Analysis of a novel waste heat recovery mechanism for an I.C. engine

Typical internal combustion engines lose about 75% of the fuel energy through the engine coolant, exhaust and surface radiation. Most of the heat generated comes from converting the chemical energy in the fuel to mechanical energy and in turn thermal energy is produced. In general, the thermal energy is unutilized and thus wasted. This report describes the analysis of a novel waste heat recovery (WHR) system that operates on a Rankine cycle. This novel WHR system consists of a second piston within the existing piston to reduce losses associated with compression and exhaust strokes in a four-cycle engine. The wasted thermal energy recovered from the coolant and exhaust systems generate a high temperature and high pressure working fluid which is used to power the modified piston assembly. Cycle simulation shows that a large, stationary natural gas spark ignition engine produces enough waste heat to operate the novel WHR system. With the use of this system, the stationary gas compression ignition engine running at 900 RPM and full load had a net increase of 177.03 kW (240.7 HP). This increase in power improved the brake fuel conversion efficiency by 4.53%.

THERMAL CHARACTERIZATION OF A GASOLINE TURBOCHARGED DIRECT INJECTION (GTDI) ENGINE UTILIZING LEAN OPERATION AND EXHAUST GAS RECIRCULATION (EGR)

The push for improved fuel economy and reduced emissions has led to great achievements in engine performance and control. These achievements have increased the efficiency and power density of gasoline engines dramatically in the last two decades. With the added power density, thermal management of the engine has become increasingly important. Therefore it is critical to have accurate temperature and heat transfer models as well as data to validate them. With the recent adoption of the 2025 Corporate Average Fuel Economy(CAFE) standard, there has been a push to improve the thermal efficiency of internal combustion engines even further. Lean and dilute combustion regimes along with waste heat recovery systems are being explored as options for improving efficiency. In order to understand how these technologies will impact engine performance and each other, this research sought to analyze the engine from both a 1st law energy balance perspective, as well as from a 2nd law exergy analysis. This research also provided insights into the effects of various parameters on in-cylinder temperatures and heat transfer as well as provides data for validation of other models. It was found that the engine load was the dominant factor for the energy distribution, with higher loads resulting in lower coolant heat transfer and higher brake work and exhaust energy. From an exergy perspective, the exhaust system provided the best waste heat recovery potential due to its significantly higher temperatures compared to the cooling circuit. EGR and lean combustion both resulted in lower combustion chamber and exhaust temperatures; however, in most cases the increased flow rates resulted in a net increase in the energy in the exhaust. The exhaust exergy, on the other hand, was either increased or decreased depending on the location in the exhaust system and the other operating conditions. The effects of dilution from lean operation and EGR were compared using a dilution ratio, and the results showed that lean operation resulted in a larger increase in efficiency than the same amount of dilution with EGR. Finally, a method for identifying fuel spray impingement from piston surface temperature measurements was found. Note: The material contained in this section is planned for submission as part of a journal article and/or conference paper in the future.

A Numerical Investigation of the Gulf Stream and Its Meanders in Response to Cold Air Outbreaks

The three-dimensional Princeton Ocean Model is used to examine the modification of the Gulf Stream and its meanders by cold air outbreaks. Two types of Gulf Stream meanders are found in the model. Meanders on the shoreward side of the Gulf Stream are baroclinically unstable. They are affected little by the atmospheric forcing because their energy source is stored at the permanent thermocline, well below the influence of the surface forcing. Meanders on the seaward side of the stream are both barotropically and baroclinically unstable. The energy feeding these meanders is stored at the surface front separating the Gulf Stream and the Sargasso Seal which is greatly reduced in case of cold air outbreaks. Thus, meanders there reduce strength and also seem to slow their downstream propagation due to the southward Ekman flow. Heat budget calculations suggest two almost separable processes. The oceanic heal released to the atmosphere during these severe cooling episodes comes almost exclusively from the upper water column. Transport of heat by meanders from the Gulf Stream to the shelf, though it is large, does not disrupt the principal balance. It is balanced nicely with the net heat transport in the downstream direction.

(Table 1) Sea-surface temperatures, intermediate-water temperatures, and latitudinal gradient at three time slices at the end of the Cretaceous

Climatic and oceanographic variations during the last 2 m.y. of the Maastrichtian inferred from high-resolution (10 k.y.) stable isotope analysis of the mid-latitude South Atlantic Deep Sea Drilling Project Site 525 reveal a major warm pulse followed by rapid cooling prior to the Cretaceous-Tertiary boundary. Between 66.85 and 65.52 Ma, cool but fluctuating temperatures average 9.9 and 15.4°C in intermediate and surface waters, respectively. This interval is followed by an abrupt short-term warming between 65.45 and 65.11 Ma, which increased temperatures by 2-3°C in intermediate waters, and decreased the vertical thermal gradient to an average of 2.7°C. This warm pulse may be linked to increased atmospheric pCO2, increased poleward heat transport, and the switch of an intermediate water source from high to low-middle latitudes. During the last 100 k.y. of the Maastrichtian, intermediate and surface temperatures decreased by an average of 2.1 and 1.4°C, respectively, compared to the maximum temperature between 65.32 and 65.24 Ma.

Daily ice production and polynya area in the Laptev Sea region during 1979-2009

Polynyas in the Laptev Sea are examined with respect to recurrence and interannual wintertime ice production.We use a polynya classification method based on passive microwave satellite data to derive daily polynya area from long-term sea-ice concentrations. This provides insight into the spatial and temporal variability of open-water and thin-ice regions on the Laptev Sea Shelf. Using thermal infrared satellite data to derive an empirical thin-ice distribution within the thickness range from 0 to 20 cm, we calculate daily average surface heat loss and the resulting wintertime ice formation within the Laptev Sea polynyas between 1979 and 2008 using reanalysis data supplied by the National Centers for Environmental Prediction, USA, as atmospheric forcing. Results indicate that previous studies significantly overestimate the contribution of polynyas to the ice production in the Laptev Sea. Average wintertime ice production in polynyas amounts to approximately 55 km3 ± 27% and is mostly determined by the polynya area, wind speed and associated large-scale circulation patterns. No trend in ice production could be detected in the period from 1979/80 to 2007/08.

Siliceous microplankton in surface sediments and the water column of the Red Sea

We studied the siliceous microplankton assemblages (mainly diatoms) from plankton tows (mesh size 20 µm) and surface sediment samples collected along a N-S transect in the northern Red Sea (28-21°N). In addition, we analyzed differences/similarities between plankton and sediment assemblages within a brine-filled basin (the southern basin) of the Shaban Deep and compared these assemblages with those from outside the brine. Plankton samples revealed the overwhelming dominance of diatoms over other siliceous groups. Diatoms accounted for ca. 97% of all biosiliceous particles at 120-20 m (vs. 2.9% silicoflagellates and 0.4% radiolarians), and ca. 94% at 200-120 m (vs. 4.5% silicoflagellates and 1.6% radiolarians). In general, a marine, warm-water (tropical/subtropical) diatom assemblage characterizes the plankton samples. Representatives of the Nitzschia bicapitata group are by far the most abundant contributors at both depth intervals (average=43%), ranging from ca. 30% in the North to ca. 60% in the South. Biogenic opal content in non-brine surface sediments is very low, (below 0.2 wt.% SiO2); and concentration of siliceous microorganisms is also low and of the order of 5*10**3-10**4 microorganisms/g dry sediment. Diatoms are the main contributors to the opal signal in the 20-40 µm fraction, while they share dominance with radiolarians in the >40 µm fraction. Total diatom concentrations average 1.2*10**4 valves/g in the 20-40 µm fraction and 4*10**3 valves/g in the >40 µm fraction. Robust taxa of warm water affinity (Alveus marinus, Azpeitia neocrenulata, Azpeitia nodulifera and Roperia tesselata) characterize the surface sediments. In contrast, biogenic opal content in brine surface sediment samples is much higher than in the non-brine samples, ranging from 2.8 to 3.8 wt.% SiO2, and concentration of siliceous microorganisms is 3-4 orders of magnitude higher. In addition here, diatoms dominate the opal signal. The taxa found in these samples are a mixture of non-brine and plankton samples, and fragile forms (e.g., N. bicapitata group, Neodelphineis indica) are well preserved in these sediments. Thus, brine sediments in this region seem to offer a great potential for palaeoenvironmental studies.

Temperature time series and physical properties of snow samples of a high-arctic permafrost site on Svalbard, Norway

Independent measurements of radiation, sensible and latent heat fluxes and the ground heat flux are used to describe the annual cycle of the surface energy budget at a high-arctic permafrost site on Svalbard. During summer, the net short-wave radiation is the dominant energy source, while well developed turbulent processes and the heat flux in the ground lead to a cooling of the surface. About 15% of the net radiation is consumed by the seasonal thawing of the active layer in July and August. The Bowen ratio is found to vary between 0.25 and 2, depending on water content of the uppermost soil layer. During the polar night in winter, the net long-wave radiation is the dominant energy loss channel for the surface, which is mainly compensated by the sensible heat flux and, to a lesser extent, by the ground heat flux, which originates from the refreezing of the active layer. The average annual sensible heat flux of -6.9 W/m**2 is composed of strong positive fluxes in July and August, while negative fluxes dominate during the rest of the year. With 6.8 W/m**2, the latent heat flux more or less compensates the sensible heat flux in the annual average. Strong evaporation occurs during the snow melt period and particularly during the snow-free period in summer and fall. When the ground is covered by snow, latent heat fluxes through sublimation of snow are recorded, but are insignificant for the average surface energy budget. The near-surface atmospheric stratification is found to be predominantly unstable to neutral, when the ground is snow-free, and stable to neutral for snow-covered ground. Due to long-lasting near-surface inversions in winter, an average temperature difference of approximately 3 K exists between the air temperature at 10 m height and the surface temperature of the snow.

Combined effects of short-term ocean acidification and heat shock in a benthic copepod Tigriopus japonicus Mori

Warming of the world's oceans is predicted to have many negative effects on organisms as they have optimal thermal windows. In coastal waters, however, both temperatures and pCO2 (pH) exhibit diel variations, and biological performances are likely to be modulated by physical and chemical environmental changes. To understand how coastal zooplankton respond to the combined impacts of heat shock and increased pCO2, the benthic copepod Tigriopus japonicus were treated at temperatures of 24, 28, 32 and 36 °C to simulate natural coastal temperatures experienced in warming events, when acclimated in the short term to either ambient (LC, 390 µatm) or future CO2 (HC, 1000 µatm). HC and heat shock did not induce any mortality of T. japonicus, though respiration increased up to 32 °C before being depressed at 36 °C. Feeding rate peaked at 28 °C but did not differ between CO2 treatments. Expression of heat shock proteins (hsps mRNA) was positively related to temperature, with no significant differences between the CO2 concentrations. Nauplii production was not affected across all treatments. Our results demonstrate that T. japonicus responds more sensitively to heat shocks rather than to seawater acidification; however, ocean acidification may synergistically act with ocean warming to mediate the energy allocation of copepods.

Optimizing rabbit production under heat stress: cage density and cage size during fattening, and breeding system and water quality on rabbit does

The aim of this work was to evaluate different management strategies to optimize rabbit production under chronic heat stress. To achieve it, three trials were conducted. In the first trial, to find the optimal cage density in tropical very dry forest condition, were measured growth performance, mortality rate, injured animals and carcass performance over an initial population of 300 cross-breed rabbits of New Zealand, California, Butterfly, Dutch and Satin, weaned at 30 days (535 ± 8 g, standard error). Treatments evaluated were: 6, 12, 18 and 24 rabbits/m2 (3, 6, 9 and 12 rabbits/cage, respectively, each cage of 0.5 m2). The maximal temperature-humidity index indicated a severe heat stress from weaning to 2.2 kg body weight (experimental time). At the end of experimental period 10, 20, 30 and 30 rabbits from the treatments of 6, 12, 18 and 24 rabbits/m2, respectively, were slaughtered and carcass performance recorded. Average daily gain and feed intake decreased by 0.31 ± 0.070 and 1.20 ± 0.25 g, respectively, per each unit that the density increased at the beginning of the experiment (P = 0.001). It increased the length of the fattening period by 0.91 ± 0.16 d (P = 0.001) per each unit of increment of density. However, rabbit production (kg/m2) increased linear and quadratically with the density (P < 0.008). Animals housed at the highest density compared to the lower one tended to show a higher incidence of ringworm (68.9 vs 39.4%; P = 0.075), injured animals (16.8 vs 3.03%; P = 0.12) and mortality (20.5 vs 9.63%; P = 0.043). The proportion of scapular fat (P = 0.042) increased linearly with increasing levels of density. Increasing density reduced linearly dorsal length (P = 0.001), and reduced linear and quadratically drip loss percentage (P = 0.097 and 0.018, respectively). In the second trial, 46 nulliparous rabbit does (23 clipped and 23 unclipped) with a BW of 3.67 ± 0.05 kg (s.e.) were used to evaluate heat stress and circadian rhythms comparing unclipped and clipped rabbit does, and to study if a more extensive breeding system increase litters performance at weaning without impairing rabbit doe performance,. Rectal temperature, feed and water 4 intake were recorded for 24 h. Rabbit does were mated 7 d after circadian measurements, and randomly assigned to two breeding systems. Control (C): mated at 14 d after parturition + litter weaned at 35 d of age. Extensive (E): mate at 21 after parturition + litter weaned at 42 d of age. The first three cycles were evaluated concerning to rabbit doe and litter performance. Two hundred twenty eight weaned rabbits, were divided into two cage sizes: 0.5 and 0.25 m2 with same density (16 rabbit/m2) and growing performance was recorded. Farm and rectal temperatures were minimal and feed and water intake maximal during the night (P < 0.001). Unclipped rabbit does showed higher rectal temperature (P = 0.045) and lower feed intake respect to clipped does (P = 0.019) which suggest a lower heat stress in the latter. Kits weaned per litter was reduced by 33% (P=0.038) in C group. This reduction was more important in the 2nd and 3rd cycles compared to the first (P ≤ 0.054). Rabbit doe feed efficiency tended to decrease in E respect C group (P = 0.093), whereas it was impaired from the first to the third cycle by 48% (P = 0.014). Growing rabbits from the E group were heavier at weaning (by 38%. P < 0.001), showed a higher feed intake (+7.4%) and lower feed efficiency (-8.4%) throughout the fattening period (P ≤ 0.056) respect to C group. Cage size had minor influence in growing performance. In the third trial, forty five non pregnant and non lactating rabbit does (21 nulliparous and 24 multiparous) were assigned randomly to farm water and to potable water to study if a water quality improvement can affect positively rabbit doe response to heat stress during pregnancy and lactation. A transponder was implanted in each animal to record subcutaneous temperature at 07:30 and 14:30 h. Experimental period extended from pregnancy (with no lactation) to the next lactation (until day 28). Body temperature and milk production were recorded daily, and body condition, feed and water intake weekly. Water quality did not affect any trait (P ≥ 0.15). Pregnant rabbit does were classified as does that weaned (W: 47%), not weaned (NW: 44%) or those pregnant that did not deliver (NB: 9%). Body temperature and feed intake decreased during pregnancy (P ≤ 0.031), but water intake remained constant. In this period body temperature decreased with metabolic weight (P ≤ 0.009). In W and NW does, 5 from mating to birth energy and protein balance impaired (P≤0.011). Body temperature of W does tended to be the lowest (P ≤ 0.090). Pregnancy length and total number of kits born tended to be longer and higher in NW than in W does (P = 0.10 and 0.053, respectively). Kit mortality at birth and from birth to 14 d of lactation was high, being worse for NW than for W does (97 vs. 40%; P<0.001). Body temperature during lactation was maximal at day 12, and milk production increased it (P ≤ 0.025). . In conclusion, in our heat stress conditions densities higher than 18 rabbits/m2 (34 kg/m2) at the end of fattening, are not recommended despite cage size, gestation and lactation productivity impaired not only when lactation is extended and along successive reproductive cycles but also due to a reduced embryo/kit survival and finally water quality improvement did not attenuate negative effect of heat stress. RESUMEN El propósito de éste trabajo fue evaluar diferentes estrategias de manejo para optimizar la producción de conejos bajo estrés térmico. Para lo cual se desarrollaron tres experimentos. En el primer experimento, para encontrar el número óptimo de gazapos por m2 de jaula durante el cebo en condiciones de bosque muy seco tropical, se estudiaron los rendimientos durante el cebo, mortalidad, animales lesionados y rendimiento de la canal sobre una población inicial de 300 conejos mestizos de Nueva Zelanda, California, Mariposa, Holandés y Satin, destetados a los 30 días de edad (535 ± 8g, error estándar). Los tratamientos evaluados fueron: 6, 12, 18 y 24 conejos/m2 (3, 6, 9 y 12 conejos/jaula, respectivamente, en jaulas de 0.5 m2). Durante el período experimental (destete a 2.2 kg de peso vivo), se observaron valores de THI correspondientes con un estrés térmico severo (THI max. De 31 a 35). Al final del período experimental, 10, 20, 30, y 30 conejos de los tratamientos con densidades de 6, 12, 18 y 24 conejos/m2, respectivamente, fueron sacrificados y su canal fue valorada. El promedio de la ganancia diaria y el consumo de alimento disminuyeron en 0.31 ± 0.070 y 1.20 ± 0.25 g, respectivamente, por cada unidad de incremento en la densidad al inicio del experimento (P=0.001). Esto alargó el período de engorde en 0.91 ± 0.16 d (P=0.001) por cada unidad de incremento de la densidad. Sin embargo, la producción de conejos (kg/m2) aumentó lineal y cuadráticamente con la densidad (P<0.008). Los animales alojados en las mayores densidades en comparación con el resto tendieron a mostrar una mayore incidencia de tiña (68.9 vs 39.4%; P=0.075), de cantidad de animales heridos (16.8 vs 3.03%; P=0.12), así como de mortalidad (20.5 vs 9.63%; P=0.043). El aumento en la densidad aumentó linealmente la proporción de grasa escapular (P=0.042) y redujo linealmente la longitud dorsal (P=0.001), y lineal y cuadráticamente el porcentaje de pérdida por goteo (P=0.018). En el segundo experimento, 46 conejas nulliparas (23 rasuradas y 23 no rasuradas) con un peso vivo de 3.67 ± 0.05 kg (e.e.) fueron usadas para evaluar el estrés 8 térmico y los ritmos circadianos comparando conejas rasuradas o no, y estudiar si un sistema de crianza más extensivo mejora el desempeño de la camada al destete sin perjudicar la productividad de la coneja. Durante 24 h se midió la temperatura rectal, consumo de alimento y de agua. Las conejas fueron montadas 7 días después, y distribuidas en dos sistemas de crianza. El control (C): monta a 14 días posparto y destete a 35 d de edad. El extensivo (E): monta a 21 días posparto y destete a 42 d de edad. Se controló la productividad de la coneja y la camada durante los tres primeros ciclos. Doscientos veintiocho gazapos fueron distribuidos en dos tamaños de jaulas (0.5 y 0.25 m2) con la misma densidad (16 conejos/m2) y se controlaron sus rendimientos productivos. Durante la noche se observaron los valores mínimos para la temperatura ambiental y rectal, y los máximos para consumo de alimento y agua (P< 0.001). Las conejas no rasuradas mostraron mayor temperatura rectal (P=0.045) y menores valores de consumo de alimento con respecto a las conejas rasuradas (P=0.019), lo que sugiere un menor estrés térmico en las últimas. El número de gazapos destetados por camada se redujo en 33% (P=0.038) en el grupo C. Este comportamiento se acentuó en el 2do y 3er ciclo en comparación con el primero (P≤0.054). La eficiencia alimenticia de las conejas tendió a disminuir en el grupo E con respecto al grupo C (P=0.093), dicha tendencia se acentúa del primer al tercer ciclo en un 48% (P=0.014). Los gazapos en fase de crecimiento provenientes del grupo E fueron más pesados al momento del destete (en 38% P<0.001), mostrando un mayor consumo de alimento (+7.4%) y menor eficiencia alimenticia (-8.4%) a lo largo del engorde (P≤0.056) con respecto al grupo C. El tamaño de la jaula tuvo una mínima influencia en el comportamiento durante el crecimiento de éstos gazapos. En el tercer experimento, cuarenta y cinco conejas no gestantes ni lactantes (21 nulíparas y 24 multíparas) se les asignó al azar agua dos tipos de agua: común de la granja y agua potable, con el fin de estudiar si una mejora en la calidad del agua puede afectar positivamente la respuesta de la coneja al estrés térmico durante la gestación y la lactancia. Se les implantó un transponder para registrar la temperatura subcutánea a las 7:30 y a las 14:30 h. El período experimental se extendió desde la gestación (sin 9 lactancia) hasta la lactanción consecutiva (hasta los 28 días). La temperatura corporal y la producción de leche se controlaron diariamente, y la condición corporal, consumo de agua y alimento, semanalmente. La calidad del agua no afectó a ninguna variable (P≥0.15). Las conejas preñadas fueron clasificadas como conejas que destetaron (W: 47%), que no destetaron (NW:44%) o aquellas que no parieron (NB: 9%). La temperatura corporal y consumo de alimento disminuyeron durante la gestación (P≤0.031), mientras que el consumo de agua se mantuvo constante. La temperatura corporal descendió con el peso metabólico durante la gestación (P≤0.009). El balance de energía y proteína disminuyó desde la monta al parto para las conejas W y NW (P≤0.011). Durante la gestación la temperatura corporal tendió a ser menor en las conejas W (P≤0.090). La longitud de la gestación y el número total de gazapos nacidos tendieron a ser mayores en conejas NW que en conejas W (P=0.10 y 0.053, respectivamente). La mortalidad de los gazapos al parto y del parto a los 14 días de lactancia fue alta, siendo peor para las conejas NW que para las W (97 vs 40%; P<0.001). Durante la lactancia la temperatura corporal alcanzó su valor máximo para el día 12, y la producción de leche indujo un incremento en la misma (P≤0.025). En conclusión, en nuestras condiciones de estrés térmico y sin importar el tamaño de la jaula, no se recomiendan densidades mayores a 18 conejos/m2 (34 kg/m2) al final del engorde. La productividad de la gestación y la lactancia disminuyen cuando la lactancia es mayor y se suceden varios ciclos reproductivos seguidos. Esto se debe al efecto negativo del estrés térmico sobre la vitalidad y supervivencia del embrión/gazapo. La mejora de la calidad del agua atenuó el efecto negativo del estrés térmico. Las conejas más productoras parece que son aquéllas que consiguen manejar mejor el estrés térmico.

Surface velocity and mass balance of Livingston Island ice cap, Antarctica

The mass budget of the ice caps surrounding the Antarctica Peninsula and, in particular, the partitioning of its main components are poorly known. Here we approximate frontal ablation (i.e. the sum of mass losses by calving and submarine melt) and surface mass balance of the ice cap of Livingston Island, the second largest island in the South Shetland Islands archipelago, and analyse variations in surface velocity for the period 2007–2011. Velocities are obtained from feature tracking using 25 PALSAR-1 images, and used in conjunction with estimates of glacier ice thicknesses inferred from principles of glacier dynamics and ground-penetrating radar observations to estimate frontal ablation rates by a flux-gate approach. Glacier-wide surface mass-balance rates are approximated from in situ observations on two glaciers of the ice cap. Within the limitations of the large uncertainties mostly due to unknown ice thicknesses at the flux gates, we find that frontal ablation (−509 ± 263 Mt yr−1, equivalent to −0.73 ± 0.38 m w.e. yr−1 over the ice cap area of 697 km2) and surface ablation (−0.73 ± 0.10 m w.e. yr−1) contribute similar shares to total ablation (−1.46 ± 0.39 m w.e. yr−1). Total mass change (δM = −0.67 ± 0.40 m w.e. yr−1) is negative despite a slightly positive surface mass balance (0.06 ± 0.14 m w.e. yr−1). We find large interannual and, for some basins, pronounced seasonal variations in surface velocities at the flux gates, with higher velocities in summer than in winter. Associated variations in frontal ablation (of ~237 Mt yr−1; −0.34 m w.e. yr−1) highlight the importance of taking into account the seasonality in ice velocities when computing frontal ablation with a flux-gate approach.

A global budget for fine root biomass, surface area, and nutrient contents

Global biogeochemical models have improved dramatically in the last decade in their representation of the biosphere. Although leaf area data are an important input to such models and are readily available globally, global root distributions for modeling water and nutrient uptake and carbon cycling have not been available. This analysis provides global distributions for fine root biomass, length, and surface area with depth in the soil, and global estimates of nutrient pools in fine roots. Calculated root surface area is almost always greater than leaf area, more than an order of magnitude so in grasslands. The average C:N:P ratio in living fine roots is 450:11:1, and global fine root carbon is more than 5% of all carbon contained in the atmosphere. Assuming conservatively that fine roots turn over once per year, they represent 33% of global annual net primary productivity.

Electrochemical performance of carbon gels with variable surface chemistry and physics

This study describes the electrochemical characterization of N-doped carbon xerogels in the form of microspheres and of carbon aerogels with varied porosities and surface oxygen complexes. The interfacial capacitance of N-doped carbon xerogels decreased with increased micropore surface area as determined by N2 adsorption at −196 °C. The interfacial capacitance showed a good correlation with the areal NXPS concentration, and the best correlation with the areal concentration of pyrrolic or pyridonic nitrogen functionalities. The gravimetric capacitance decreased with greater xerogel microsphere diameter. The interfacial capacitance of carbon aerogels increased with higher percentage of porosity as determined from particle and true densities. The interfacial capacitance showed a linear relationship with the areal oxygen concentration and with the areal concentrations of CO- and CO2-evolving groups.

Functionalization of carbon nanotubes using aminobenzene acids and electrochemical methods. Electroactivity for the oxygen reduction reaction

Functionalized carbon nanotubes (CNTs) using three aminobenzene acids with different functional groups (carboxylic, sulphonic, phosphonic) in para position have been synthesized through potentiodynamic treatment in acid media under oxidative conditions. A noticeable increase in the capacitance for the functionalized carbon nanotubes mainly due to redox processes points out the formation of an electroactive polymer thin film on the CNTs surface along with covalently bonded functionalities. The CNTs functionalized using aminobenzoic acid rendered the highest capacitance values and surface nitrogen content, while the presence of sulfur and/or phosphorus groups in the aminobenzene structure yielded a lower functionalization degree. The oxygen reduction reaction (ORR) activity of the functionalized samples was similar to that of the parent CNTs, independently of the functional group present in the aminobenzene acid. Interestingly, a heat treatment in N2 atmosphere with a very low O2 concentration (3125 ppm) at 800 °C of the CNTs functionalized with aminobenzoic acid produced a material with high amounts of surface oxygen and nitrogen groups (12 and 4% at., respectively), that seem to modulate the electron-donor properties of the resulting material. The onset potential and limiting current for ORR was enhanced for this material. These are promising results that validates the use of electrochemistry for the synthesis of novel N-doped electrocatalysts for ORR in combination with adequate heat treatments.

Thermodynamic, surface and structural properties of liquid Co-Si alloys

The knowledge of thermophysical properties of liquid Co-Si alloys is a key requirement for manufacturing of composite materials by infiltration method. Despite this need, the experimental and predicted property data of the Co-Si system are scarce and often inconsistent between the various sources. In the present work the mixing behaviour of Co-Si melts has been analysed through the study of the concentration dependence of various thermodynamic, surface (surface tension and surface composition) and structural properties (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) in the framework of the Compound Formation Model (CFM) and Quasi Chemical Approximation for regular solutions (QCA). In addition, the surface tension of the Co22·5Si77.5 (in at%) eutectic alloy, that is proposed to be used as the infiltrant, has been measured by the pendant drop method at temperatures ranging from 1593 to 1773 K. The results obtained were discussed with respect to both, temperature and concentration, and subsequently compared with the model predictions and literature data.

Recommendations and guidelines for the performance of accurate heat transfer measurements in rapid forming processes

The published requirements for accurate measurement of heat transfer at the interface between two bodies have been reviewed. A strategy for reliable measurement has been established, based on the depth of the temperature sensors in the medium, on the inverse method parameters and on the time response of the sensors. Sources of both deterministic and stochastic errors have been investigated and a method to evaluate them has been proposed, with the help of a normalisation technique. The key normalisation variables are the duration of the heat input and the maximum heat flux density. An example of application of this technique in the field of high pressure die casting is demonstrated. The normalisation study, coupled with previous determination of the heat input duration, makes it possible to determine the optimum location for the sensors, along with an acceptable sampling rate and the thermocouples critical response-time (as well as eventual filter characteristics). Results from the gauge are used to assess the suitability of the initial design choices. In particular the unavoidable response time of the thermocouples is estimated by comparison with the normalised simulation. (c) 2006 Elsevier Ltd. All rights reserved.