Investigation of the effects of phase transformations in micro and nano aluminum powders on kinetics of oxidation using thermogravimetric analysis.

Aluminum micro and nanoparticles are key ingredients in the synthesis of nano energetic materials. Hence it is important to characterize the kinetics and the rate controlling process of their oxidation. The literature shows that the mass diffusion and phase transformation within the aluminum oxide shell are important. However, the description of physical processes regarding simultaneous oxidation and phase transformation is lacking. In this paper, the controlled thermogravimetric (TGA) oxidation of 40-60 nm and 1 µm Al powders is investigated at constant heating rates and under isothermal conditions, respectively, upon varying the partial pressure of oxygen. It is found that the core-shell model of homogenous oxidation is applicable to explain the TGA results when the shell does not undergo phase transformation, which predicts the apparent activation energy in good agreement with the literature data. On the other hand, the simultaneous oxidation and phase transformation is able to be addressed using the JMAK model which reveals key parameters of the rate controlling processes. Mass diffusion is indeed rate determining during the oxidation of Al micro and nanopowders while the kinetics of the reaction is fast. Unlike the micron powders, the particle size distribution has a significant effect on the shape of the oxidation curves of the nanopowders.

Cascade electrocatalysis via AgCu single-atom alloy and Ag nanoparticles in CO2 electroreduction toward multicarbon products.

Electrocatalytic CO2 reduction into value-added multicarbon products offers a means to close the anthropogenic carbon cycle using renewable electricity. However, the unsatisfactory catalytic selectivity for multicarbon products severely hinders the practical application of this technology. In this paper, we report a cascade AgCu single-atom and nanoparticle electrocatalyst, in which Ag nanoparticles produce CO and AgCu single-atom alloys promote C-C coupling kinetics. As a result, a Faradaic efficiency (FE) of 94 ± 4% toward multicarbon products is achieved with the as-prepared AgCu single-atom and nanoparticle catalyst under ~720 mA cm-2 working current density at -0.65 V in a flow cell with alkaline electrolyte. Density functional theory calculations further demonstrate that the high multicarbon product selectivity results from cooperation between AgCu single-atom alloys and Ag nanoparticles, wherein the Ag single-atom doping of Cu nanoparticles increases the adsorption energy of *CO on Cu sites due to the asymmetric bonding of the Cu atom to the adjacent Ag atom with a compressive strain.

Influence of Surface Properties of Nanostructured Ceria-Based Catalysts on Their Stability Performance.

As the poor cycling stability of CeO2 catalysts has become the major obstacle for applications of diesel particulate filters (DPF), it is necessary to investigate how to reduce their structural and compositional changes during soot oxidation. In this study, different ratios of Samarium (Sm) were doped into the lattice of CeO2 nanoparticles to improve the catalytic performance as well as surface properties. The stability was investigated by recycling the catalyst, mixing it with soot again, and repeating the thermogravimetric analysis (TGA) tests seven times. Consistent observations were expected for more cycles. It was found that doping 5%, 10%, and 20% samarium into the CeO2 lattice can improve the catalyst stability but at the cost of losing some activity. While the catalyst became more stable with the increasing Sm doping, the 10% Sm-doped catalyst showed the best compromise between stability and activity. Ce3+ and Oα were found to play important roles in controlling catalytic soot oxidation activity. These two species were directly related to oxygen vacancies and oxygen storage capacity of the catalyst. Sm-doped catalysts showed a minimized decrease in the Ce3+ and Oα content when the fresh and spent catalysts were compared.

Temporal resolution of solid-phase microextraction: measurement of real-time concentrations within a dynamic system.

To address the challenge of measuring real-time analyte concentrations within dynamic systems, the temporal resolution of the solid-phase microextraction (SPME) approach has been investigated. A mass-uptake model for SPME within a dynamic system was developed and validated, with experimental factors affecting the temporal resolution (sampling time, agitation, SPME fiber dimensions, sample concentration and change rate, and instrument sensitivity) characterized. Calibration methods for time-resolved sampling in a dynamic system were compared. To demonstrate the efficacy of time-resolved SPME, this approach was successfully applied to investigate the binding kinetics between plasma proteins and pharmaceuticals, which verified a decrease in free pharmaceutical concentrations over time in the presence of bovine serum albumin. The current study provides the theoretical and logistical framework for applying SPME to the real-time measurement of dynamic systems, facilitating future SPME applications such as in vivo metabolomic studies.

Real-Time Observation of Carbon Oxidation by Driven Motion of Catalytic Ceria Nanoparticles within Low Pressure Oxygen.

Carbon particulate matter (PM) is an undesirable aerosol pollutant formed from combustors such as power plants, refineries, and engines. The most common and effective method of mitigating PM emission is the capture of particulates using a filter, before particles are released into the atmosphere. In order to develop and improve advanced filtering materials, a better understanding is required of their chemical and mechanical behavior. We report on a novel phenomenon on the mobility and oxidation behavior of catalytic iron doped ceria nanoparticles in contact with mobile carbon black nanoparticles. The process is recorded by real time imaging within an environmental transmission electron microscope. In contrast to observations in previous studies, the separated ceria nanoparticles are found to actively move on the substrate and consume the connecting carbon particles one-by-one. The velocity of particle motion is correlated to the reaction temperature and oxygen pressure, both determining the reaction rate. Modeling using the Density Functional Theory suggests this motion is driven by the chemical bonding between the surface oxygen of the catalyst and the graphite layers of carbon black, initiated through the Van der Waals force between two types of nanoparticles.

Large scale combustion synthesis of single-walled carbon nanotubes and their characterization.

Since its invention in 1991, premixed combustion synthesis of fullerenic materials has been established as the major industrial process for manufacturing of these materials. Large-scale production of fullerenes such as C60, C70 and C84 has been implemented. More recently, combustion technology has been extended to the targeted synthesis of single-walled carbon nanotubes (SWCNT). Addition of catalyst precursor and operation at well-controlled fuel-rich but non-sooting conditions are required. Extensive parametric studies have allowed for the optimization of the formation of high-quality SWCNT. Purification techniques previously reported in the literature have been adjusted and used successfully for the nearly complete removal of metal and metal oxide. Material has been characterized using Raman spectroscopy, scanning (SEM) and transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), atomic force microscopy (AFM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). Correlations between process conditions and nanotube properties such as length have been established. Product reproducibility and process scalability of the combustion process have been demonstrated. Sample preparation was found to affect significantly the apparent characteristics of nanotubes as seen in electron microscopy images.

Combustion Characteristics of Physically Mixed 40 nm Aluminum/Copper Oxide Nanothermites Using Laser Ignition.

This paper reports on the ignition and flame propagation characteristics of aluminum/copper oxide (Al/CuO) nanothermite at different packing density, manufactured from 40 nm commercial Al and CuO nanopowders. A 3.5 W continuous wave laser was used to ignite the samples in argon at atmospheric pressure, and a high speed camera captured the flame propagation. The high speed images revealed that the fast laser heating creates significant material ablation, followed by heat transfer along the heated surface. The bulk ignition occurs near the edge of the top surface, followed by the self-sustained burning. Lightly pressed powders (90% porosity) ignited in ~0.1 ms and the burning front propagated at around 200 m/s, while the dense pellets (40-60% porosity) ignited in ~1 ms and the burning front propagated at around 10 m/s. These results indicate that the reaction mechanism changes from mass convection to heat diffusion with increasing the packing density. The ignition and burn speeds of these Al/CuO nanothermites at different equivalence ratios (ERs), along with SEM images of pre- and post-combustion, illustrate that the homogeneity of the mixture is a critical parameter for optimizing the performance. The Al rich mixtures show significantly lower ignition delays and higher burn speeds.

Hydrodynamic shrinkage of liquid CO2 Taylor drops in a straight microchannel.

Hydrodynamic shrinkage of liquid CO2 drops in water under a Taylor flow regime is studied using a straight microchannel (length/width ~100). A general form of a mathematical model of the solvent-side mass transfer coefficient (k s) is developed first. Based on formulations of the surface area (A) and the volume (V) of a general Taylor drop in a rectangular microchannel, a specific form of k s is derived. Drop length and speed are experimentally measured at three specified positions of the straight channel, namely, immediately after drop generation (position 1), the midpoint of the channel (position 2) and the end of the channel (position 3). The reductions of drop length (L x , x = 1, 2, 3) from position 1 to 2 and down to 3 are used to quantify the drop shrinkage. Using the specific model, k s is calculated mainly based on L x and drop flowing time (t). Results show that smaller CO2 drops produced by lower flow rate ratios ([Formula: see text]) are generally characterized by higher (nearly three times) k s and Sherwood numbers than those produced by higher [Formula: see text], which is essentially attributed to the larger effective portion of the smaller drop contributing in the mass transfer under same levels of the flowing time and the surface-to-volume ratio (~104 m-1) of all drops. Based on calculated pressure drops of the segmented flow in microchannel, the Peng-Robinson equation of state and initial pressures of drops at the T-junction in experiments, overall pressure drop (ΔP t) in the straight channel as well as the resulted drop volume change are quantified. ΔP t from position 1-3 is by average 3.175 kPa with a ~1.6% standard error, which only leads to relative drop volume changes of 0.3‰ to 0.52‰.

Highly pressurized partially miscible liquid-liquid flow in a micro-T-junction. I. Experimental observations.

This is the first part of a two-part study on a partially miscible liquid-liquid flow (liquid carbon dioxide and deionized water) which is highly pressurized and confined in a microfluidic T-junction. Our main focuses are to understand the flow regimes as a result of varying flow conditions and investigate the characteristics of drop flow distinct from coflow, with a capillary number, Ca_{c}, that is calculated based on the continuous liquid, ranging from 10^{-3} to 10^{-2} (10^{-4} for coflow). Here in part I, we present our experimental observation of drop formation cycle by tracking drop length, spacing, frequency, and after-generation speed using high-speed video and image analysis. The drop flow is chronologically composed of a stagnating and filling stage, an elongating and squeezing stage, and a truncating stage. The common "necking" time during the elongating and squeezing stage (with Ca_{c}∼10^{-3}) for the truncation of the dispersed liquid stream is extended, and the truncation point is subsequently shifted downstream from the T-junction corner. This temporal postponement effect modifies the scaling function reported in the literature for droplet formation with two immiscible fluids. Our experimental measurements also demonstrate the drop speed immediately following their generations can be approximated by the mean velocity from averaging the total flow rate over the channel cross section. Further justifications of the quantitative analysis by considering the mass transfer at the interface of the two partially miscible fluids are provided in part II.

Highly pressurized partially miscible liquid-liquid flow in a micro-T-junction. II. Theoretical justifications and modeling.

This is the second part of a two-part study on a partially miscible liquid-liquid flow (carbon dioxide and deionized water) that is highly pressurized and confined in a microfluidic T-junction. In the first part of this study, we reported experimental observations of the development of flow regimes under various flow conditions and the quantitative characteristics of the drop flow including the drop length, after-generation drop speed, and periodic spacing development between an emerging drop and the newly produced one. Here in part II we provide theoretical justifications to our quantitative studies on the drop flow by considering (1) CO_{2} hydration at the interface with water, (2) the diffusion-controlled dissolution of CO_{2} molecules in water, and (3) the diffusion distance of the dissolved CO_{2} molecules. Our analyses show that (1) the CO_{2} hydration at the interface is overall negligible, (2) a saturation scenario of the dissolved CO_{2} molecules in the vicinity of the interface will not be reached within the contact time between the two fluids, and (3) molecular diffusion does play a role in transferring the dissolved molecules, but the diffusion distance is very limited compared with the channel geometry. In addition, mathematical models for the drop length and the drop spacing are developed based on the observations in part I, and their predictions are compared to our experimental results.

Synthesis of Vertically-Aligned Zinc Oxide Nanowires and Their Application as a Photocatalyst.

Vertically aligned zinc oxide (ZnO) nanowires were hydrothermally synthesized on a glass substrate with the assistance of a pre-coated ZnO seeding layer. The crystalline structure, morphology and transmission spectrum of the as-synthesized sample were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and ultraviolet-visible (UV-Vis) spectrophotometry, respectively, indicating a wurzite ZnO material of approximately 100 nm wire diameter and absorbance at 425 nm and lower wavelengths. The photocatalytic activity of the sample was tested via the degradation of methyl orange in aqueous solution under UV-A irradiation. The synthesized nanowires showed a high photocatalytic activity, which increased up to 90% degradation in 2 h as pH was increased to 12. It was shown that the photocatalytic activity of the nanowires was proportional to the length to diameter ratio of the nanowires, which was in turn controlled by the growth time and grain size of the seed layer. Estimates suggest that diffusion into the regions between nanowires may be significantly hindered. Finally, the reusability of the prepared ZnO nanowire samples was also investigated, with results showing that the nanowires still showed 97% of its original photoactivity after ten cycles of use.

Characterization of thermochemical properties of Al nanoparticle and NiO nanowire composites.

Thermochemical properties and microstructures of the composite of Al nanoparticles and NiO nanowires were characterized. The nanowires were synthesized using a hydrothermal method and were mixed with these nanoparticles by sonication. Electron microscopic images of these composites showed dispersed NiO nanowires decorated with Al nanoparticles. Thermal analysis suggests the influence of NiO mass ratio was insignificant with regard to the onset temperature of the observed thermite reaction, although energy release values changed dramatically with varying NiO ratios. Reaction products from the fuel-rich composites were found to include elemental Al and Ni, Al2O3, and AlNi. The production of the AlNi phase, confirmed by an ab initio molecular dynamics simulation, was associated with the formation of some metallic liquid spheres from the thermite reaction.

Electroosmotic flow in a water column surrounded by an immiscible liquid.

In this paper, we conducted numerical simulation of the electroosmotic flow in a column of an aqueous solution surrounded by an immiscible liquid. While governing equations in this case are the same as that in the electroosmotic flow through a microchannel with solid walls, the main difference is the types of interfacial boundary conditions. The effects of electric double layer (EDL) and surface charge (SC) are considered to apply the most realistic model for the velocity boundary condition at the interface of the two fluids. Effects on the flow field of ς-potential and viscosity ratio of the two fluids were investigated. Similar to the electroosmotic flow in microchannels, an approximately flat velocity profile exists in the aqueous solution. In the immiscible fluid phase, the velocity decreases to zero from the interface toward the immiscible fluid phase. The velocity in both phases increases with ς-potential at the interface of the two fluids. The higher values of ς-potential also increase the slip velocity at the interface of the two fluids. For the same applied electric field and the same ς-potential at the interface of the two fluids, the more viscous immiscible fluid, the slower the system moves. The viscosity of the immiscible fluid phase also affects the flatness of the velocity profile in the aqueous solution.