Síntese e caracterização de catalisadores de LaNiO3 não suportados e suportados em Al2O3 e ZrO2 para a reforma a vapor do metano

Ionic oxides with ABO3 structure, where A represents a rare earth element or an alkaline metal and B is a transition metal from group VIII of the periodic table are potential catalysts for oxidation and good candidates for steam reforming reaction. Different methods have been considered for the synthesis of the oxide materials with perovskite structure to produce a high homogeneous material with low amount of impurities and low calcination temperatures. In the current work, oxides with the LaNiO3 formula had been synthesized using the method of the polymeric precursors. The thermal treatment of the materials took place at 300 ºC for 2h. The material supported in alumina and/or zirconia was calcined at 800 ºC temperature for 4h. The samples had been characterized by the following techniques: thermogravimetry; infrared spectroscopy; X-ray diffraction; specific surface area; distribution of particle size; scanning electron microscopy and thermo-programmed reduction. The steam reforming reaction was carried out in a pilot plant using reducing atmosphere in the reactor with a mixture of 10% H2-Argon, a mass about 5g of catalyst, flowing at 50 mL.min-1. The temperature range used was 50 - 1000 oC with a heating rate of 10 oC.min-1. A thermal conductivity detector was used to analyze the gas after the water trapping, in order to permit to quantify the consumption of hydrogen for the lanthanum nickelates (LaNiO3). The results showed that lanthanum nickelate were more efficient when supported in alumina than when supported in zirconia. It was observed that the methane conversion was approximately 100% and the selectivity to hydrogen was about 70%. In all cases were verified low selectivity to CO and CO2

Compósitos de matriz metálica à base níquel com adição de TaC e NbC produzidos via metalurgia do pó

Carbide reinforced metallic alloys potentially improve some important mechanical properties required for the overall use of important engineering materials such as steel and nickel. Nevertheless, improved performance is achieved not only by composition enhancement but also by adequate processing techniques, such as novel sintering methods in the case of powder metallurgy. The method minimizes energy losses in addition to providing uniform heating during sintering. Thus, the general objective of this study was to evaluate the density, hardness, flexural strength, dilatometric behavior and to analyze the microstructure of metal matrix composites based nickel with addition of carbides of tantalum and / or niobium when sintered in a conventional furnace and Plasma assisted debinding and sintering (PADS). Initially, were defineds best parameters of granulation, screening and mixing procedure. After, mixtures of carbonyl Ni and 5%, 10% and 15 wt.% NbC and TaC were prepared in a Y-type mixer under wet conditions during 60 minutes. The mixtures were then dried and granulated using 1.5 wt. % paraffin diluted in hexane. Granulates were cold pressed under 600 MPa. Paraffin was then removed from the pressed pellets during a pre-sintering process carried out in a tubular furnace at 500 °C during 30 min. The heating rate was 3 ºC/min. The pellets were then sintered using either a plasma assisted reactor or a conventional resistive tubular furnace. For both methods, the heating rate was set to 8 ºC/min up to 1150 °C. The holding time was 60 minutes. The microstructure of the sintered samples was evaluated by SEM. Brinell hardness tests were also carried out. The results revealed that higher density and higher hardness values were observed in the plasma-assisted sintered samples. Hardness increased with the concentration of carbides in the Ni-matrix. The flexural strength also increased by adding the carbides. The decline was larger for the sample with addition of 5% 5% TaC and NbC. In general, compositions containing added carbide 10% showed less porous and more uniform distribution of carbides in the nickel matrix microstructural appearance. Thus, both added carbide and plasma sintering improved density, hardness, flexural strength and microstructural appearance of the composites

Avaliação da incorporação combinada dos resíduos de cascalho de perfuração de poço de petróleo e de polimento do porcelanato em cerâmica vermelha

Among the industries, those that produce ceramic porcelain for use in construction industry and oil, during the exploration and production period, play an important role in the production of waste. Much research has been carried out both by academia and the productive sector, sometimes reintroducing them in the same production line that generated them, sometimes in areas unrelated to their generation, as in the production of concrete and mortar for the construction, for example, but each one in an isolated way. In this research, the aim is to study the combined incorporation of the waste drill cuttings of oil well and the residue of the polishing of porcelain, generated in the final stage of finishing of this product in a clay matrix, for the production of red pottery, specifically bricks, ceramic blocks and tiles. The clay comes from the municipality of São Gonçalo, RN, the drilling waste is from the Natal basin, in Rio Grande do Norte, and the residue of the polishing proceeds from a ceramic porcelain of the State of Paraíba. For this purpose, we used a mixture of a plastic clay with a non-plastic, in a ratio of 50% each, settling formulations with the addition of these two residues in this clay matrix. In the formulations, both residues were incorporated with a minimum percentage of 2.5% and maximum of 12.5%, varying from 2.5% each, in each formulation, which the sum of the waste be no more than 15%. It should be noted that the residue of the polishing of ceramic porcelain is a IIa class (not inert). The materials were characterized by XRF, XRD, TG, DTA, laser granulometry and the plasticity index. The technological properties of water absorption, apparent porosity, linear shrinkage of burning, flexural tensile strength and bulk density were evaluated after the sintering of the pieces to 850 °C, 950 °C and 1050 °C, with a burning time of 3 hr, 3 hr and 30 minutes, and 3 hr and 50 minutes, respectively, with a heating rate of 10 °C/minute, for all formulations and landing of 30 minutes. To better understand the influence of each residue and temperature on the evaluated properties, we used the factorial planning and its surfaces of response for the interpretation of the results. It was found that the temperature has no statistical significance at a 95% of reliability level in flexural tensile strength and that it decreases the water absorption and the porosity, but increases the shrinkage and the bulk density. The results showed the feasibility of the desired incorporation, but adjusting the temperature to each product and formulation, and that the temperatures of 850 °C and 950 °C were the one that responded to the largest number of formulations

Efeito da velocidade de aquecimento nas propriedades de produtos da cerâmica estrutural

Heating rate is one of the main variables that determine a fire cycle. In industrial processes that use high temperatures, greater fire great can reduce the cost of production and increase productivity. The use of faster and more efficient fire cycles has been little investigated by the structural ceramic industry in Brazil. However, one of the possibilities that aims at modernizing the sector is the use of roller kilns and the inclusion of natural gas as fuel. Thus, the purpose of this study is to investigate the effect of heating rate on the technological properties of structural ceramic products. Clay raw materials from the main ceramic industries in the state of Rio Grande do Norte were characterized. Some of the raw materials characterized were formulated to obtain the best physical and mechanical properties. Next, raw materials and formulations were selected to study the influence of heating rate on the final properties of the ceramic materials. The samples were shaped by pressing and extrusion and submitted to rates of 1 °C/min, 10 °C/min and 20 °C/min, with final temperatures of 850 °C, 950 °C and 1050 °C. Discontinuous cycles with rates of 10 °C/min or 15 °C/min up to 600 °C and a rate of 20 °C/min up to final temperature were also investigated. Technological properties were determined for all the samples and microstructural analysis was carried out under a number of fire conditions. Results indicate that faster and more efficient fire cycles than those currently in practice could be used, limiting only some clay doughs to certain fire conditions. The best results were obtained for the samples submitted to slow cycles up to 600 °C and fast fire sinterization up to 950 °C. This paper presents for the first time the use of a fast fire rate for raw materials and clay formulations and seeks to determine ideal dough and processing conditions for using shorter fire times, thus enabling the use of roller kilns and natural gas in structural ceramic industries

Aplicação da metodologia de planejamento de experimentos para formulação de massas cerâmicas para telhas

Rio Grande do Norte State stands out as one great producer of structural clay of the brazilian northeastern. The Valley Assu ceramic tiles production stands out obtained from ilitics ball clays that abound in the region under study. Ceramics formulation and the design of experiments with mixture approach, has been applied for researchers, come as an important aid to decrease the number of experiments necessary to the optimization. In this context, the objective of this work is to evaluate the effects of the formulation, temperature and heating rate in the physical-mechanical properties of the red ceramic body used for roofing tile fabrication of the Valley Assu, using design of mixture experiments. Four clays samples used in two ceramics industry of the region were use as raw material and characterized by X-ray diffraction, chemical composition, differential thermal analysis (DTA), thermogravimetric analysis (TGA), particle size distribution analysis and plasticity techniques. Afterwards, they were defined initial molded bodies and made specimens were then prepared by uniaxial pressing at 25 MPa before firing at 850, 950 and 1050 ºC in a laboratory furnace, with heating rate in the proportions of 5, 10 e 15 ºC/min. The following tecnologicals properties were evaluated: linear firing shrinkage, water absorption and flexural strength. Results show that the temperature 1050 ºC and heating rate of 5 ºC/min was the best condition, therefore presented significance in all physical-mechanical properties. The model was accepted as valid based of the production of three new formulations with fractions mass diferents of the initial molded bodies and heated with temperature at 1050 ºC and heating rate of 5 ºC/min. Considering the formulation, temperature and heating rate as variables of the equations, another model was suggested, where from the aplication of design of experiments with mixtures was possible to get a best formulation, whose experimental error is the minor in relation to the too much formulations

Avaliação térmica dos resíduos da destilação atmosférica das blendas - biodiesel/diesel

The worldwide concern regarding the use of sustainable energy and preserving the environment are determining factors in the search for resources and alternative sources of energy and therefore fuel less aggressive nature. In response to these difficulties Biodiesel has emerged as a good solution because it is produced from renewable sources, produces burns cleaner and is easily reproducible. This work was synthesized with biodiesel oil, sunflower via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the blends BX (a proportion of biodiesel X = 5, 10, 15 and 20 %). Atmospheric distillation of the analysis, performed in blends with and without BHT were collected residue generated by each sample and performed a study heat from the thermogravimetric analysis at a heating rate of 10 °C*min-1, nitrogen atmosphere and heating to 600 °C. According to the specifications of Resolution N 7/2008 for biodiesel, it was found that the synthesized material was in accordance with the specifications. For blends showed that the samples are in accordance with the Resolution of ANP N 42/2009. From the TG / DTG curves of the samples of biodiesel, blends and waste can be seen that these show a single loss of thermal decomposition concerning constituents present in each sample. The blends without BHT with ratios of 5%, 10% and 15% biodiesel showed a lower amount of waste (1,07%; 1,09% e 1,10%) to mineral diesel (1,15%). Therefore, it is concluded that the addition of biodiesel with diesel mineral can improve some physico-chemical parameters, but also, depending on the added amount, decreasing the amount of waste generated. This fact is of great importance because the carbonaceous residue can cause problems in mechanical equipment and parts for vehicles, causing more frequent maintenance, and this is not desirable

Estudo térmico dos resíduos gerados da destilação atmosférica das misturas diesel/biodiesel de dendê

The growing world demand for energy supplied by fossil fuels, a major contributor to the emission of pollutants into the atmosphere and causing environmental problems, has been encouraging governments and international organizations to reflect and encourage the use of alternative renewable sources. Among these new possibilities deserves attention biodiesel, fuel cleaner and easy to reproduce. The study of new technologies involving that source is necessary. From this context, the paper aims at analyzing the thermal stability by thermogravimetric analysis, of the waste generated from atmospheric distillation of mixtures with ratios of 5, 10, 15 and 20% palm biodiesel in diesel with and without addition of BHT antioxidant. It was synthesized biodiesel through palm oil, via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the diesel common indoor type (S1800) from a gas station BR. The diesel was already added with 5% biodiesel, and thus the proportions used for these blends were subtracted from the existing ratio in diesel fuel, resulting in the following proportions palm oil biodiesel: 0% (B5), 5% (B10), 10 % (B15) and 15% (B20). From atmospheric distillation analysis, performed in mixtures with and without BHT were collected residue generated by each sample and performed a thermal study from the thermogravimetric analysis at a heating rate of 10 °C.min-1, nitrogen atmosphere and heating to 600 ° C. According to the specifications of Resolution No. 7/2008 for biodiesel, it was found that the material was synthesized in accordance with the specifications. For mixtures, it was noted that the samples were in accordance with the ANP Resolution No. 42/2009. Given the TG / DTG curves of the samples of waste mixtures with and without BHT antioxidant was able to observe that they showed a single stage of thermal decomposition attributed to decomposition of heavy hydrocarbons and esters and other heavier constituents of the waste sample weighed. The thermal behavior of residues from atmospheric distillation of mixtures of diesel / biodiesel is very important to understand how this affects the proper functioning of the engine. A large amount of waste can generate a high content of particulate material, coke formation and carbonaceous deposits in engine valves, compromising their performance

Experimental and modeling studies of forced convection storage and drying systems for sweet potatoes

Sweet potato is an important strategic agricultural crop grown in many countries around the world. The roots and aerial vine components of the crop are used for both human consumption and, to some extent as a cheap source of animal feed. In spite of its economic value and growing contribution to health and nutrition, harvested sweet potato roots and aerial vine components has limited shelf-life and is easily susceptible to post-harvest losses. Although post-harvest losses of both sweet potato roots and aerial vine components is significant, there is no information available that will support the design and development of appropriate storage and preservation systems. In this context, the present study was initiated to improve scientific knowledge about sweet potato post-harvest handling. Additionally, the study also seeks to develop a PV ventilated mud storehouse for storage of sweet potato roots under tropical conditions. In study one, airflow resistance of sweet potato aerial vine components was investigated. The influence of different operating parameters such as airflow rate, moisture content and bulk depth at different levels on airflow resistance was analyzed. All the operating parameters were observed to have significant (P < 0.01) effect on airflow resistance. Prediction models were developed and were found to adequately describe the experimental pressure drop data. In study two, the resistance of airflow through unwashed and clean sweet potato roots was investigated. The effect of sweet potato roots shape factor, surface roughness, orientation to airflow, and presence of soil fraction on airflow resistance was also assessed. The pressure drop through unwashed and clean sweet potato roots was observed to increase with higher airflow, bed depth, root grade composition, and presence of soil fraction. The physical properties of the roots were incorporated into a modified Ergun model and compared with a modified Shedd’s model. The modified Ergun model provided the best fit to the experimental data when compared with the modified Shedd’s model. In study three, the effect of sweet potato root size (medium and large), different air velocity and temperature on the cooling/or heating rate and time of individual sweet potato roots were investigated. Also, a simulation model which is based on the fundamental solution of the transient equations was proposed for estimating the cooling and heating time at the centre of sweet potato roots. The results showed that increasing air velocity during cooling and heating significantly (P < 0.05) affects the cooling and heating times. Furthermore, the cooling and heating times were significantly different (P < 0.05) among medium and large size sweet potato roots. Comparison of the simulation results with experimental data confirmed that the transient simulation model can be used to accurately estimate the cooling and heating times of whole sweet potato roots under forced convection conditions. In study four, the performance of charcoal evaporative cooling pad configurations for integration into sweet potato roots storage systems was investigated. The experiments were carried out at different levels of air velocity, water flow rates, and three pad configurations: single layer pad (SLP), double layers pad (DLP) and triple layers pad (TLP) made out of small and large size charcoal particles. The results showed that higher air velocity has tremendous effect on pressure drop. Increasing the water flow rate above the range tested had no practical benefits in terms of cooling. It was observed that DLP and TLD configurations with larger wet surface area for both types of pads provided high cooling efficiencies. In study five, CFD technique in the ANSYS Fluent software was used to simulate airflow distribution in a low-cost mud storehouse. By theoretically investigating different geometries of air inlet, plenum chamber, and outlet as well as its placement using ANSYS Fluent software, an acceptable geometry with uniform air distribution was selected and constructed. Experimental measurements validated the selected design. In study six, the performance of the developed PV ventilated system was investigated. Field measurements showed satisfactory results of the directly coupled PV ventilated system. Furthermore, the option of integrating a low-cost evaporative cooling system into the mud storage structure was also investigated. The results showed a reduction of ambient temperature inside the mud storehouse while relative humidity was enhanced. The ability of the developed storage system to provide and maintain airflow, temperature and relative humidity which are the key parameters for shelf-life extension of sweet potato roots highlight its ability to reduce post-harvest losses at the farmer level, particularly under tropical climate conditions.

The effect of heat transfer mode on heart rate responses and hysteresis during heating and cooling in the estuarine crocodile Crocodylus porosus

The effect of heating and cooling on heart rate in the estuarine crocodile Crocodylus porosus was studied in response to different heat transfer mechanisms and heat loads. Three heating treatments were investigated. C. porosus were: (1) exposed to a radiant heat source under dry conditions; (2) heated via radiant energy while half-submerged in flowing water at 23degreesC and (3) heated via convective transfer by increasing water temperature from 23degreesC to 35degreesC. Cooling was achieved in all treatments by removing the heat source and with C. porosus half-submerged in flowing water at 23degreesC. In all treatments, the heart rate of C. porosus increased markedly in response to heating and decreased rapidly with the removal of the heat source. Heart rate during heating was significantly faster than during cooling at any given body temperature, i.e. there was a significant heart rate hysteresis. There were two identifiable responses to heating and cooling. During the initial stages of applying or removing the heat source, there was a dramatic increase or decrease in heart rate ('rapid response'), respectively, indicating a possible cardiac reflex. This rapid change in heart rate with only a small change or no change in body temperature (

Exploiting Pulsed Flows for Heating Improvement: Application to Determination of Total Reducing Sugars in Molasses and Sugar-Cane Juices

Laminar and pulsed flows typical of multi-commuted and multi-pumping flow systems, were evaluated in relation to analytical procedures carried out at high temperatures. As application, the spectrophotometric determination of total reducing sugars (TRS, hydrolyzed sucrose plus reducing sugars) in sugar-cane juice and molasses was selected. The method involves in-line hydrolysis of sucrose and alkaline degradation of the reducing sugars at about 98 degrees C. Better results were obtained with pulsed flows, due to the efficient radial mass transport inherent to the multi-pumping flow system. The proposed system presents favorable characteristics of ruggedness, analytical precision (r.s.d. < 0.013 for typical samples), stability (no measurable baseline drift during 4-h working periods), linearity of the analytical curve (r > 0.992, n = 5, 0.05-0.50% w/v TRS) and sampling rate (65 h(-1)). Results are in agreement with ion chromatography.

Screening of lipases for the synthesis of xylitol monoesters by chemoenzymatic esterification and the potential of microwave and ultrasound irradiations to enhance the reaction rate

Lipases from different sources, Pseudomonas fluorescens (AK lipase), Burkholderia cepacia (PS lipase), Penicillium camembertii (lipase G) and Porcine pancreas lipase (PPL), previously immobilized on epoxy SiO(2)-PVA, were screened for the synthesis of xylitol monoesters by esterification of the protected xylitol using oleic acid as acyl donor group. Among all immobilized derivatives, the highest esterification yield was achieved by P. camembertii lipase, showing to be attractive alternative to bulk chemical routes to satisfy increasing commercial demands. Further experiments were performed to determine the influence of fatty acids chain size on the reaction yield and the feasibility of using non-conventional heating systems (microwave and ultrasound irradiations) to enhance the reaction rate. (C) 2010 Elsevier B.V. All rights reserved.

Brood production increases when artificial heating is provided to colonies of stingless bees

Although stingless bees are capable of maintaining their nest temperature within certain limits, brood production of several species declines or even completely stops during periods of low ambient temperature. In the present study, we investigated whether the brood production of the meliponine species Nannotrigona testaceicornis can be artificially increased through heating the colonies during the cold season. For this, we monitored the rate of brood cell production of seven hives in intervals of 24 hours under two different experimental conditions: 1. without; and 2. with heating. Each treatment (first with and subsequently without heating) lasted for nine consecutive days. The ambient temperature (TA) during both experimental periods was very similar (TA(WITH) = 16.1 degrees C; TA(WITHOUT) = 16.3 degrees C). On average, the colonies built 3.6 brood cells per day without and 15.8 brood cells per day with artificial heating (Wilcoxon Rank Sum test: T = 10, Z = 4, P < 0.001). In both treatments, the rate of brood cell production increased with increasing environmental temperature (Spearman Rank Correlation: R(WITH) = 0.71, P = 0.02; R(WITHOUT) = 0.66, P = 0.05). We concluded that artificial heating during cold periods increased the brood cell production in N. testaceicornis Our results indicate that the use of heaters for stingless bee hives during periods of low ambient temperature may be helpful for stingless beekeeping.

Control of heart rate during thermoregulation in the heliothermic lizard Pogona barbata: importance of cholinergic and adrenergic mechanisms

During thermo regulation in the bearded dragon Pogona barbata, heart rate when heating is significantly faster than when cooling at any given body temperature (heart rate hysteresis), resulting in faster rates of heating than cooling. However, the mechanisms that control heart rate during heating and cooling are unknown. The aim of this study was to test the hypothesis that changes in cholinergic and adrenergic tone on the heart are responsible for the heart rate hysteresis during heating and cooling in P. barbata. Heating and cooling trials were conducted before and after the administration of atropine, a muscarinic antagonist, and sotalol, a beta-adrenergic antagonist. Cholinergic and beta-adrenergic blockade did not abolish the heart rate hysteresis, as the heart rate during heating was significantly faster than during cooling in all cases. Adrenergic tone was extremely high (92.3%) at the commencement of heating, and decreased to 30.7% at the end of the cooling period. Moreover, in four lizards there was an instantaneous drop in heart rate (up to 15 beats min(-1)) as the heat source was switched off, and this drop in heart rate coincided with either a drop in beta-adrenergic tone or an increase in cholinergic tone. Rates of heating were significantly faster during the cholinergic blockade, and least with a combined cholinergic and beta-adrenergic blockade. The results showed that cholinergic and beta-adrenergic systems are not the only control mechanisms acting on the heart during heating and cooling, but they do have a significant effect on heart rate and on rates of heating and cooling.

Anomalous crystallization of hydrogenated amorphous silicon during fast heating ramps

Thermal crystallization experiments carried out using calorimetry on several a-Si:H materials with different microstructures are reported. The samples were crystallized during heating ramps at constant heating rates up to 100 K/min. Under these conditions, crystallization takes place above 700 C and progressively deviates from the standard kinetics. In particular, two crystallization processes were detected in conventional a-Si:H, which reveal an enhancement of the crystallization rate. At100 K/min, such enhancement is consistent with a diminution of the crystallization time by a factor of 7. In contrast, no systematic variation of the resulting grain size was observed. Similar behavior was also detected in polymorphous silicon and silicon nanoparticles, thus showing that it is characteristic of a variety of hydrogenated amorphous silicon materials.

Anomalous crystallization of hydrogenated amorphous silicon during fast heating ramps

Thermal crystallization experiments carried out using calorimetry on several a-Si:H materials with different microstructures are reported. The samples were crystallized during heating ramps at constant heating rates up to 100 K/min. Under these conditions, crystallization takes place above 700 C and progressively deviates from the standard kinetics. In particular, two crystallization processes were detected in conventional a-Si:H, which reveal an enhancement of the crystallization rate. At100 K/min, such enhancement is consistent with a diminution of the crystallization time by a factor of 7. In contrast, no systematic variation of the resulting grain size was observed. Similar behavior was also detected in polymorphous silicon and silicon nanoparticles, thus showing that it is characteristic of a variety of hydrogenated amorphous silicon materials