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- ItemUnraveling the H2 Promotional Effect on Palladium-Catalyzed CO Oxidation Using a Combination of Temporally and Spatially Resolved Investigations(Washington, DC : ACS, 2018) Stewart, Caomhán; Gibson, Emma K.; Morgan, Kevin; Cibin, Giannantonio; Dent, Andrew J.; Hardacre, Christopher; Kondratenko, Evgenii V.; Kondratenko, Vita A.; McManus, Colin; Rogers, Scott; Stere, Cristina E.; Chansai, Sarayute; Wang, Yi-Chi; Haigh, Sarah J.; Wells, Peter P.; Goguet, AlexandreThe promotional effect of H2 on the oxidation of CO is of topical interest, and there is debate over whether this promotion is due to either thermal or chemical effects. As yet there is no definitive consensus in the literature. Combining spatially resolved mass spectrometry and X-ray absorption spectroscopy (XAS), we observe a specific environment of the active catalyst during CO oxidation, having the same specific local coordination of the Pd in both the absence and presence of H2. In combination with Temporal Analysis of Products (TAP), performed under isothermal conditions, a mechanistic insight into the promotional effect of H2 was found, providing clear evidence of nonthermal effects in the hydrogen-promoted oxidation of carbon monoxide. We have identified that H2 promotes the Langmuir-Hinshelwood mechanism, and we propose this is linked to the increased interaction of O with the Pd surface in the presence of H2. This combination of spatially resolved MS and XAS and TAP studies has provided previously unobserved insights into the nature of this promotional effect.
- ItemQuantifying Rate-and Temperature-Dependent Molecular Damage in Elastomer Fracture(College Park, Md. : APS, 2020) Slootman, Juliette; Waltz, Victoria; Yeh, C. Joshua; Baumann, Christoph; Göstl, Robert; Comtet, Jean; Creton, CostantinoElastomers are highly valued soft materials finding many applications in the engineering and biomedical fields for their ability to stretch reversibly to large deformations. Yet their maximum extensibility is limited by the occurrence of fracture, which is currently still poorly understood. Because of a lack of experimental evidence, current physical models of elastomer fracture describe the rate and temperature dependence of the fracture energy as being solely due to viscoelastic friction, with chemical bond scission at the crack tip assumed to remain constant. Here, by coupling new fluorogenic mechanochemistry with quantitative confocal microscopy mapping, we are able to quantitatively detect, with high spatial resolution and sensitivity, the scission of covalent bonds as ordinary elastomers fracture at different strain rates and temperatures. Our measurements reveal that, in simple networks, bond scission, far from being restricted to a constant level near the crack plane, can both be delocalized over up to hundreds of micrometers and increase by a factor of 100, depending on the temperature and stretch rate. These observations, permitted by the high fluorescence and stability of the mechanophore, point to an intricate coupling between strain-rate-dependent viscous dissipation and strain-dependent irreversible network scission. These findings paint an entirely novel picture of fracture in soft materials, where energy dissipated by covalent bond scission accounts for a much larger fraction of the total fracture energy than previously believed. Our results pioneer the sensitive, quantitative, and spatially resolved detection of bond scission to assess material damage in a variety of soft materials and their applications. © 2020 authors. Published by the American Physical Society.
- ItemLength distributed measurement of temperature effects in Yb-doped fibers during pumping(Bellingham : SPIE, 2014) Leich, M.; Fiebrandt, J.; Schwuchow, A.; Jetschke, S.; Unger, S.; Jäger, M.; Rothhardt, M.; Bartelt, H.We demonstrate a distributed measurement technique to observe temperature changes along pumped Yb-doped fibers. This technique is based on an array of fiber Bragg gratings acting as a temperature sensor line. The Bragg gratings are inscribed directly into the Yb-doped fiber core using high-intensity ultrashort laser pulses and an interferometric setup. We studied the temperature evolution in differently co-doped Yb fibers during optical pumping and identified different effects contributing to the observed temperature increase. We found that preloading of fibers with hydrogen supports the formation of Yb2+ during UV irradiation and has a large impact on fiber temperature during pumping. The proposed technique can be applied to investigate the homogeneity of pump absorption in active fibers and to support spatially resolved photodarkening measurements.
- ItemRaman imaging with a fiber-coupled multichannel spectrograph(Basel : MDPI AG, 2014) Schmälzlin, E.; Moralejo, B.; Rutowska, M.; Monreal-Ibero, A.; Sandin, C.; Tarcea, N.; Popp, J.; Roth, M.M.Until now, spatially resolved Raman Spectroscopy has required to scan a sample under investigation in a time-consuming step-by-step procedure. Here, we present a technique that allows the capture of an entire Raman image with only one single exposure. The Raman scattering arising from the sample was collected with a fiber-coupled high-performance astronomy spectrograph. The probe head consisting of an array of 20 × 20 multimode fibers was linked to the camera port of a microscope. To demonstrate the high potential of this new concept, Raman images of reference samples were recorded. Entire chemical maps were received without the need for a scanning procedure.
- ItemEvaluating Experimental Design of ERT for Soil Moisture Monitoring in Contour Hedgerow Intercropping Systems(Hoboken, NJ : Wiley, 2012) Garré, S.; Günther, T.; Diels, J.; Vanderborght, J.Contour hedgerow intercropping systems have been proposed as an alternative to traditional agricultural practice with a single crop, as they are effective in reducing run-off and soil erosion. However, competition for water and nutrients between crops and associated hedgerows may reduce the overall performance of these systems. To get a more detailed understanding of the competition for water, spatially resolved monitoring of soil water contents in the soil-plant-atmosphere system is necessary. Electrical resistivity tomography (ERT) is potentially a valuable technique to monitor changes in soil moisture in space and time. In this study, the performance of different ERT electrode arrays to detect the soil moisture dynamics in a mono- and an intercropping system was tested. Their performance was analyzed based on a synthetic study using geophysical measures, such as data recovery and resolution, and using spatial statistics of retrieved water content, such as an adjusted coefficient of variation and semivariances. The synthetic ERT measurements detected differences between the cropping systems and retrieved spatial structure of the soil moisture distribution, but the variance and semivariance were underestimated. Sharp water content contrasts between horizons or in the neighborhood of a root water uptake bulb were smoothened. The addition of electrodes deeper in the soil improved the performance, but sometimes only marginally. ERT is therefore a valuable tool for soil moisture monitoring in the field under different cropping systems if an electrode array is used which can resolve the patterns expected to be present in the medium. The use of spatial statistics allowed to not only identify the overall model recovery, but also to quantify the recovery of spatial structures.
- ItemMetrological large range magnetic force microscopy(College Park, MD : American Institute of Physics, 2018) Dai, G.; Hu, X.; Sievers, S.; Fernández, Scarioni, A.; Neu, V.; Fluegge, J.; Schumacher, H.W.A new metrological large range magnetic force microscope (Met. LR-MFM) has been developed. In its design, the scanner motion is measured by using three laser interferometers along the x, y, and z axes. Thus, the scanner position and the lift height of the MFM can be accurately and traceably determined with subnanometer accuracy, allowing accurate and traceable MFM measurements. The Met. LR-MFM has a measurement range of 25 mm × 25 mm × 5 mm, larger than conventional MFMs by almost three orders of magnitude. It is capable of measuring samples from the nanoscale to the macroscale, and thus, it has the potential to bridge different magnetic field measurement tools having different spatially resolved scales. Three different measurement strategies referred to as Topo&MFM, MFMXY, and MFMZ have been developed. The Topo&MFM is designed for measuring topography and MFM phase images, similar to conventional MFMs. The MFMXY differs from the Topo&MFM as it does not measure the topography profile of surfaces at the second and successive lines, thus reducing tip wear and saving measurement time. The MFMZ allows the imaging of the stray field in the xz- or yz-planes. A number of measurement examples on a multilayered thin film reference sample made of [Co(0.4 nm)/Pt(0.9 nm)]100 and on a patterned magnetic multilayer [Co(0.4 nm)/Pt(0.9 nm)]10 with stripes with a 9.9 μm line width and 20 μm periodicity are demonstrated, indicating excellent measurement performance.