Preliminary in-Situ X-Ray Absorption Fine Structure Examination of Pt/C and PtCo/C Cathode Catalysts in an Operational Polymer Electrolyte Fuel Cell

State-of-the-art polymer electrolyte fuel cells require a conditioning period to reach optimized cell performance. There is insuffi cient understanding about the behavior of catalysts during this period, especially with regard to the changing environment of the cathode electrocatalyst, which is typically Pt nanoparticles supported on high surface area Vulcan XC-72 carbon (Pt/C). The purpose of this research was to record preliminary observations of the changing environment during the conditioning phase using X-Ray Absorption Fine Structure (XAFS) spectroscopy. XAFS was recorded for a Pt/C cathode at the Pt L3-edge and a PtCo/C cathode at both the Pt L3-edge and Co K-edge. Using precision machined graphite cell-blocks, both transmission and fl uorescence data were recorded at Sector 12-BM-B of Argonne National Laboratory’s Advanced Photon Source. The fl uorescence and transmission edge steps allow for a working description of the changing electrocatalyst environment, especially water concentration, at the anode and cathode as functions of operating parameters. These features are discussed in the context of how future analysis may correlate with potential, current and changing apparent thickness of the membrane electrode assembly through loss of catalyst materials (anode, cathode, carbon support). Such direct knowledge of the effect of the conditioning protocol on the electrocatalyst may lead to better catalyst design. In turn, this may lead to minimizing, or even eliminating, the conditioning period

Evaluation of a Diagnostic Reasoning Program (DxR): Exploring Student Perceptions and Addressing Faculty Concerns

Abstract: Clinical reasoning is essentially a problem-solving process, in which medical students must learn to gather and interpret data, generate hypotheses and make decisions. To develop skills in problem-solving it is argued that students need more tools, rather than more answers (Masys, 1989). DxR is a computerised case series, in which students use 'doctor tools' to investigate a patient problem. This report describes a pilot evaluation of DxR in fourth year medicine at the University of Sydney. It addresses faculty concerns regarding the program, explores student perceptions, and looks at the capacity of the program to stimulate and support the development of clinical reasoning skills. It finally discusses possibilities for using DxR to support learning in medicine. Reviewers: Stig Andersen (Virtual Centre for Health Informatics, Aalborg, DK), David Good (U. Cambridge), Timothy Koschmann (U. Colorado) Interactive elements: 'Details are provided for obtaining a DxR demonstration CD.' DxR is distributed by NOVARTIS, although the DxR cases described in this article are not the same as those listed in the Diagnosis category of their bookshop/website. A Macromedia Director demonstration of DxR can be obtained by contacting Tanaya Patel, Project Director, DxR Development Group ([email protected]). Alternatively, a demonstration CD, and complimentary catalogue of patient cases and price list can be obtained by calling 800-631-1181 (USA)

The Spitzer c2d Survey of Large, Nearby, Interstellar Clouds. VIII. Serpens Observed with MIPS

We present maps of 1.5 deg^2 of the Serpens dark cloud at 24, 70, and 160 μm observed with the Spitzer Space Telescope MIPS camera. We describe the observations and briefly discuss the data processing carried out by the c2d team on these data. More than 2400 compact sources have been extracted at 24 μm, nearly 100 at 70 μm, and four at 160 μm. We estimate completeness limits for our 24 μm survey from Monte Carlo tests with artificial sources inserted into the Spitzer maps. We compare source counts, colors, and magnitudes in the Serpens cloud to two reference data sets: a 0.50 deg^2 set on a low-extinction region near the dark cloud, and a 5.3 deg^2 subset of the SWIRE ELAIS N1 data that was processed through our pipeline. These results show that there is an easily identifiable population of young stellar object candidates in the Serpens cloud that is not present in either of the reference data sets. We also show a comparison of visual extinction and cool dust emission illustrating a close correlation between the two and find that the most embedded YSO candidates are located in the areas of highest visual extinction

From Molecular Cores to Planet-forming Disks: An SIRTF Legacy Program

Crucial steps in the formation of stars and planets can be studied only at mid‐ to far‐infrared wavelengths, where the Space Infrared Telescope (SIRTF) provides an unprecedented improvement in sensitivity. We will use all three SIRTF instruments (Infrared Array Camera [IRAC], Multiband Imaging Photometer for SIRTF [MIPS], and Infrared Spectrograph [IRS]) to observe sources that span the evolutionary sequence from molecular cores to protoplanetary disks, encompassing a wide range of cloud masses, stellar masses, and star‐forming environments. In addition to targeting about 150 known compact cores, we will survey with IRAC and MIPS (3.6–70 μm) the entire areas of five of the nearest large molecular clouds for new candidate protostars and substellar objects as faint as 0.001 solar luminosities. We will also observe with IRAC and MIPS about 190 systems likely to be in the early stages of planetary system formation (ages up to about 10 Myr), probing the evolution of the circumstellar dust, the raw material for planetary cores. Candidate planet‐forming disks as small as 0.1 lunar masses will be detectable. Spectroscopy with IRS of new objects found in the surveys and of a select group of known objects will add vital information on the changing chemical and physical conditions in the disks and envelopes. The resulting data products will include catalogs of thousands of previously unknown sources, multiwavelength maps of about 20 deg^2 of molecular clouds, photometry of about 190 known young stars, spectra of at least 170 sources, ancillary data from ground‐based telescopes, and new tools for analysis and modeling. These products will constitute the foundations for many follow‐up studies with ground‐based telescopes, as well as with SIRTF itself and other space missions such as SIM, JWST, Herschel, and TPF/Darwin

The Spitzer c2d Survey of Weak-line T Tauri Stars II: New Constraints on the Timescale for Planet Building

One of the central goals of the Spitzer Legacy Project ``From Molecular Cores to Planet-forming Disks'' (c2d) is to determine the frequency of remnant circumstellar disks around weak-line T Tauri stars (wTTs) and to study the properties and evolutionary status of these disks. Here we present a census of disks for a sample of over 230 spectroscopically identified wTTs located in the c2d IRAC (3.6, 4.5, 4.8, and 8.0 um) and MIPS (24 um) maps of the Ophiuchus, Lupus, and Perseus Molecular Clouds. We find that ~20% of the wTTs in a magnitude limited subsample have noticeable IR-excesses at IRAC wavelengths indicating the presence of a circumstellar disk. The disk frequencies we find in these 3 regions are ~3-6 times larger than that recently found for a sample of 83 relatively isolated wTTs located, for the most part, outside the highest extinction regions covered by the c2d IRAC and MIPS maps. The disk fractions we find are more consistent with those obtained in recent Spitzer studies of wTTs in young clusters such as IC 348 and Tr 37. From their location in the H-R diagram, we find that, in our sample, the wTTs with excesses are among the younger part of the age distribution. Still, up to ~50% of the apparently youngest stars in the sample show no evidence of IR excess, suggesting that the circumstellar disks of a sizable fraction of pre-main-sequence stars dissipate in a timescale of ~1 Myr. We also find that none of the stars in our sample apparently older than ~10 Myrs have detectable circumstellar disks at wavelengths < 24 um. Also, we find that the wTTs disks in our sample exhibit a wide range of properties (SED morphology, inner radius, L_DISK/L*, etc) which bridge the gaps observed between the cTTs and the debris disk regimes.Comment: 54 pages, 13 figures, Accepted by Ap

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The Spitzer c2d Survey of Large, Nearby, Interstellar Clouds. VII. Ophiuchus Observed with MIPS

We present maps of 14.4 deg^2 of the Ophiuchus dark clouds observed by the Spitzer Space Telescope Multiband Imaging Photometer for Spitzer (MIPS). These high-quality maps depict both numerous point sources and extended dust emission within the star-forming and non–star-forming portions of these clouds. Using PSF-fitting photometry, we detect 5779 sources at 24 μm and 81 sources at 70 μm at the 10 σ level of significance. Three hundred twenty-three candidate young stellar objects (YSOs) were identified according to their positions on the MIPS/2MASS K versus color-magnitude diagrams, as compared to 24 μm detections in the SWIRE extragalactic survey. We find that more than half of the YSO candidates, and almost all those with protostellar Class I spectral energy distributions, are confined to the known cluster and aggregates

The Spitzer c2d survey of Large, Nearby, Interstellar Clouds. V. Chamaeleon II Observed with IRAC

We present IRAC (3.6, 4.5, 5.8, and 8.0 micron) observations of the Chamaeleon II molecular cloud. The observed area covers about 1 square degree defined by $A_V >2$. Analysis of the data in the 2005 c2d catalogs reveals a small number of sources (40) with properties similar to those of young stellaror substellar objects (YSOs). The surface density of these YSO candidates is low, and contamination by background galaxies appears to be substantial, especially for sources classified as Class I or flat SED. We discuss this problem in some detail and conclude that very few of the candidate YSOs in early evolutionary stages are actually in the Cha II cloud. Using a refined set of criteria, we define a smaller, but more reliable, set of 24 YSO candidates.Comment: 19 pages, 10 figures, in press Ap

Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application.

In situ electrochemical diagnostics designed to probe ionomer interactions with platinum and carbon were applied to relate ionomer coverage and conformation, gleaned from anion adsorption data, with O2 transport resistance for low-loaded (0.05 mgPt cm-2) platinum-supported Vulcan carbon (Pt/Vu)-based electrodes in a polymer electrolyte fuel cell. Coupling the in situ diagnostic data with ex situ characterization of catalyst inks and electrode structures, the effect of ink composition is explained by both ink-level interactions that dictate the electrode microstructure during fabrication and the resulting local ionomer distribution near catalyst sites. Electrochemical techniques (CO displacement and ac impedance) show that catalyst inks with higher water content increase ionomer (sulfonate) interactions with Pt sites without significantly affecting ionomer coverage on the carbon support. Surprisingly, the higher anion adsorption is shown to have a minor impact on specific activity, while exhibiting a complex relationship with oxygen transport. Ex situ characterization of ionomer suspensions and catalyst/ionomer inks indicates that the lower ionomer coverage can be correlated with the formation of large ionomer aggregates and weaker ionomer/catalyst interactions in low-water content inks. These larger ionomer aggregates resulted in increased local oxygen transport resistance, namely, through the ionomer film, and reduced performance at high current density. In the water-rich inks, the ionomer aggregate size decreases, while stronger ionomer/Pt interactions are observed. The reduced ionomer aggregation improves transport resistance through the ionomer film, while the increased adsorption leads to the emergence of resistance at the ionomer/Pt interface. Overall, the high current density performance is shown to be a nonmonotonic function of ink water content, scaling with the local gas (H2, O2) transport resistance resulting from pore, thin film, and interfacial phenomena