Three‐dimensional imaging of chemical phase transformations at the nanoscale with full‐field transmission X‐ray microscopy

The ability to probe morphology and phase distribution in complex systems at multiple length scales unravels the interplay of nano‐ and micrometer‐scale factors at the origin of macroscopic behavior. While different electron‐ and X‐ray‐based imaging techniques can be combined with spectroscopy at high resolutions, owing to experimental time limitations the resulting fields of view are too small to be representative of a composite sample. Here a new X‐ray imaging set‐up is proposed, combining full‐field transmission X‐ray microscopy (TXM) with X‐ray absorption near‐edge structure (XANES) spectroscopy to follow two‐dimensional and three‐dimensional morphological and chemical changes in large volumes at high resolution (tens of nanometers). TXM XANES imaging offers chemical speciation at the nanoscale in thick samples (>20 µm) with minimal preparation requirements. Further, its high throughput allows the analysis of large areas (up to millimeters) in minutes to a few hours. Proof of concept is provided using battery electrodes, although its versatility will lead to impact in a number of diverse research fields.     

Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces

Polycrystalline copper electrocatalysts have been experimentally shown to be capable of reducing CO₂ into CH₄ and C₂H₄ with relatively high selectivity, and a mechanism has recently been proposed for this reduction on the fcc(211) surface of copper, which was assumed to be the most active facet. In the current work, we use computational methods to explore the effects of the nanostructure of the copper surface and compare the effects of the fcc(111), fcc(100) and fcc(211) facets of copper on the energetics of the electroreduction of CO₂. The calculations performed in this study generally show that the intermediates in CO₂ reduction are most stabilized by the (211) facet, followed by the (100) facet, with the (111) surface binding the adsorbates most weakly. This leads to the prediction that the (211) facet is the most active surface among the three in producing CH₄ from CO₂, as well as the by-products H₂ and CO. HCOOH production may be mildly enhanced on the more close-packed surfaces ((111) and (100)) as compared to the (211) facet, due to a change in mechanism from a carboxyl intermediate to a formate intermediate. The results are compared to published experimental data on these same surfaces; the predicted trends in voltage requirements are consistent between the experimental and computational data.     

Enzymatic hydrolysis of ammonia-treated sugar beet pulp

Sugar beet pulp is a carbohydrate-rich coproduct generated by the table sugar industry. Beet pulp has shown promise as a feedstock for ethanol production using enzymesto hydroly zepolymeric carbohydrates and engineered bacteria to ferment sugars to ethanol. In this study, sugar beet pulp underwent an ammonia pressurization depressurization (APD) pretreatment in which the pulp was exploded by the sudden evaporation of ammonia in a reactor vessel. APD was found to substantially increase hydrolysis efficiency of the cellulose component, but when hemicellulose- and pectindegrading enzymes wereadded, treated pulp hydrolysis was no better than the untreated control.     

High-performance liquid chromatographic determination of 4,4'-methylenedianiline in human urine

A method is described for the determination of urinary 4,4'-methylenedianiline (MDA) by high-performance liquid chromatography (HPLC). MDA was extracted from hydrolyzed urine using C18 solid-phase extraction columns. The extract was analyzed by reversed-phase HPLC with electrochemical detection at a cell potential of 0.8 V. The method was very sensitive (detection limit 2.5 micrograms/l) and quantitation using 4,4'-ethylenedianiline as an internal standard correlated well with results by gas chromatography-mas spectrometry. Run-to-run precision (n = 25) averaged 8.9%. In analysis of more than 160 potentially exposed workers, MDA was detected in less than 20% of the urines and concentrations ranged up to 210 micrograms MDA per g of creatinine.     

Stability and performance analysis of rate-based feedback flow controlled ATM networks

Motivated by ABR class of service in ATM networks, we study a continuous time queueing system with a feedback control of the arrival rate of some of the sources. The feedback about the queue length or the total workload is provided at regular intervals (variations on it, especially the traffic management specification TM 4.0, are also considered). The propagation delays can be nonnegligible. For a general class of feedback algorithms, we obtain the stability of the system in the presence of one or more bottleneck nodes in the virtual circuit. Our system is general enough that it can be useful to study feedback control in other network protocols. We also obtain rates of convergence to the stationary distributions and finiteness of moments. For the single botterneck case, we provide algorithms to compute the stationary distributions and the moments of the sojourn times in different sets of states. We also show analytically (by showing continuity of stationary distributions and moments) that for small propagation delays, we can provide feedback algorithms which have higher mean throughput, lower probability of overflow and lower delay jitter than any open loop policy. Finally these results are supplemented by some computational results. This revised version was published online in June 2006 with corrections to the Cover Date.     

The analogue of Weyl's conformal curvature tensor in a Michal functional geometry

The purpose of this note is to obtain a set of functionals conformally invariant in a Michal functional geometry. The author is indebted to prof.A. D. Michal for calling his attention to this problem and for helpful suggestions and criticisms in the preparation of this paper.     

Evidence for the decay D0-->K(-)pi(+)pi(-)e(+)nu(e)

Using a 281 pb{-1} data sample collected at the psi(3770) with the CLEO-c detector, we present the first absolute branching fraction measurement of the decay D0-->K(-)pi(+)pi(-)e(+)nu(e) at a statistical significance of about 4.0 standard deviations. We find 10 candidates consistent with the decay D0-->K(-)pi(+)pi(-)e(+)nu(e). The probability that a background fluctuation accounts for this signal is less than 4.1 x 10{-5}. We find B(D0-->K(-)pi(+)pi(-)e(+)nu(e)) = [2.8{-1.1}{+1.4}(stat)+/-0.3(syst)]x10{-4}. By restricting the invariant mass of the hadronic system to be consistent with K1(1270), we obtain the product of branching fractions B(D{0}-->K{1}{-}(1270)e{+}nu{e})xB(K1-(1270)-->K{-}pi{+}pi{-})=[2.5{-1.0}{+1.3}(stat)+/-0.2(syst)]x10{-4}. Using B(K1-(1270)-->K{-}pi{+}pi{-})=(33+/-3)%, we obtain B(D{0}-->K{1}{-}(1270)e{+}nu{e})=[7.6{-3.0}{+4.1}(stat)+/-0.6(syst)+/-0.7]x10{-4}. The last error accounts for the uncertainties in the measured K1-(1270)-->K{-}pi{+}pi{-} branching fractions.     

The turbulent wake of a circular cylinder rotating about the streamwise axis

This paper presents measurements in the turbulent wake of a circular cylinder rotating with its axis normal to the free-stream velocity; in other words, the axis of rotation was parallel to the streamwise direction. All three mean velocities and six Reynolds stresses were obtained at three positions downstream of the cylinder, with and without rotation of the free-stream. Most emphasis is given to the latter results because of the better flow quality. The ratio of the circumferential velocity of the cylinder to the free-stream velocity — the swirl number — had a maximum value of 0.6. Measurements for two combinations of the free-stream and angular velocities showed the velocity deficit in the wake to be a multi-valued function of the swirl number, implying that the rotation affected the separation of the cylinder's boundary layer in a complex manner. In the turbulent wake, the rotation did not significantly alter the magnitudes of the normal stresses, but caused large changes to the shape of the profiles of the axial and cross-stream normal stresses. Eventually, the primary (cross-stream) shear stress became almost entirely positive, but there was no corresponding change to the (cross-stream) gradient of the streamwise mean velocity. Despite these alterations to the turbulence, the rotationally-activated generation terms in the Reynolds transport equations never dominated the terms that are common to the wakes of rotating and non-rotating cylinders.This work was supported by the Australian Research Council. Most of the data acquisition software was written by Mr J. J. Smith.