Study of Fast Etching of Silicon for the Fabrication of Bulk Micromachined MEMS Structures

The present research reports the investigation of fast etching of silicon for the fabrication of microelectromechanical systems (MEMS) structures using silicon wet bulk micromachining. Low concentration tetramethyl-ammonium hydroxide (TMAH) and hydroxylamine (NH2OH) are used as main etchant and additive, respectively. The concentration of NH2OH is varied to optimize the composition to achieve best etching characteristics such as high etch rate, significantly high undercutting at convex corner for the fast release of the microstructures from the substrate, and improved etched surface morphology. These etching characteristics are studied on Si{100} and Si{110} wafers as they are most widely used in the fabrication of MEMS structures as wells diode, transistors and integrated circuits.

A Study of the Replacement of Natural Coarse Aggregate by Spherically-Shaped and Crushed Waste Cathode Ray Tube Glass in Concrete

The aim of this study is to conduct an experimental investigation on the influence of complete replacement of natural coarse aggregate with spherically-shape and crushed waste cathode ray tube (CRT) glass to the aspect of workability, density, and compressive strength of the concrete. After characterizing the glass, a group of concrete mixes was prepared to contain a 40% spherical CRT glass and 60% crushed CRT glass as a complete (100%) replacement of natural coarse aggregates. From a total of 16 types of concrete mixes, the optimum proportion was selected based on its best performance. The test results showed that the use of spherical and crushed glass that possesses a smooth surface, rounded, irregular and elongated shape, and low water absorption affects the workability of concrete. Due to a higher specific gravity of crushed glass, concrete mixes containing CRT glass had a higher density compared to ordinary concrete. Despite the spherical and crushed CRT glass being stronger than gravel, the results revealed a reduction in compressive strength of the concrete. However, using a lower water to binder (w/b) ratio and a higher superplasticizer (SP) dosage, it is found to enhance the compressive strength of 60.97 MPa at 28 days that is lower by 13% than the control specimen. These findings indicate that waste CRT glass in the form of spherical and crushed could be used as an alternative of coarse aggregate that may pave the way for the disposal of hazardous e-waste.

Analysis of Impact Load Induced by Ultrasonic Cavitation Bubble Collapse Using Thin Film Pressure Sensors

The understanding of generation and collapse of acoustic cavitation bubbles are prerequisites for application of cavitation erosion. Microbubbles generated due to rapid fluctuation of pressure induced by propagation of ultrasonic wave lead to formation of high velocity microjets and or shock waves upon collapse. Due to vast application of ultrasonic, it is important to characterize and understand cavitation collapse pressure under the radiating surface at different conditions. A comparative investigation is carried out to determine impact load and dynamic pressure distribution exerted upon bubble collapse using thin film pressure sensors. Measurements were recorded at different input conditions such as amplitude, stand-off distance, insertion depth of the horn inside the liquid and pulse on-off time of acoustic vibrations. Impact force of 2.97 N is recorded at amplitude of 108 μm and stand-off distance of 1 mm from the sensor film, whereas impulsive force as low as 0.4 N is recorded at amplitude of 12 μm and stand-off distance of 5 mm from the sensor film. The results drawn from the investigation indicated that variety of impact loads can be achieved by controlling generation and collapse of bubbles, making it suitable to use for numerous application.

Nanofluid-Based Emulsion Liquid Membrane for Selective Extraction and Separation of Dysprosium

Dysprosium is a rare earth element which is essential for many growing high-technology applications. Dysprosium along with neodymium plays a significant role in different applications such as metal halide lamps, permanent magnets, and nuclear reactor control rods preparation. The purification and separation of rare earth elements are challenging because of their similar chemical and physical properties. Among the various methods, membrane processes provide many advantages over the conventional separation processes such as ion exchange and solvent extraction. In this work, selective extraction and separation of dysprosium from aqueous solutions containing an equimolar mixture of dysprosium and neodymium by emulsion liquid membrane (ELM) was investigated. The organic membrane phase of the ELM was a nanofluid consisting of multiwalled carbon nanotubes (MWCNT), Span80 as surfactant, Cyanex 272 as carrier, kerosene as base fluid, and nitric acid solution as internal aqueous phase. Factors affecting separation of dysprosium such as carrier concentration, MWCNT concentration, feed phase pH and stripping phase concentration were analyzed using Taguchi method. Optimal experimental condition was obtained using analysis of variance (ANOVA) after 10 min extraction. Based on the results, using MWCNT nanofluid in ELM process leads to increase the extraction due to higher stability of membrane and mass transfer enhancement and separation factor of 6 for dysprosium over neodymium can be achieved under the optimum conditions. Additionally, demulsification process was successfully performed and the membrane phase reused effectively in the optimum condition.

The Dependence of the Liquid Application on the Coverage of the Sprayed Objects in Terms of the Characteristics of the Sprayed Object during Spraying

When assessing the quality of the spraying procedure, three indicators are used: uneven distribution of precipitation of liquid sprayed, degree of coverage of sprayed surfaces, and deposition of liquid spraying However, there is a lack of information on the relationship between the quality parameters of the procedure. Therefore, the research was carried out at the Institute of Agricultural Engineering of Wrocław University of Environmental and Life Sciences. The aim of the study was to determine the relationship between the degree of coverage of sprayed surfaces and the deposition of liquid in the aspect of the parametric characteristics of the protected plant using selected single and double stream nozzles. Experiments were conducted under laboratory conditions. The carrier of nozzles acted as an independent self-propelled sprayer used for spraying, whereas the parametric characteristics of plants were determined using artificial plants as the ratio of the vertical projection surface and the horizontal projection surface. The results and their analysis showed a strong and very strong correlation between the analyzed parameters in terms of the characteristics of the sprayed object.

Photocatalytic Active Surface of LWSCC Architectural Concretes

Current trends in the building industry are oriented towards the reduction of maintenance costs and the ecological benefits of buildings or building materials. Surface treatment of building materials with photocatalytic active titanium dioxide added into concrete can offer a good solution in this context. Architectural concrete has one disadvantage – dust and fouling keep settling on its surface, diminishing its aesthetic value and increasing maintenance e costs. Concrete surface – silicate material with open porosity – fulfils the conditions of effective photocatalysis, in particular, the self-cleaning properties of surfaces. This modern material is advantageous in particular for direct finishing and architectural concrete applications. If photoactive titanium dioxide is part of the top layers of road concrete on busy roads and the facades of the buildings surrounding these roads, exhaust fumes can be degraded with the aid of sunshine; hence, environmental load will decrease. It is clear that options for removing pollutants like nitrogen oxides (NOx) must be found. Not only do these gases present a health risk, they also cause the degradation of the surfaces of concrete structures. The photocatalytic properties of titanium dioxide can in the long term contribute to the enhanced appearance of surface layers and eliminate harmful pollutants dispersed in the air, and facilitate the conversion of pollutants into less toxic forms (e.g., NOx to HNO3). This paper describes verification of the photocatalytic properties of titanium dioxide and presents the results of mechanical and physical tests on samples of architectural lightweight self-compacting concretes (LWSCC). The very essence of the use of LWSCC is their rheological ability to seep into otherwise extremely hard accessible or inaccessible construction areas, or sections thereof where concrete compacting will be a problem, or where vibration is completely excluded. They are also able to create a solid monolithic element with a large variety of shapes; the concrete will at the same meet the requirements of both chemical aggression and the influences of the surrounding environment. Due to their viscosity, LWSCCs are able to imprint the formwork elements into their structure and thus create high quality lightweight architectural concretes.

A Comparative Study of Indoor Radon Concentrations between Dwellings and Workplaces in the Ko Samui District, Surat Thani Province, Southern Thailand

The Ko Samui district of Surat Thani province is located in the high amounts of equivalent uranium in the ground surface that is the source of radon. Our research in the Ko Samui district aimed at comparing the indoor radon concentrations between dwellings and workplaces. Measurements of indoor radon concentrations were carried out in 46 dwellings and 127 workplaces, using CR-39 alpha-track detectors in closed-cup. A total of 173 detectors were distributed in 7 sub-districts. The detectors were placed in bedrooms of dwellings and workrooms of workplaces. All detectors were exposed to airborne radon for 90 days. After exposure, the alpha tracks were made visible by chemical etching before they were manually counted under an optical microscope. The track densities were assumed to be correlated with the radon concentration levels. We found that the radon concentrations could be well described by a log-normal distribution. Most concentrations (37%) were found in the range between 16 and 30 Bq.m-3. The radon concentrations in dwellings and workplaces varied from a minimum of 11 Bq.m-3 to a maximum of 305 Bq.m-3. The minimum (11 Bq.m-3) and maximum (305 Bq.m-3) values of indoor radon concentrations were found in a workplace and a dwelling, respectively. Only for four samples (3%), the indoor radon concentrations were found to be higher than the reference level recommended by the WHO (100 Bq.m-3). The overall geometric mean in the surveyed area was 32.6±1.65 Bq.m-3, which was lower than the worldwide average (39 Bq.m-3). The statistic comparison of the geometric mean indoor radon concentrations between dwellings and workplaces showed that the geometric mean in dwellings (46.0±1.55 Bq.m-3) was significantly higher than in workplaces (28.8±1.58 Bq.m-3) at the 0.05 level. Moreover, our study found that the majority of the bedrooms in dwellings had a closed atmosphere, resulting in poorer ventilation than in most of the workplaces that had access to air flow through open doors and windows at daytime. We consider this to be the main reason for the higher geometric mean indoor radon concentration in dwellings compared to workplaces.

Surface Elevation Dynamics Assessment Using Digital Elevation Models, Light Detection and Ranging, GPS and Geospatial Information Science Analysis: Ecosystem Modelling Approach

Surface elevation dynamics have always responded to disturbance regimes. Creating Digital Elevation Models (DEMs) to detect surface dynamics has led to the development of several methods, devices and data clouds. DEMs can provide accurate and quick results with cost efficiency, in comparison to the inherited geomatics survey techniques. Nowadays, remote sensing datasets have become a primary source to create DEMs, including LiDAR point clouds with GIS analytic tools. However, these data need to be tested for error detection and correction. This paper evaluates various DEMs from different data sources over time for Apple Orchard Island, a coastal site in southeastern Australia, in order to detect surface dynamics. Subsequently, 30 chosen locations were examined in the field to test the error of the DEMs surface detection using high resolution global positioning systems (GPSs). Results show significant surface elevation changes on Apple Orchard Island. Accretion occurred on most of the island while surface elevation loss due to erosion is limited to the northern and southern parts. Concurrently, the projected differential correction and validation method aimed to identify errors in the dataset. The resultant DEMs demonstrated a small error ratio (≤ 3%) from the gathered datasets when compared with the fieldwork survey using RTK-GPS. As modern modelling approaches need to become more effective and accurate, applying several tools to create different DEMs on a multi-temporal scale would allow easy predictions in time-cost-frames with more comprehensive coverage and greater accuracy. With a DEM technique for the eco-geomorphic context, such insights about the ecosystem dynamic detection, at such a coastal intertidal system, would be valuable to assess the accuracy of the predicted eco-geomorphic risk for the conservation management sustainability. Demonstrating this framework to evaluate the historical and current anthropogenic and environmental stressors on coastal surface elevation dynamism could be profitably applied worldwide.

Historical and Future Rainfall Variations in Bangladesh

Climate change has become a major concern across the world as the intensity along with quantity of the rainfall, mean surface temperature and other climatic parameters have been changed not only in Bangladesh but also in the entire globe. Bangladesh has already experienced many natural hazards. Among them changing of rainfall pattern, erratic and heavy rainfalls are very common. But changes of rainfall pattern and its amount is still in question to some extent. This study aimed to unfold how the historical rainfalls varied over time and how would be their future trends. In this context, historical rainfall data (1975-2014) were collected from Bangladesh Metrological Department (BMD) and then a time series model was developed using Box-Jenkins algorithm in IBM SPSS to forecast the future rainfall. From the historical data analysis, this study revealed that the amount of rainfall decreased over the time and shifted to the post monsoons. Forecasted rainfall shows that the pre-monsoon and early monsoon will get drier in future whereas late monsoon and post monsoon will show huge fluctuations in rainfall magnitudes with temporal variations which means Bangladesh will get comparatively drier seasons in future which may be a serious problem for the country as it depends on agriculture.

Nanomaterial Based Electrochemical Sensors for Endocrine Disrupting Compounds

Main sources of endocrine disrupting compounds in the ecosystem are hormones, pesticides, phthalates, flame retardants, dioxins, personal-care products, coplanar polychlorinated biphenyls (PCBs), bisphenol A, and parabens. These endocrine disrupting compounds are responsible for learning disabilities, brain development problems, deformations of the body, cancer, reproductive abnormalities in females and decreased sperm count in human males. Although discharge of these chemical compounds into the environment cannot be stopped, yet their amount can be retarded through proper evaluation and detection techniques. The available techniques for determination of these endocrine disrupting compounds mainly include high performance liquid chromatography (HPLC), mass spectroscopy (MS) and gas chromatography-mass spectrometry (GC–MS). These techniques are accurate and reliable but have certain limitations like need of skilled personnel, time consuming, interference and requirement of pretreatment steps. Moreover, these techniques are laboratory bound and sample is required in large amount for analysis. In view of above facts, new methods for detection of endocrine disrupting compounds should be devised that promise high specificity, ultra sensitivity, cost effective, efficient and easy-to-operate procedure. Nowadays, electrochemical sensors/biosensors modified with nanomaterials are gaining high attention among researchers. Bioelement present in this system makes the developed sensors selective towards analyte of interest. Nanomaterials provide large surface area, high electron communication feature, enhanced catalytic activity and possibilities of chemical modifications. In most of the cases, nanomaterials also serve as an electron mediator or electrocatalyst for some analytes.

Failure Analysis and Fatigue Life Estimation of a Shaft of a Rotary Draw Bending Machine

Human consumption of the Earth's resources increases the need for a sustainable development as an important ecological, social, and economic theme. Re-engineering of machine tools, in terms of design and failure analysis, is defined as steps performed on an obsolete machine to return it to a new machine with the warranty that matches the customer requirement. To understand the future fatigue behavior of the used machine components, it is important to investigate the possible causes of machine parts failure through design, surface, and material inspections. In this study, the failure modes of the shaft of the rotary draw bending machine are inspected. Furthermore, stress and deflection analysis of the shaft subjected to combined torsion and bending loads are carried out by an analytical method and compared with a finite element analysis method. The theoretical fatigue strength, correction factors, and fatigue life sustained by the shaft before damaged are estimated by creating a stress-cycle (S-N) diagram. In conclusion, it is seen that the shaft can work in the second life, but it needs some surface treatments to increase the reliability and fatigue life.

Wet Sliding Wear and Frictional Behavior of Commercially Available Perspex

The tribological behavior of commercially used Perspex was evaluated under dry and wet sliding condition using a pin-on-disc wear tester with different applied loads ranging from 2.5 to 20 N. Experiments were conducted with varying sliding distance from 0.2 km to 4.6 km, wherein the sliding velocity was kept constant, 0.64 ms-1. The results reveal that the weight loss increases with applied load and the sliding distance. The nature of the wear rate was very similar in both the sliding environments in which initially the wear rate increased very rapidly with increasing sliding distance and then progressed to a slower rate. Moreover, the wear rate in wet sliding environment was significantly lower than that under dry sliding condition. The worn surfaces were characterized by optical microscope and SEM. It is found that surface modification has significant effect on sliding wear performance of Perspex.

Corrosion Behaviour of Hypereutectic Al-Si Automotive Alloy in Different pH Environment

Corrosion behaviour of hypereutectic Al-19Si automotive alloy in different pH=1, 3, 5, 7, 9, 11, and 13 environments was carried out using conventional gravimetric measurements and was complemented by resistivity, optical micrograph, scanning electron microscopy (SEM) and X-ray analyzer (EDX) investigations. Gravimetric analysis confirmed that the highest corrosion rate is shown at pH 13 followed by pH 1. Minimum corrosion occurs in the pH range of 3.0 to 11 due to establishment of passive layer on the surface. The highest corrosion rate at pH 13 is due to the presence of sodium hydroxide in the solution which dissolves the surface oxide film at a steady rate. At pH 1, it can be attributed that the presence of aggressive chloride ions serves to pick up the damage of the passive films at localized regions. With varying exposure periods by both, the environment complies with the normal corrosion rate profile that is an initial steep rise followed by a nearly constant value of corrosion rate. Resistivity increases in case of pH 1 solution for the higher pit formation and decreases at pH 13 due to formation of thin film. The SEM image of corroded samples immersed in pH 1 solution clearly shows pores on the surface and in pH 13 solution, and the corrosion layer seems more compact and homogenous and not porous.

Parking Space Detection and Trajectory Tracking Control for Vehicle Auto-Parking

On-board available parking space detecting system, parking trajectory planning and tracking control mechanism are the key components of vehicle backward auto-parking system. Firstly, pair of ultrasonic sensors is installed on each side of vehicle body surface to detect the relative distance between ego-car and surrounding obstacle. The dimension of a found empty space can be calculated based on vehicle speed and the time history of ultrasonic sensor detecting information. This result can be used for constructing the 2D vehicle environmental map and available parking type judgment. Finally, the auto-parking controller executes the on-line optimal parking trajectory planning based on this 2D environmental map, and monitors the real-time vehicle parking trajectory tracking control. This low cost auto-parking system was tested on a model car.

Permeable Asphalt Pavement as a Measure of Urban Green Infrastructure in the Extreme Events Mitigation

Population growth in cities has led to an increase in the infrastructures construction, including buildings and roadways. This aspect leads directly to the soils waterproofing. In turn, changes in precipitation patterns are developing into higher and more frequent intensities. Thus, these two conjugated aspects decrease the rainwater infiltration into soils and increase the volume of surface runoff. The practice of green and sustainable urban solutions has encouraged research in these areas. The porous asphalt pavement, as a green infrastructure, is part of practical solutions set to address urban challenges related to land use and adaptation to climate change. In this field, permeable pavements with porous asphalt mixtures (PA) have several advantages in terms of reducing the runoff generated by the floods. The porous structure of these pavements, compared to a conventional asphalt pavement, allows the rainwater infiltration in the subsoil, and consequently, the water quality improvement. This green infrastructure solution can be applied in cities, particularly in streets or parking lots to mitigate the floods effects. Over the years, the pores of these pavements can be filled by sediment, reducing their function in the rainwater infiltration. Thus, double layer porous asphalt (DLPA) was developed to mitigate the clogging effect and facilitate the water infiltration into the lower layers. This study intends to deepen the knowledge of the performance of DLPA when subjected to clogging. The experimental methodology consisted on four evaluation phases of the DLPA infiltration capacity submitted to three precipitation events (100, 200 and 300 mm/h) in each phase. The evaluation first phase determined the behavior after DLPA construction. In phases two and three, two 500 g/m2 clogging cycles were performed, totaling a 1000 g/m2 final simulation. Sand with gradation accented in fine particles was used as clogging material. In the last phase, the DLPA was subjected to simple sweeping and vacuuming maintenance. A precipitation simulator, type sprinkler, capable of simulating the real precipitation was developed for this purpose. The main conclusions show that the DLPA has the capacity to drain the water, even after two clogging cycles. The infiltration results of flows lead to an efficient performance of the DPLA in the surface runoff attenuation, since this was not observed in any of the evaluation phases, even at intensities of 200 and 300 mm/h, simulating intense precipitation events. The infiltration capacity under clogging conditions decreased about 7% on average in the three intensities relative to the initial performance that is after construction. However, this was restored when subjected to simple maintenance, recovering the DLPA hydraulic functionality. In summary, the study proved the efficacy of using a DLPA when it retains thicker surface sediments and limits the fine sediments entry to the remaining layers. At the same time, it is guaranteed the rainwater infiltration and the surface runoff reduction and is therefore a viable solution to put into practice in permeable pavements.

Depth-Averaged Modelling of Erosion and Sediment Transport in Free-Surface Flows

A fast finite volume solver for multi-layered shallow water flows with mass exchange and an erodible bed is developed. This enables the user to solve a number of complex sediment-based problems including (but not limited to), dam-break over an erodible bed, recirculation currents and bed evolution as well as levy and dyke failure. This research develops methodologies crucial to the under-standing of multi-sediment fluvial mechanics and waterway design. In this model mass exchange between the layers is allowed and, in contrast to previous models, sediment and fluid are able to transfer between layers. In the current study we use a two-step finite volume method to avoid the solution of the Riemann problem. Entrainment and deposition rates are calculated for the first time in a model of this nature. In the first step the governing equations are rewritten in a non-conservative form and the intermediate solutions are calculated using the method of characteristics. In the second stage, the numerical fluxes are reconstructed in conservative form and are used to calculate a solution that satisfies the conservation property. This method is found to be considerably faster than other comparative finite volume methods, it also exhibits good shock capturing. For most entrainment and deposition equations a bed level concentration factor is used. This leads to inaccuracies in both near bed level concentration and total scour. To account for diffusion, as no vertical velocities are calculated, a capacity limited diffusion coefficient is used. The additional advantage of this multilayer approach is that there is a variation (from single layer models) in bottom layer fluid velocity: this dramatically reduces erosion, which is often overestimated in simulations of this nature using single layer flows. The model is used to simulate a standard dam break. In the dam break simulation, as expected, the number of fluid layers utilised creates variation in the resultant bed profile, with more layers offering a higher deviation in fluid velocity . These results showed a marked variation in erosion profiles from standard models. The overall the model provides new insight into the problems presented at minimal computational cost.

Homogenization of Cocoa Beans Fermentation to Upgrade Quality Using an Original Improved Fermenter

Cocoa beans (Theobroma cocoa L.) are the main components for chocolate manufacturing. The beans must be correctly fermented at first. Traditional process to perform the first fermentation (lactic fermentation) often consists in confining cacao beans using banana leaves or a fermentation basket, both of them leading to a poor product thermal insulation and to an inability to mix the product. Box fermenter reduces this loss by using a wood with large thickness (e>3cm), but mixing to homogenize the product is still hard to perform. Automatic fermenters are not rentable for most of producers. Heat (T>45°C) and acidity produced during the fermentation by microbiology activity of yeasts and bacteria are enabling the emergence of potential flavor and taste of future chocolate. In this study, a cylindro-rotative fermenter (FCR-V1) has been built and coconut fibers were used in its structure to confine heat. An axis of rotation (360°) has been integrated to facilitate the turning and homogenization of beans in the fermenter. This axis permits to put fermenter in a vertical position during the anaerobic alcoholic phase of fermentation, and horizontally during acetic phase to take advantage of the mid height filling. For circulation of air flow during turning in acetic phase, two woven rattan with grid have been made, one for the top and second for the bottom of the fermenter. In order to reduce air flow during acetic phase, two airtight covers are put on each grid cover. The efficiency of the turning by this kind of rotation, coupled with homogenization of the temperature, caused by the horizontal position in the acetic phase of the fermenter, contribute to having a good proportion of well-fermented beans (83.23%). In addition, beans’pH values ranged between 4.5 and 5.5. These values are ideal for enzymatic activity in the production of the aromatic compounds inside beans. The regularity of mass loss during all fermentation makes it possible to predict the drying surface corresponding to the amount being fermented.

Adsorption of Phenolic Compounds on Activated Carbon DSAC36-24

Activated carbon DSAC36-24 iy is adsorbent materials, characterized by a specific surface area of 548.13 m²g⁻¹. Their manufacture uses the natural raw materials like the nucleus of dates. In this study the treatment is done in two stages: A chemical treatment by H3PO4 followed by a physical treatment under nitrogen for 1 hour then under stream of CO2 for 24 hours. A characterization of the various parameters was determined such as the measurement of the specific surface area, determination of pHPZC, bulk density, iodine value. The study of the adsorption of organic molecules (hydroquinone, paranitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol) indicates that the adsorption phenomena are essentially due to the van der Waals interaction. In the case of organic molecules carrying the polar substituents, the existence of hydrogen bonds is also proved by the donor-acceptor forces. The study of the pH effect was done with modeling by different models (Langmuir, Freundlich, Langmuir-Freundlich, Redlich-Peterson), a kinetic treatment is also followed by the application of Lagergren, Weber, Macky.

The Use of Thermal Infrared Wavelengths to Determine the Volcanic Soils

In this study, an application was carried out to determine the Volcanic Soils by using remote sensing.  The study area was located on the Golcuk formation in Isparta-Turkey. The thermal bands of Landsat 7 image were used for processing. The implementation of the climate model that was based on the water index was used in ERDAS Imagine software together with pixel based image classification. Soil Moisture Index (SMI) was modeled by using the surface temperature (Ts) which was obtained from thermal bands and vegetation index (NDVI) derived from Landsat 7. Surface moisture values were grouped and classified by using scoring system. Thematic layers were compared together with the field studies. Consequently, different moisture levels for volcanic soils were indicator for determination and separation. Those thermal wavelengths are preferable bands for separation of volcanic soils using moisture and temperature models.

O-Functionalized CNT Mediated CO Hydro-Deoxygenation and Chain Growth

Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H2) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H2, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.