Ammonia borane and ammonium borohydride have been considered extensively as potential hydrogen storage materials. This thesis reports their structure and functional properties, emphasising the key role that dihydrogen bonding plays in both materials. The formation of a 'mobile phase' is considered to be the preliminary step in the decomposition of ammonia borane. The formation of this mobile phase has been studied using neutron diffraction, inelastic neutron spectroscopy and NMR. It has been found that in the mobile phase, 'end-to-end' flipping of the ammonia borane molecule occurs. This is an important precursor to the next step in the decomposition: the formation of the diammoniate of diborane. The dihydrogen bonding networks which occur in both the orthorhombic and the tetragonal phases of ammonia borane, and are the controlling factor in the decomposition process, were investigated using Density Functional Theory Molecular Dynamics (DFT-MD) simulations. It was hence shown that in the high-temperature tetragonal phase of ammonia borane, dihydrogen bonding is still an important stabilising interaction and there is little to distinguish between the three crystallographically distinct dihydrogen bonds. A closely related hydrogen storage material, ammonium borohydride, was also studied using the same techniques. Its low temperature phase progression was examined using variable temperature neutron diffraction. The vibrational modes of ammonium borohydride were assigned by comparing vibrational spectra determined using inelastic neutron spectroscopy with the results of DFT-MD simulations. Quasielastic neutron spectroscopy was used to show that both the ammonium and borohydride groups in ammonium borohydride perform discrete 'hopping' reorientational motions at a wide range of temperatures, and that the ammonium group has a mean residence time approximately 100 times less than that of the borohydride group. Hydrogen atom densities in the ammonium group were determined from DFT-MD simulations, and from refinements of high-resolution neutron diffraction data using cubic harmonic basis functions.

ENGLISH ABSTRACT: Leaching of nickel laterite was conducted with a solution of ammonia and ammonium carbonate in a closed vessel. The vessel used in this study was designed to leach and perform solid-liquid separation at the same time. For solid-liquid separation, stainless steel sintered metal filter media were used. The sintered metal filter medium was selected for its high strength to withstand pressure, chemical resistance to caustic solution and back flushing properties. Optimum leaching conditions were determined by varying temperature, ammonia concentration, ammonium carbonate concentration and oxygen pressure. After leaching and filtration, the pH of the leach liquor was measured and samples were analyzed for dissolved metals (Ni, Fe and Co) using atomic absorption spectrophotometry. The most significant variable effect on leaching of nickel was the ammonia concentration. The maximum dissolution of nickel from the unroasted ore was 11.90% at 4 M NH3, 100oC, 2 M (NH4)2CO3 and 2 bar O2 pressure. Optimization from the leaching data was done using response profiling and desirability in Statistica software. Optimum leaching conditions were determined to be 3 M NH3, 2 M (NH4)2CO2, 100oC and 2 bar O2 pressure. The mineralogy of the ore before and after leaching was studied to understand why nickel extraction from unroasted ore was poor. XRF analysis of solids after leaching showed that iron, silicon, and magnesium remained the same. The only metal which showed significant decrease from solids was nickel. XRD analysis of solids after and before leaching showed that most mineral phases present in the ore are not affected by the leaching solution. SEM with EDS detection was used to determine nickel distribution within the ore. The results showed that nickel is mostly associated with iron. The iron is surrounded by magnesium and silicon. Silicate minerals do not react with ammonia and ammonium carbonate solution. From filtration experiments, the filtration differential pressure had no significant effect on the filtration rate. An average filtration rate of 0.29±0.07 ml/min.cm2 was obtained. The filtration rate from these experiments was very low. The main reason was due to quick pore clogging of sintered metals. Pore clogging was found to be mainly on the surface of the filter medium. Laterites have been found to have low permeability due a lot of clay present in the ore. Rheological studies on this ore showed that the ore has shear thickening behavior. However, a very clear filtrate was obtained. After each leach and filtration experiment, the sintered metals was unblocked by back flushing with water and air. Back flushing was successful because all 18 experiments were carried out using the same sintered filter medium. The effect of roasting the ore prior to leaching was investigated using optimum conditions obtained when leaching the unroasted ore. There was a slight improvement in nickel extraction when the ore was roasted. The average percentage extraction of nickel from 3 experimental runs was 19.25%±0.19 at 100oC, 3M NH3, 2M (NH4)2CO3, and 5 bar oxygen pressure. Some part of nickel in the ore was unextractable due to association of nickel with recrystallized silicate minerals in the reduced ore. Roasting improved permeability of the ore. The filtration rate improved significantly after roasting the ore. The average filtration rate was 2.60±0.05 ml/min.cm2. Dissolution kinetics of the unroasted and roasted saprolitic laterite were investigated with regard to the effects of temperature, ammonia concentration, ammonium carbonate concentration, and oxygen pressure. For the unroasted ore, it was found that dissolution rate and degree of nickel extraction increases with increasing temperature. Increase in ammonia concentration improves the degree of nickel extraction. Nevertheless, nickel extraction does not depend entirely on ammonia concentration because even when ammonia concentration is high and ammonium carbonate concentration is zero nickel extraction is low. An increase in ammonium carbonate concentration also increases the degree of nickel extraction. Ammonium carbonate is critical for the extraction, since ammonium ions in the solution prevent hydrolysis of the nickel ammine complex. Oxygen did not have a significant effect on the degree of nickel extraction. The leaching of nickel laterite was found to be a two stage leaching process. In the first stage, the dissolution of nickel is faster but after 15 minutes, the reaction rate is reduced. The reaction rate is reduced by inert minerals which host nickel. These minerals contain iron magnesium and silicon. The fast dissolution of nickel in the first stage represents leaching of free nickel in the ore. The data for the second stage of leaching was analyzed by the shrinking core model, and the results suggested that the dissolution rate is controlled by mixture kinetics (ash layer diffusion and surface reaction control). The activation energy for the dissolution reaction was calculated as 56.5 KJ/mol. The reaction order with respect to ammonia and ammonium carbonate were determined to be 0.3 and 0.26 respectively. For the roasted ore, the highest degree of nickel extraction was obtained at 60oC, 3M NH3, 2M (NH4)2CO3, and 5 bar oxygen pressure. The percentage extraction under these conditions was 28.7%. Temperature did not have a significant effect on the leaching rate. An increase in NH3 and (NH4)2CO3 increased the final extraction of nickel but did not have any effect on leaching rate in the first stage of leaching. In the absence of ammonium carbonate, nickel extraction is almost zero. The experimental data did not give linear fit to the shrinking core models investigated for the unroasted ore. The reason for this could be due to the sampling time interval which was too far apart, or the leaching behavior of roasted nickel is complicated and cannot explained by shrinking core model alone. Leaching experiments demonstrate that for a high degree metal extraction and improved reaction kinetics with ammonia and ammonium carbonate, the solution temperature should be high (>100oC) for the unroasted ore. In order to leach at high temperature with ammonia and ammonium carbonate a closed vessel is required to prevent reagent loses. The reaction kinetics showed that the reaction is controlled mostly by ash layer diffusion; this indicates that a low degree of nickel extraction in the unroasted saprolitic laterite is due to inert minerals (ash layer) which host nickel within the ore. In order to obtain a high degree of nickel extraction, the ore needs to be roasted under reducing conditions. Roasting conditions need to be carefully controlled to ensure high dissolution of nickel. In fact optimum roasting conditions which will give maximum dissolution of nickel, must be determined before working with the bulk of the ore. / AFRIKAANSE OPSOMMING: Logingstoetse van saprolitiese lateriet met 'n oplossing van ammonia en ammonium karbonaat is gedoen in 'n druk houer. Die logingsvat vir hierdie studie is ontwikkel om die loging sowel as die vloeistof – vastestof skeiding te doen. Gesinterde metaal filter medium was gebruik vir die vloeistof – vastestof skeiding aangesien dit die volgende eienskappe vertoon; die vermoë om druk te weerstaan, die chemiese weerstand teen bytsoda oplossing, asook voordelige terugspoel eienskappe. Optimum loogkondisies is bepaal deur die temperatuur, ammoniak konsentrasie, ammonium karbonaat konsentrasie, en suurstof druk te varieer. Na loging en filtrasie is die pH van die loogvloeistof gemeet en monsters is deur atoom absorpsie spektrofotometrie geanaliseer vir opgeloste metale (Ni, Fe en Co). Die veranderlike wat die grootste effek op die loging van nikkel gehad het was die ammoniak konsentrasie. Die maksimum herwinning van nikkel van uit ongeroosterde erts was 11.9 % by 4 M NH3, 100 oC, 2 M (NH4)2CO3 en 2 bar O2 druk. Optimisering van die loogdata is gedoen deur die respons profiel te analiseer met Statistica sagteware. Optimum loogkondisies was bepaal as 3 M NH3, 2 M (NH4)2CO2, 100 oC en 2 bar O2 druk. Die mineralogie van die erts voor en na loging is bestudeer om te bepaal waarom die nikel opbrengs van ongeroosterde erts so laag was. XRF analise van die vastestof na loging het gewys dat yster, silikon en magnesium nie deur loging affekteer is nie. Slegs nikkel het 'n merkwaardige afname getoon. XRD analsiese van die vastestof voor en na loging wys dat die meeste mineraal fases teenwoordig in die erts nie deur die loogoplossing affekteer is nie. SEM met EDS deteksie is gebruik om die nikkel verspreiding in die erts te bepaal. Die resultate wys dat nikkel meestal met yster assosieer. Die yster is omring deur magnesium en silikon. Silikaat minerale reageer nie met ammoniak en ammonium karbonaat oplossing nie. In filtrasie eksperimente is daar gevind dat die filtrasie differensiële druk geen noemenswaardige effek op die filtrasie tempo gehad het nie. Die gemiddelde filtrasietempo was 0.29+0.07 ml/min.cm2. Die filtrasie tempo van hierdie eksperimente was baie laag, hoofsaaklik as gevolg van blokkasie van porieë van die sinter metaal filter medium. Dit is gevind dat blokkasie van porieë hoofsaaklik op die oppervlak van die filter medium plaasvind. Lateriedes toon 'n lae deurlaatbaarheid as gevolg van die erts se hoë klei inhoud. Rheologiese studies op hierdie erts wys dat die erts skuif verdikking (“shear thickening”) gedrag vertoon. 'n Baie helder filtraat is egter verkry. Die gesinterde metale is na elke loog en filtrasie eksperiment skoongemaak deur terugspoeling met water en lug. Hierdie procedure was suksesvol, aangesien al 18 eksperimente met dieselfde filter medium uitgevoer is. Die effek van erts roostering voor loging is ondersoek by die optimum kondisies wat verkry was vir die loging van ongeroosterde erts. Nikkel ekstraksie het effens verbeter met geroosterde erts. Die gemiddelde persentasie ekstraksie van nikkel van drie eksperimentele lopies was 19.25 % + 0.19 by 100 oC, 3 M NH3, 2 M (NH4)2CO3, en 5 bar suurstofdruk. 'n Gedeelte van die nikkel in die erts was onherwinbaar as gevolg van die assosiasie van nikkel met her-gekristaliseerde sillikaat-minerale in die gereduseerde erts. Die porositeit van die erts is verbeter deur dit te rooster. Die filtrasie tempo het merkwaardig verbeter nadat die erts gerooster is. Die gemiddelde filtrasie tempo was 2.6+0.05 ml/min.cm2. Kinetika vir die oplossing van ongeroosterde en geroosterde saprolitiese lateriet is ondersoek, met in ag geneem die effekte van temperatuur, ammonia konsentrasie, ammonium karbonaat konsentrasie en suurstofdruk. Vir ongeroosterde erts is gevind dat die oplossingstempo en graad van nikkel ekstraksie toeneem met toenemende temperatuur. Toename in ammoniak konsentrasie lei tot 'n toename in nikkel ekstraksie, maar nikkel ekstraksie is nie alleenlik afhanklik van ammoniak nie. 'n Toename in ammonium karbonaat konsentrasie lei ook tot 'n toename in nikkel ekstraksie. Ammonium karbonaat is krities vir die ekstraksie, aangesien ammonium ione in die oplossing die hidrolise van die nikkel-amien kompleks verhoed. Suurstof het nie 'n merkwaardige effek op die totale nikkel ekstraksie gehad nie. Vir die bepaling van reaksie kinetika is 100˚C gebruik as die logingstemperatuur. Die loging van saprolitiese nikkel lateriet vind in twee stadia plaas. In die eerste fase is die oplossing van nikkel vinnig, maar na 15 minute neem die reaksietempo af. Die reaksietempo word verlaag deur inerte minerale wat teenwoordig is in die nikkel erts. Hierdie minerale bevat yster, magnesium en silikon. Die vinnige oplossing van nikkel in die eerste fase verteenwoordig die loging van vry nikkel in die erts. Die data vir die tweede stadium is geanaliseer deur die krimpende kern model, en die resultate dui aan dat die oplossingstempo deur 'n gemengde meganisme beheer word (as laag diffusie en oppervlak reaksie beheer). Die aktiveringsengergie vir die oplossingsreaksie was bereken as 56.5 kJ/mol. Die reaksieorde ten opsigte van ammoniak en ammonium karbonaat is onderskeidelik bepaal as 0.3 en 0.26. Die hoogste graad van nikkel ekstraksie vir die geroosterde erts is verkry by 60oC, 3 M NH3, 2 M (NH4)2CO3, en 5 bar O2 druk. Die persentasie ekstraksie by hierdie kondisies was 28.7 %. Temperatuur het nie 'n merkwaardige effek op loogtempo gehad nie. 'n Toename in NH3 en (NH4)2CO3 het die graad van nikkel ekstraksie laat toeneem, maar het nie enige effek op die loogtempo gehad nie. In die afwesigheid van ammonium karbonaat het byna geen nikkel ekstraksie plaasgevind nie. Die eksperimentele data het nie 'n lineêre passing vir die krimpende kern model soos vir die ongeroosterde erts ondersoek gegee nie. Die rede hiervoor is dat die monsternemings interval te groot was, of dat die logings karakteristiek van geroosterde nikel gekompliseerd is en nie alleen deur die krimpende kern model voorspel kan word nie. Logings eksperimente wys dat die temperatuur hoog moet wees (> 100 oC) om 'n hoë graad van nikkel ekstraksie te verkry met die ongeroosterde erts. 'n Geslote reaktor word benodig om by 'n hoë temperatuur met ammoniak en ammonium karbonaat te loog om reagens verliese te verhoed. Die reaksie kinetika word grootliks deur aslaag diffusie beheer. Hieruit kan gesien word dat 'n lae graad van nikkel ekstraksie uit die ongeroosterde saprolitiese lateriet die gevolg is van nie-reaktiewe minerale (aslaag) waarin die nikkel binne die erts bevat word. Om 'n hoë graad van nikkel ekstraksie te verkry moet die erts onder reduserende kondisies gerooster word. Rooster kondisies moet versigtig beheer word om hoë oplossing van nikkel te verseker. Optimum rooster kondisies om maksimum nikkel oplossing te verkry, moet bepaal word voordat daar met groter hoeveelhede erts gewerk kan word.

published_or_final_version / Civil Engineering / Master / Master of Philosophy

Studies have shown that significant amounts of nitrate-N is leached beyond root zones of annual crops while small amounts of nitrate-N is leached beyond the root zones of perennial forage grasses. This study investigated short-term ammonium-N persistence and root nitrogen content of annual crop and perennial forage grasses following application of pig manure to a sandy loam soil at Carman, Manitoba. Results showed that ammonium-N in liquid pig manure (LPM) amended treatment peaked four days after manure application (DAM) in perennial cropping system (PCS; 50 - 74 kg ha-1) and annual cropping system (ACS; 18 - 29 kg ha-1) in 2014 and 2015. Ammonium-N persisted up to 7 DAM in LPM amended PCS, but did not persist beyond 4 DAM in LPM amended ACS. Ammonium-N measured in solid pig manure (SPM) amended ACS and PCS was low throughout the sampling days in both years. There was a greater percentage increase in accumulation of nitrate-N at 15 - 30 cm soil depth of LPM and SPM amended ACS than PCS. In both years, dry weight below-ground plant biomass ranged from 5,258 to 9,627 kg ha-1 at 0 - 60 cm depth in PCS while that of ACS ranged from 1,088 to 1,456 kg ha-1. Also, root N content in PCS ranged from 43 to 118 kg N ha-1 in both years while that of ACS ranged from 9 to 20 kg N ha-1. In conclusion, ammonium-N persisted longer in PCS than ACS in the short-term and total plant N was greater in PCS than ACS. Greater total plant N in PCS than ACS was mainly due to its greater root N content rather than above-ground N uptake. The order of magnitude of the difference in root N content (34 to 98 kg N ha-1) between ACS and PCS was sufficient to account for the 20 to 60 kg N/ha of nitrate-N leached in ACS in previous study at the same site. / October 2016

Denna studie handlar om en metod som används för att lokalisera inläckage av tillskottsvatten på spillvattennät. Grunden är de praktikperioder som författaren har haft hos VA-bolaget Helsinge Vatten AB och då det utförts flera försök till att utreda inläckage i spillvattenledningarna. Metoden går ut på att analysera koncentrationen av ammonium i flödet som hämtas från brunnarna ute på nätet. Analyserna sker med hjälp av en portabel spektrofotometer tillsammans med reagenskyvetter som analyserar koncentrationen på bara 15 minuter. Detta ger en indikation på hur utspätt spillvattnet är, om det är utspätt av tillskottsvatten så visar analysen ett lågt värde vilket tyder på inläckage av dagvatten, grundvatten eller dricksvatten. Denna metod är framtagen av Norrköping Vatten och Avfall som har lyckats bra med att lokalisera inläckage med metoden. Norrköping Vatten och Avfall är en stor källa till denna studie med sin rapport ”Minskning av in- och utläckage genom aktiv läcksökning”(Uusijärvi, 2013).  I rapporten redovisas de ammoniumanalyser som har gjorts med tillhörande diagram för att tydliggöra resultaten. Eftersom spillvattennät ofta hör samman med pumpstationer och reningsverk som påverkar elförbrukning har statistik tagits fram för den pumpstation som analysområdet hör samman med. Elförbrukning har jämförts med nederbördsmätning för att se om ledningsnätet är påverkat av nederbörd, eftersom pumpstationen får arbeta mer om det är tillskottsvatten i ledningarna.  För att få fram en uppskattad mängd inläckage så har en beräkning gjorts med hjälp av en mall som Norrköping vatten och avfall har tagit fram. Där används analysvärden som tyder på inläckage tillsammans med antal abonnenter, ledningssträcka och storförbrukares avlopp. Tillsammans blir det ett värde på uppskattat inläckage i liter per dygn och meter ledning(L/D/M).  I rapporten finns det tre områden som ingår i byn Rengsjö som är utredda med ammoniummetoden. I ett testområde blev resultatet inte som önskat men lärorikt för personalen. Ett område gav resultat som visar på god kvalitet av nätet med en jämförelse av torr- och regnväder. Samt ett område där ett troligt inläckage upptäckts som kommer utredas vidare under sommaren. Detta fynd kan ge stora mängder tillskottsvatten, vilket uppfyller delar av de mål som formulerats i rapporten, dvs. att hitta inläckage för att planera vidare utredning. Tillsammans med resultaten för varje område finns en omfattande diskussion där alla aspekter som påverkar de uppmätta analysvärdena tas upp.  Som slutsats konstateras ammoniummetoden som mycket framgångsrik i syfte för Helsinge Vatten att systematiskt kunna kartlägga och utreda sina spillvattennät. Det är en kostnadseffektiv och inte så resurskrävande metod som företaget själv kan använda på en lagom nivå. / This study aims to locate the intrusion of excess water in the sewage networks, analyzing the concentration of ammonium in the flow that is obtained from the wells in the network. The foundation for the work is the author’s previous attempts to investigate stormwater at the VA-company Helsinge Vatten AB. The analysis is carried out by using a portable spectrophotometer with such reagents that can measure ammonium concentration in just 15 minutes. This gives an indication of how diluted effluent is. If  it is diluted by excess water the analysis shows a low value which is indicating intrusion of possibly surface water, groundwater or drinking water. This method is developed by Norrköping vatten och avfall, who have been a major reference of this report, with their study “Minskning av in- och utläckage genom aktiv läcksökning”(Uusijärvi, 2013).  Results from the ammonium analyses have been presented with associated charts. Because the sewage networks often are associated with pumping stations and wastewater treatment plants, which effect the electricity consumption, the electricity consumption has been documented for the pump stations in the area of study. The electricity consumption increases when the pumps are working. A analysis has been made by comparing the electricity consumption and the precipitation to see if the sewage network is influenced by precipitation.  In order to obtain an estimated amount of excess water intrusion, a calculation have been made by using a template produced by Norrköping Vatten och Avfall. In the calculation, values indicating water intrusion along with the number of subscribers, management and those who discharge most wastewater have been used. Together it gives a result of estimated intrusion in liters per day and meter network (L/D/M).  In the report, three areas located in the village Rengsjö have been investigated by using this method. The first area where the outcome was not as desired, but very instructive for the staff. The second area gave results that show the good quality of the net with a comparison of dry and wet weather. And also an area where a likely intrusion is detected and will be investigated further during the summer. This finding can indicate large amounts of stormwater. Those findings compiles with parts of the objectives formulated in the report, to find the intrusion and to plan for further investigation. Together with the results for each area, include an extensive discussion in which all aspects that influence the measured analyses have been taken up.  The report shows that the ammonium method  has been proved to be successful in identifying excess water intrusion in Helsinge Vatten’s sewage networks. This method does not rely on many resources, and therefore it is suitable for companies that wish investigate excess water instruction in a cost-effective way.

Master of Science / Food Science / Kelly J. K. Getty / Dry-processing environments are particularly challenging to clean and sanitize because water introduced into systems not designed for wet cleaning can favor growth and establishment of pathogenic microorganisms such as Salmonella. The objective was to determine the efficacy of isopropyl alcohol quaternary ammonium (IPAQuat) formula and carbon dioxide (CO[subscript]2) sanitizer system for eliminating Enterococcus faecium and Salmonella on food contact surfaces. Coupons of stainless steel and conveyor belting material used in dry-processing environments were spot-inoculated in the center of 5 × 5 cm coupons with approximately 7.0 log CFU/ml of E. faecium and up to 10 log CFU/ml of a six-serotype composite of Salmonella and subjected to IPAQuat-CO[subscript]2 sanitation treatments using exposure times of 30 s, 1 or 5 min. After sanitation treatments, wet coupons were swabbed for post-treatment survivors. Preliminary experiments included coupons which were soiled with a flour and water solution prior to inoculation and subsequent sanitation treatments. For the main study, inoculated surfaces were soiled with a breadcrumb flour blend and allowed to sit on the lab bench for a minimum of 16 h before sanitation. Preliminary results showed that IPAQuat-CO[subscript]2 sanitizing system was effective in reducing approximately 3.0 logs of E. faecium and Salmonella from clean and soiled surfaces after 1 min exposure but higher initial inoculum levels were needed to demonstrate >5 log reductions. For the main study, pre-treatment Salmonella populations were approximately 7.0 log CFU/25 cm[superscript]2 and post-treatment survivors were 1.3, < 0.7 (detection limit), and < 0.7 log CFU/25 cm[superscript]2 after 30 s, 1 or 5 min sanitizer exposures, respectively, for both clean and soiled surfaces. Treatment with IPAQuat-CO[subscript]2 sanitation system using 30 s sanitizer exposures resulted in 5.7 log CFU/25 cm[superscript]2 reductions whereas, greater than 6.0 log CFU/25 cm[superscript]2 reductions were observed for sanitizer exposures of 1 and 5 min. The IPAQuat-CO[subscript]2 sanitation system reduced 6 logs CFU/25 cm[superscript]2 of Salmonella with sanitizer exposure times of at least 1 min. The IPAQuat-CO[subscript]2 system would, therefore, be an effective sanitation system to eliminate potential contamination from Salmonella on food contact surfaces and have application in facilities that process dry ingredients or low-moisture products.

<pre>The plethora of potential homemade explosive (HME) formulations combined with the fact they often exhibit large critical diameters make them expensive to characterize with traditional large-scale tests. A relatively new method for small-scale characterization was investigated using non-ideal explosive charges consisting of ammonium nitrate (AN) and various fuels. This optical characterization technique utilizes the rate of reaction wave velocity decay in the failing detonations of sub-critical diameter charges as a metric for the shock sensitivity of an explosive. The conditions for detonation initiation and failure have long been used to investigate shock sensitivity (critical diameter, gap tests, run-to-detonation experiments); however, the failure regime still remains largely unexplored. The utility of this small-scale characterization technique lies in its ability to determine the relative shock sensitivity of explosive with minimal material and tests while simultaneously providing transient velocity data for potential use in modeling efforts. In this work, high speed imaging was used and analyzed to determine rates of reaction wave velocity decay in the AN-fuel samples. Among the fuels tested with AN were diesel (ANFO), nitromethane (ANNM), and aluminum (ANAl). It was found that nitromethane was the most effective at sensitizing the AN of the systems considered. In both ANNM and ANAl, maximum shock sensitivity occurred at fuel percentages below stoichiometric mixtures. This was speculated to be due to the competing effects of stoichiometry and hot spot criticality. Sensitivity results were compared to run-to-failure distances and published critical diameter trends and showed good agreement. </pre>

Foi conduzido experimento em casa-de-vegetação do Departamento de Solos e Nutrição de Plantas da ESALQ - USP, durante o período de fevereiro a maio de 2002, com o objetivo de avaliar respostas produtivas, fisiológicas e nutricionais a proporções de nitrato e amônio, das forrageiras Panicum maximum cv. Aruana e Brachiaria brizantha cv. Marandu, cultivados em solução nutritiva, utilizando sílica como substrato. Foi empregado o delineamento experimental de blocos completos ao acaso, com quatro repetições e seis tratamentos. O nitrogênio foi estudado na dose de 210 mg L -1 e nas proporções respectivas de nitrato e amônio de 100/0; 85/15;70/30; 55/45; 40/60 e 25/75%. As soluções foram preparadas a partir da solução completa de Sarruge (1975), devidamente modificada para as proporções desses íons no suprimento de nitrogênio. Dois corte foram realizados nas plantas, separando-se os componentes da parte aérea em folhas emergentes, lâminas de folhas recém-expandidas, lâminas de folhas maduras e colmos mais bainhas. Após o segundo corte, as raízes foram separadas da sílica e lavadas. Durante o crescimento das plantas foram determinados a atividade da redutase do nitrato e o valor SPAD e na ocasião dos cortes foram contados os perfilhos e as folhas das plantas e foi medida a área foliar. No material seco foi obtido a produção de massa e nas amostras moídas foram determinadas as concentrações de nitrogênio total, de nitrato e de amônio. Nas raízes foram avaliadas a superfície e comprimento total. As proporções de 85/15 a 55/45 de nitrato/amônio propiciaram aumento do número de perfilhos e de folhas. A área foliar e a massa seca da parte aérea responderam positivamente ao nitrogênio fornecido em proporção 100/0 a 55/45 de nitrato/amônio. A massa seca, a superfície e o comprimento de raízes foram beneficiadas pelo fornecimento de nitrato/amônio em proporções de 70/30 e 55/45. A aplicação de nitrato e amônio nas proporções de 40/60 e 25/75 resultou em mais elevada concentração de nitrogênio total nos colmos mais bainhas e de amônio nas lâminas de folhas maduras. Os atributos produtivos dos capins foram prejudicados pelo uso da proporção de nitrato/amônio de 25/75. A inclusão de amônio em substituição de parte do nitrato na solução completa de Sarruge beneficia os capins estudados. / A greenhouse experiment was carried out in the Soils and Plant Nutrition Department, at ESALQ-USP from February to May 2002. The objective was to evaluate the response in relation to proportions of nitrate and ammonium in the nutrient solutions of Panicum maximum cv. Aruana and Brachiaria brizantha cv. Marandu. Plants grew in a ground quartz substrate. The experiment was set in complete randomized block design, with four replications. Nitrogen at 210 mg L -1 was studied in proportions 100/0; 85/15; 70/30; 55/45; 40/60 and 25/75% of nitrate and ammonium, respectively. A complete Sarruge (1975) solution was modified to supply nitrogen in the studied proportions. Plants were harvest twice and plant tops was separated in emerging leaves, lamina of recently expanded leaves, lamina of mature leaves and steams plus sheaths. After the second harvest, roots were taken from the substrate and washed. During the growth period the nitrate reductase activity and SPAD units were determined and at the plant harvesting the number of tillers and leaves were counted and leaf area was measured. Dry matter yield was obtained in the oven, dry plants and the concentration of total nitrogen, nitrate and ammonium were determined in the ground sample. Roots were evaluated for the total surface and length. Increases in the number of tillers and leaves were found with the 85/15 to 55/45 proportions of nitrate/ammonium. Leaf area and plant tops dry weight positively responded to the nitrogen supplied form 100/0 to 55/45 as nitrate/ammonium. Nitrate and ammonium applied in the 40/60 and 25/75 proportions showed the highest total nitrogen concentration in stems plus sheaths and the highest ammonium concentration in the lamina of mature leaves. Grasses production was decreased by the use of nitrate/ammonium at 25/75 proportion. The inclusion of ammonium as part of the nitrogen supply in the Sarruge’s nutrient solution is beneficial to the studied forage grasses.

Em uma das etapas do processo de produção do dióxido de urânio, obtém-se como subproduto o fluoreto de amônio em solução. O dióxido de urânio é utilizado na confecção dos elementos que abastecem às Usinas Nucleares.Na unidade fabril da empresa Indústrias Nucleares do Brasil S. A.,esse material sintético é cristalizado em um oneroso e delicado processo de secagem, utilizando grandes equipamentos e considerável quantidade de insumos.A unidade fabril em questão é capaz de produzir anualmente pouco mais de 130 toneladasde fluoreto de amônio seco e a perspectiva atual é favorável à expansão da capacidade instalada. Atualmente, não há destinação final ou aplicação prevista para esse material seco, ou seja, o material é armazenado por tempo indeterminado, onerando ainda mais a produção do combustível nuclear com os custos de manuseio e armazenagem. Este trabalho propõe-se a estudar uma rota alternativapara a síntese da fluorita, ou fluoreto de cálcio (CaF2), a partir da solução de fluoreto de amônio obtida como subproduto do processode produção do Dióxido de Urânio, verificando qual o melhor agente precipitante e estabelecendo as melhores condições para o processo de síntese. A fluorita possui uma vasta aplicação, principalmente nos campos da química, siderurgia e cerâmica. Os melhores resultados foram obtidos utilizando-se calcita (CaCO3) como agente precipitante, mantidas as condições de processo: temperatura (Treação) =70 ºC; tempo de residência (treação) = 2 h e relação estequiométrica entre os reagentes (RE) = 1:1. A calcita foi caracterizada por ICP/OES, difratometria de raios-X (DRX) e microscopia eletrônica de varredura acoplada a espectrômetro de energia dispersiva (MEV/EDS).Os produtos foram caracterizados por DRX e MEV/EDS. / At the uranium dioxide production process, ammonium fluoride is obtainedas a byproduct. Uranium dioxide is used at the production of fuel assemblies for Nuclear Mills.At Indústrias Nucleares do Brasil S. A. site, synthetic ammonium fluoride is crystallized in a costly and delicate drying process, which spends importantamounts of supplies. The industrial site in question is able to annually produce over 130 tons ofdryammonium fluoride and the current outlook is favorable to the expansion of installed capacity. Currently, there is no final destination or application provided for this dry material, i.e.,the material is stored indefinitely, further burdening the production of nuclear fuel with the handling and storage costs. This work proposes to study an alternative route for the synthesis of fluorite, or calcium fluoride (CaF2), from ammonium fluoride solution obtained as a by-product of uranium dioxide production process, checkingthe best precipitant agent and establishing the best conditions for the synthesis process.The fluorite has a wide application, particularly in the fields of chemistry, steel and ceramic. The best results were achievedusing calcite (CaCO3) as precipitating agent, keeping the process conditions: temperature (Treação) = 70 ° C; residence time (treação) = 2 h stoichiometric ratio between the reagents (ER) = 1:1.The calcite was characterized by X-ray diffraction (XRD) and scanning electron microscopy coupled with energy dispersive spectrometer (SEM/EDS).The products were characterized by XRD and SEM/EDS.

Amostras da água subterrânea foram coletadas em poços piezométricos localizados em dois transectos ao longo das vertentes e dois transectos ao longo da cabeceira de drenagem de uma microbacia experimental, durante o período de maio de 2005 a abril de 2006. Em cada transecto os poços piezométricos estavam localizados respectivamente na parte alta da vertente, sob floresta plantada de Eucalyptus, na meia encosta, sob mata ciliar, e adjacente ao riacho. As análises destas amostras também foram comparadas com a análise simultânea da água do riacho, coletada na calha da estação linimétrica da microbacia. As análises químicas incluíram principalmente nitrato (N-NO3 -) e amônio (N-NH4 +), além do ferro, silício, alumínio, carbono orgânico dissolvido (DOC) e pH. O objetivo foi inferir sobre aspectos do funcionamento hidrológico da zona ripária, em termos de alteração da concentração dos íons analisados entre os pontos amostrados. A fim de inferir sobre o efeito da vegetação e das características do solo nas modificações da água subterrânea ao longo da vertente, foi realizado inventário para determinação da área basal da vegetação e análise granulométrica e química do solo. Os principais resultados mostram que na zona ripária adjacente ao riacho há maior concentração de matéria orgânica no solo e de amônio na água subterrânea. As concentrações de amônio e nitrato na água do riacho foram sempre menores do que as concentrações nos piezômetros adjacentes ao riacho próximo ao vertedor. Isso indica que na zona ripária ocorrem modificações na água subterrânea que garantem a manutenção do ecossistema lótico. Também foi possível identificar diferenças ao longo da microbacia, entre a cabeceira de drenagem e a área próxima ao vertedor, o que demonstra que a zona ripária não é homogênea na área da microbacia. A geologia, a granulometria e o teor de matéria orgânica do solo, a precipitação, o aumento do nível freático e a influência da água subterrânea, foram os principais fatores de alteração das demais variáveis do estudo. / Groundwater samples were collected in piezometers located in two transects through the hillslope and two in the headwater of an experimental catchment from May 2005 to April 2006. In each transect there were one piezometer in the upland under the Eucalyptus planted forest, one piezometer at the middle slope in the riparian area, and the other piezometer was located by the stream with a total of 12 piezometers. The samples collected fortnightly were analyzed and compared with the stream water collected in the stream gauging station. The main variables analyzed were nitrate (N-NO3 -) and ammonium (N-NH4 +) as well as iron, silicon, aluminum, dissolved organic carbon (DOC) and pH. The objective was to infer about riparian zone hydrology, based on the difference among chemical composition of the samples. A characterization of the experimental catchment was performed from a vegetation inventory and soil analysis in order to assess the influence of soil properties and vegetation nutritional demand on the chemistry of the solutions. Chemical analyses demonstrated that in the riparian zone close to the stream soil organic matter content was higher than in other topographic positions as well as concentrations of ammonium in the groundwater throughout the year. The concentrations of ammonium and nitrate in the groundwater beside the stream were always higher. These results indicated that in riparian zone the modifications in the groundwater contribute to the lotic ecosystem maintenance. The results also indicated that the riparian zone is heterogeneous along the catchment area and that the behavior of headwater and downstream may be different. The geology, soil granulometric and organic matter level, precipitation and groundwater level were the main factors that influenced the studied variables.