An experimental test system was designed to simulate the operating conditions found in nonslagging coal gasifiers. The reaction products that form when refractory linings in coal gasifiers are exposed to alkali impurities (sodium or potassium) were experimentally determined. Analysis of selected physical and chemical properties of the reaction products, which typically form between the alkali and the refractory will lead to a better understanding of the mechanisms behind refractory failures associated with alkali attack. The reaction products sodium aluminate (Na₂O·Al₂O₃), N₂C₃A₅ (2Na₂O·3CaO·5A1₂O₃), nepheline (Na₂0·Al₂0₃·2SiO₂), potassium aluminate, (K₂Oâ·Al₂0₃), and kaliophilite (K₂O·Al₂0₃·2Si0₂) were synthesized and their solubility in water and coefficients of linear thermal expansion were: measured. Of the compounds tested, the formation of potassium aluminate would be the most detrimental to the gasifier lining. The linear thermal expansion of potassium aluminate was 2.05% from room temperature to 800°C, which was twice as large as the other compounds. Potassium aluminate also possessed the highest solubility in water which was 8.893/L at 90°C. / Master of Science

The effects of stainless steel fiber additions on the resistance of castables to CO and steam were investigated. A series of high and intermediate alumina calcium-aluminate bonded castables was prepared containing several commercial stainless steel fibers. Compressive strength and abrasion resistance of the castables were measured after exposure to high pressure carbon monoxide and steam at 500ºC. Strength and abrasion resistance values were comparable to those of samples without stainless steel fibers. The addition of stainless steel fibers to refractory castables was found to not decrease resistance to carbon monoxide only if the castables were not fired in air prior to CO exposure. Firing in air was found to create oxide layers on the fibers which catalyze CO decomposition, ultimately causing disintegration of the castable. / Master of Science

Three monolithic refractories (a 90+ wt.% alumina Castable, a 50+ wt.% alumina castable, and a 90+ wt.% alumina phosphate-bonded ramming mix) doped with up to 2.0 wt.% Fe and 2.0 Fe wt.% Fe₂O₃ were tested for CO disintegration in a 100 hr. test similar to. ASTM C-288. The effects of CO₂, NH₃, H₂, H₂S, and H₂O on CO disintegration were observed. Prefired samples of all three refractories were found to be susceptible to disintegration in a CO atmosphere when 0.5 wt.% Fe or more was added. Castables doped with up to 2.0 Fe wt.% Fe₂O₃ were not affected by CO, while the ramming mix doped with 1.5 Fe wt.% Fe₂O₃ or more was. H₂ and H₂O proved most effective in retarding CO disintegration in all three refractories. CO₂, H₂S, and NH₃, in descending order, also retarded CO disintegration in both castables. The retarding effect of up to 15% CO₂ in CO is questionable for the ramming mix. NH3 did not slow CO disintegration in this refractory and H₂S actually accelerated the disintegration process. The effect of gas pressure is also found to be especially important, for it greatly accelerates CO disintegration in all three monoliths and appears to be a more significant factor than the disintegration~inhibiting gases. An optimum iron-impurity size range, neither a maximum nor a minimum, for which CO disintegration resistance was greatest was also found for the 90+ wt.% alumina castable. / Master of Science

M.S.

With the need for stealth in defense applications steadily increasing, noise reduction continues to play an important role in the world of aeronautics. With the ever increasing number of small UAV flight vehicle designs and their stringent weight requirements, acoustic solutions become progressively more complex. This thesis investigates the use of refractory foam, a new class of porous material, for designing effective silencers for small IC engines. The solution must be lightweight, compact, conformable, and capable of handling the rigors of flight. Throughout the course of this research, many silencer designs were fabricated to take advantage of refractory foam technology. These silencer designs were then tested against existing designs using both anechoic and outdoor testing techniques. These results proved refractory foam to be a superior broadband noise absorber that can survive harsh flight environment. Silencer designs using this material showed overall improvements in the areas of noise reduction, weight, size, and backpressure, compared to commercial designs. The final silencer design boasted an Aweighted overall sound pressure level that was 12.1 dBA lower than the reference case. This result was accomplished using nearly half the volume required by other designs to attain similar results. / Master of Science

Although bacterial leaching of sulphidic minerals is a well-known phenomenon, it is only in the last ten years that full-scale bacterial leaching plants have been commissioned for gold processing. In order for bacterial leaching to compete successfully with other pretreatment processes for refractory ores, particularly with established technologies such as roasting and pressure leaching, it needs to be efficient. This requires the optimization of the parameters affecting the leaching reaction and the growth of bacteria. The entire biotreatment process is agitation leaching, carried out in stirred reactors or Pachuca type reactors. The bacterial oxidation is a complex reaction involving gaseous, liquid and solid phases. The interactions are highly complex, and analysis is complicated by the presence of solids in the leaching medium. Inspite of the amount of research that has been performed, kinetic and process models are underdeveloped. Since kinetic data varies widely with the type and source of concentrate, experimental data should be generated before doing the full-scale reactor design. In sizing reactors for a commercial scale process, it would be useful to have a mathematical model that one could use to predict the amount and rate of release of metal, as a function of the various operating parameters of the system. G.R.Halli arsenical gold sulphide concentrate obtained from Hutti Gold Mines Ltd., Karnataka, was chosen for our study, because of its high refractoriness. An indegenous strain of Thiobacillus ferrooxidans was used for biooxidation. The experiments were conducted in a well-agitated stirred tank reactor under controlled conditions. Sparged air was supplemented with carbon-dioxide for optimized growth. In this work, more than 90% gold and 95% silver could be recovered from the sulphidic gold concentrate when bioleaching was used ahead of cyanidation, compared to 40% and 50% by direct cyanidation. A generalized model, which accounts for both direct bacterial attack and indirect chemical leaching, has been proposed for the biooxidation of refractory gold concentrates. The bacterial balance, therefore, accounts for its growth both on solid substrate and in solution, and for the attachment to and detachment from the surface. The overall process is considered to consist of several sub-processes, each of which can be described in terms of a mechanism and related rate expressions. These sub-processes were studied seperately under kinetically controlled conditions. The key parameters appearing in the rate equations were evaluated using the experimental data. Since the refractory concentrate contains pyrite and arsenopyrite as the major leachable entities, leaching studies have been done on pure pyrite and arsenopyrite as test minerals and the key parameters in the rate equations are evaluated using this data. The model so developed is tested with the leaching kinetics of the concentrate. The growth of bacteria is dependent on the availability of the substrate, ferrous iron, and the dependence is modelled by the widely accepted Monod equation. The effect of carbon dioxide supplementation on the bacterial activity was studied and the optimal concentration for growth was found to be l%(v/v). Studies on indirect chemical leaching showed that the rate is sensitive to surface area of concentrate. Indirect rate constant of arsenopyrite was found to be greater than that of pyrite, since pyrite is more nobler than arsenopyrite. Conditions of direct leaching alone was obtained at high pulp density and using substrate adapted bacteria. The rate constant of arsenopyrite was found to be greater than that of pyrite. The parameters obtained were tested with the overall batch leaching data of the concentrate and favourable comparision was obtained. Thus, it has been possible to isolate the various simultaneous sub-processes occurring during the leaching and propose useful models to describe these processes in some detail. The model has been extended successfully to predict the continuous leaching behaviour using the parameters obtained from the batch data. Studies on the effect of residence time and pulp density on steady state behaviour showed that there is a critical residence time and pulp density below which washout conditions occur. The critical residence time at 10% pulp density was found to be 11 hrs. Operation at pulp densities lower than 5% and residence times lower than 72 hrs is not favourable for efficient leaching. Studies on the effect of initial ferric iron concentration showed that there exists an optimum concentration of ferric iron at which the time required to reach steady state is minimum.

No description available.

The submerged entry nozzle (SEN) has been used to transport the molten steel from tundish to the mould. The main purpose of the SEN usage is both to prevent oxygen and nitrogen pick-up by molten steel and to achieve the desired flow condition in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. Furthermore, the steelmaking processes occur at high temperatures around 1873 K so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during pre-heating and casting is necessary for the design of the steelmaking processes. The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during pre-heating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied in supplement 1. The results of the study indicated the penetration of the formed alkaline-rich glaze into the Alumina/graphite base refractory during pre-heating. More specifically, the alkaline-rich glaze reacts with graphite to form carbon monoxide gas. Thereafter, dissociation of CO at the SEN/molten metal interface takes place. This leads to reoxidation of dissolved REM (Rare Earth Metal), which form the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, the interaction of the penetrated glaze with alumina in the SEN base refractory materials leads to a formation of a high-viscous alumina-rich glaze during the SEN pre-heating process. This in turn, creates a very uneven surface at the SEN internal surface. The “In Situ” formation of the REM oxides together with the uneven internal surface of the SEN may facilitate the accumulation of the primary inclusions. Supplement 1 revealed the disadvantages of the glass/silicon powder layer. On the other hand the carbon oxidation is a main industrial problem for un-coated Alumina/Graphite Submerged Entry Nozzles (SEN) during pre-heating. This led to the proposal of a new refractory material for the SEN. In supplement 2, the effect of ZrSi2 antioxidant and the coexistence of antioxidant additive and (4B2O3 ·BaO) glass powder on carbon oxidation were investigated at simulated non-isothermal heating conditions in a  controlled atmosphere. Also, the effect of ZrSi2 antioxidant on carbon oxidation was investigated at isothermal temperatures at 1473 K and 1773 K. The specimens’ weight losses and temperatures were plotted versus time and compared to each others. The thickness of the oxide areas were measured and also examined using XRD, FEG-SEM and EDS. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 ·BaO) glass powder of the total alumina/Graphite base refractory materials, presented the most effective resistance to carbon oxidation. The 121% volume expansion due to the Zircon formation during heating and filling up the open pores by (4B2O3 ·BaO) glaze during green body sintering led to an excellent carbon oxidation resistance. In supplement 3, decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials constituting a commercial Submerged Entry Nozzle (SEN), have been investigated in different gas atmosphere consisting of CO2, O2 and Ar. The (CO2/O2) ratio values were kept the same as it is in propane combustion flue gas at Air Fuel Ratio (AFR) values equal to 1.5 and 1 for both Air-fuel and Oxygen-fuel combustions. Laboratory experiments were carried out non-isothermally in the temperature range 873 K to 1473 K at 15 K/min followed by isothermal heating at 1473 K for 60 min. The decarburization ratio (α) values of the three refractory types were determined by measuring the weight losses of the samples. The results showed that the decarburization ratio (α) values of the MgO-C refractory became 3.1 times higher for oxygen-fuel combustion compared to air-fuel combustion both at AFR equal to 1.5 in the temperature range 873 K to 1473 K. The decarburization ratio (α) values for Al2O3-C samples were the same as for the isothermal heating at 1473 K and non-isothermal heating in the temperature range 473  to 1773 K with a 15 K/min heating rate. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times instead of heating at lower temperatures for longer holding times. Jander’s diffusion model was proposed for estimating the decarburization rate of Al2O3-C refractory in the SEN. The activation energy for Al2O3-C samples heated at AFR equal to 1.5, for air-fuel and oxygen-fuel combustions were found to be 84.5 KJ/mol and 95.5 KJ/mol respectively during non-isothermal heating in the temperature range 873 K to 1473 K. / QC 20101008

Naftos krekinge naudotas katalizatorius yra ceolitinė medžiaga, kurios unikalios savybės mažai išnaudojamos cementinių medžiagų gamybos technologijoje. Ugniai atspariuose betonuose naudojami įvairūs priedai-modifikatoriai yra labai brangūs, todėl naudoto katalizatoriaus panaudojimas, kaip modifikuojančio betono savybes priedo, turi ne tik ekologinį (atliekų utilizavimas) bet ir ekonominį pagrindą. Vykdant šį darbą sukurti vidutinio cemento kiekio ugniai atsparūs šamotbetoniai su 70 % ir 40 % aliuminio oksido turinčiais aliuminatiniais cementais ir naudoto katalizatoriaus priedu atitinkamai 2,5 % ir 5,0 %. Darbe taip pat atskleistas efektyvus katalizatoriaus poveikis aliuminatinio cemento hidratacijai, cemento akmens struktūros susidarymui kietėjimo metu ir jos pokyčiams veikiant aukštoms temperatūroms. / Fluidized bed catalytic cracking catalyst waste is a zeolite material. Its unique properties are underused in cementitious materials production technology. Various additives, modifiers used in refractory castables are very expensive, so the use of catalyst waste as a modifying additive of castable properties has not only an ecological (waste recycling) but also an economical basis. Medium cement refractory castable was developed using 70 % and 40 % of aluminium oxide containing aluminate cement and catalyst waste additive, respectively 2,5 % and 5,0 %. The work also reveals an efficient effect of catalyst waste on alumina cement hydration, structure formation during cement solidification and after treatment at high temperature.

Focal epilepsy in childhood is associated with increased risk for developing behavioral, emotional, cognitive and social–adaptive impairments. The present thesis focused on mental health difficulties in paediatric refractory focal epilepsy. It undertook a detailed evaluation of the predictive power of several demographic (gender, age at assessment), clinical (age at onset and duration of epilepsy, seizure frequency), localization (lobe and lateralization of pathology) and cognitive variables (performance in intellectual, memory and academic attainment measures) for mood, conduct, inattention/hyperactivity and peer relationship difficulties, as assessed by parental report. Data from a population of 282 children and adolescents, previously collected for clinical purposes, were examined, using a series of univariate and multivariate analyses. Mental health difficulties were found to be highly prevalent, with peer relationships the most frequently reported area of difficulty, followed by inattention/hyperactivity and emotional difficulties. Different patterns of associations between the variables examined here and individual emotional/behavioural difficulties were revealed, partially confirming and extending previous findings in the literature. Longer duration of epilepsy was found to increase the risk for developing emotional difficulties; male gender and earlier age at onset the risk for conduct difficulties; male gender, earlier age at onset, longer duration and frontal lobe localization the risk for attention/hyperactivity difficulties; and finally longer duration, higher seizure frequency and right hemisphere lateralization the risk for peer difficulties. Lower cognitive functioning was found associated with overall increased mental health difficulties and a lower VIQ was predictive of all types of difficulties. Developing a firm understanding of the risk factors that contribute to mental health comorbidities in focal paediatric epilepsy can help identify and provide assessment and intervention to children who are at higher risk earlier, thus significantly improving quality of life.