxiliar no desenvolvimento do plano de gerenciamento de rejeitos de tal instalação. / Brazil intends to build a facility for the 99Mo production through 235U fission, once this radioisotope is largely used in nuclear medicine. This study aimed at estimating the physical, chemical and radiological characteristics of radioactive waste expected to be generated in that facility, and to provide theoretical subsides that can be used on the definition of a proper waste management system. Two production scenarios were established and the radioisotope inventories of the wastes were calculated by Scale®. From the chemical processing of the uranium targets the wastes were characterized on their chemical and radiological features. MicroShield® was used to determine the activity concentrations up to three months of 99Mo production. In addition, this work presents dose rate calculation for several sizes of shielding and different amount of wastes, collected in a proper package for in-site transportation. Radionuclides responsible for higher doses were identified in order to facilitate choosing the most appropriate method for managing the wastes after their chemical separation and before their storage. These results are part of what is expected on radioactive wastes at a 99Mo production facility and might help on the development of the waste management planning for that facility.

Com objetivo de avaliar a eficiência do uso de fertilizante (contendo macronutrientes - nitrogênio, fósforo e potássio - e micronutrientes - cobalto e molibdênio), associado a fungicida e a inoculante, no tratamento de sementes de soja (variedade cultivada FT-Abyara), foram realizados dois experimentos, em laboratório (2007) e em campo (safra agrícola de 2007/2008), no Departamento de Biologia da Universidade Federal de Santa Maria, em Santa Maria-RS. O experimento I constou de tratamentos de doses de macronutrientes e micronutrientes em mistura com os fungicidas Thiram e Carbendazim aplicados em Bradyrhizobium spp. em meio de cultura YMA. O experimento II foi realizado para avaliar o efeito do tratamento de sementes de soja com micronutrientes e fungicidas na sobrevivência de Bradyrhizobium spp. e sua influência no crescimento da planta. Com relação aos diferentes fertilizantes avaliados, verifica-se que o maior número de nódulos por planta e maior massa de matéria seca de nódulos foi obtido com os compostos que continham cobalto e molibdênio, resultado também observado em relação aos tratamentos com fungicidas. Os resultados experimentais permitem inferir que todos os tratamentos com fertilizantes aplicados via sementes aumentaram significativamente a altura de planta, o comprimento de raiz, e a massa de matéria seca da parte aérea e de raiz quando comparados à testemunha sem tratamento com fertilizante, fungicida e inoculante. Em função dos resultados obtidos neste trabalho com a cultura de soja, pode-se concluir que: (i) o tratamento de sementes com fungicidas diminui o número de células viáveis de Bradyrhizobium spp.; (ii) a utilização de cobalto e molibdênio no tratamento de sementes proporciona aumento na quantidade de células de Bradyrhizobium spp.; e (iii) o melhor parâmetro para avaliar a eficiência da inoculação no tratamento de sementes é o número de células viáveis de Bradyrhizobium spp. / With the purpose of evaluating the efficiency of fertilizers (with macronutrients - nitrogen, phosphorus and potassium - and micronutrients - cobalt e molybdenum), fungicides and inoculant utilization in the soybean (cultivar \'FT-Abyara\') seed treatment, two experiments were carried out, in laboratory (2007) and in field (season 2007/2008), at Biology Department of Federal University of Santa Maria, in Santa Maria, \'Rio Grande do Sul\' State, Brazil. The experiment I consisted of evaluating the macronutrients and micronutrients doses treatments mixed with fungicides (Thiram and Carbendazim) applied in the YMA culture medium of Bradyrhizobium spp. The experiment II consisted of evaluating the soybean seed treatment (with micronutrients and fungicides) effect on Bradyrhizobium spp. survival and its influence on the plant growth. In relation to different evaluated fertilizers, the higher number of nodules per plant and higher nodules dry mass were obtained with cobalt and molybdenum seed treatments. Similar results also were obtained with fungicides treatments. According to the results, all treatments with fertilizers increased the soybean plant height, root length, dry matter of canopy and roots when compared to the control (without fertilizers, fungicides and inoculant). According to the results, there are the following conclusions: (i) the seed treatment with fungicides decreases the viable cells number of Bradyrhizobium spp.; (ii) the utilization of cobalt and molybdenum in the seed treatment increases the Bradyrhizobium spp. cells number; and (iii) the best parameter to evaluate the seed treatment inoculation efficiency is the viable cells number of Bradyrhizobium spp.