Measuring stress-induced martensite microstructures using far-field high-energy diffraction microscopy.

Modern X-ray diffraction techniques are now allowing researchers to collect long-desired experimental verification data sets that are in situ, three-dimensional, on the same length scales as critical microstructures, and using bulk samples. These techniques need to be adapted for advanced material systems that undergo combinations of phase transformation, twinning and plasticity. One particular challenge addressed in this article is direct analysis of martensite phases in far-field high-energy diffraction microscopy experiments. Specifically, an algorithmic forward model approach is presented to analyze phase transformation and twinning data sets of shape memory alloys. In the present implementation of the algorithm, the crystallographic theory of martensite (CTM) is used to predict possible martensite microstructures (i.e. martensite orientations, twin mode, habit plane, twin plane and twin phase fractions) that could form from the parent austenite structure. This approach is successfully demonstrated on three single- and near-single-crystal NiTi samples where the fundamental assumptions of the CTM are not upheld. That is, the samples have elastically strained lattices, inclusions, precipitates, subgrains, R-phase transformation and/or are not an infinite plate. The results indicate that the CTM still provides structural solutions that match the experiments. However, the widely accepted maximum work criterion for predicting which solution of the CTM should be preferred by the material does not work in these cases. Hence, a more accurate model that can simulate these additional structural complexities can be used within the algorithm in the future to improve its performance for non-ideal materials.

In-situ X-ray diffraction combined with scanning AC nanocalorimetry applied to a Fe0.84Ni0.16 thin-film sample.

We combine the characterization techniques of scanning AC nanocalorimetry and x-ray diffraction to study phase transformations in complex materials system. Micromachined nanocalorimeters have excellent performance for high-temperature and high-scanning-rate calorimetry measurements. Time-resolved X-ray diffraction measurements during in-situ operation of these devices using synchrotron radiation provide unprecedented characterization of thermal and structural material properties. We apply this technique to a Fe0.84Ni0.16 thin-film sample that exhibits a martensitic transformation with over 350 K hysteresis, using an average heating rate of 85 K/s and cooling rate of 275 K/s. The apparatus includes an array of nanocalorimeters in an architecture designed for combinatorial studies.

Compact integrated X-ray intensity and beam position monitor based on rare gas scintillation.

We have created and tested a compact integrated X-ray beam intensity and position monitor using Ar-gas scintillation. The light generated inside the device's cavity is detected by diametrically opposed PIN diodes located above and below the beam. The intensity is derived from the sum of the top and bottom signals, while the beam position is calculated from the difference-over-sum of the two signals. The device was tested at Cornell High Energy Synchrotron Source with both 17 keV and 59 keV x-rays. For intensity monitoring, the Ar-scintillation monitor performance is comparable to standard ion chambers in terms of precision. As an X-ray beam position monitor the new device response is linear with vertical beam position over a 2 mm span with a precision of 2 µm.

Correlating superlattice polymorphs to internanoparticle distance, packing density, and surface lattice in assemblies of PbS nanoparticles.

Assemblies of 3.5 nm PbS nanoparticles (NPs) nucleate in three dominant superlattice polymorphs: amorphous, body-centered-cubic (bcc) and face-centered-cubic (fcc) phase. This superlattice relationship can be controlled by the inter-NP distance without changing the NP size. Upon increase of inter-NP distance, the packing density decreases, and the capping molecules at NP surfaces change in structure and accordingly modify the surface energy. The driving force for NP assembly develops from an entropic maximization to a reduction of total free energy through multiple interactions between surface molecules and NPs and resulting variation of surface molecules. Upon long-term aging and additional thermal treatment, fcc undergoes a tetragonal distortion and subsequently transforms to bcc phase, and simultaneously, the NPs embedded in supercrystals reduce surface energy primarily in {200} facets. Linking molecule-NP interactions with a series of changes of packing density and surface lattice spacings of NPs allows for an interpretation of principles governing the nucleation, structure stability, and transformation of PbS NP-assembled supercrystals.

The effect of caffeine on maximal oxygen uptake and vertical jump performance in male basketball players.

This study investigated whether performance enhancement from caffeine described by other researchers transfers to male basketball players. The effects of caffeine ingestion were studied in a maximal-effort test on a treadmill that was followed by a vertical-jump test. Five elite-level male basketball players completed a graded treadmill test that measured maximal oxygen uptake, blood lactate profiles, respiratory exchange ratio, and rating of perceived exertion at each 3-minute stage. After a 15-minute warm-down, the subjects performed 10 vertical rebound jumps. Each subject completed the test twice--once with a 3 mg·kg(-1) of body weight dose of caffeine and once with a placebo, with the dosage administered 60 minutes before commencement of exercise. The test was thus administered according to a double-blind protocol. No substantial trends were found between caffeine and control trials, regardless of trial order. The study showed that the specified dosage had negligible effects on the players' power and endurance performance and had no efficacy as an ergogenic aid for male basketball players.

Tracking Baltic hypoxia and cod migration over millennia with natural tags.

Growing hypoxic and anoxic areas in coastal environments reduce fish habitat, but the interactions and impact on fish in these areas are poorly understood. Using "natural tag" properties of otoliths, we found significant correlations between the extent of Baltic Sea hypoxia and Mn/Ca ratios in regions of cod (Gadus morhua) otoliths corresponding to year 1 of life; this is associated with elevated bottom water dissolved manganese that increases with hypoxia. Elevated Mn/Ca ratios were also found in other years of life but with less frequency. We propose that cod exhibiting enhanced Mn/Ca ratios were exposed to dissolved manganese from hypoxia-induced redox dynamics in nursery areas. Neolithic (4500 B.P.) cod otoliths (n = 12) had low levels of Mn/Ca ratios, consistent with low hypoxia, but a single otolith dated to the younger Iron Age had a distinct growth band with an elevated Mn/Ca ratio. Sr/Ca patterns reflecting changes in environmental salinity and temperature were similar in both modern and Stone Age otoliths, indicating consistent migration habits across time, and Ba/Sr ratios in modern cod otoliths indicate increasing use of a more saline habitat with age. Using elemental ratios, numerous existing archival collections of otoliths could provide the means to reconstruct hypoxia exposure histories and major patterns of fish movement near "dead zones" globally.

A wavelet transform algorithm for peak detection and application to powder x-ray diffraction data.

Peak detection is ubiquitous in the analysis of spectral data. While many noise-filtering algorithms and peak identification algorithms have been developed, recent work [P. Du, W. Kibbe, and S. Lin, Bioinformatics 22, 2059 (2006); A. Wee, D. Grayden, Y. Zhu, K. Petkovic-Duran, and D. Smith, Electrophoresis 29, 4215 (2008)] has demonstrated that both of these tasks are efficiently performed through analysis of the wavelet transform of the data. In this paper, we present a wavelet-based peak detection algorithm with user-defined parameters that can be readily applied to the application of any spectral data. Particular attention is given to the algorithm's resolution of overlapping peaks. The algorithm is implemented for the analysis of powder diffraction data, and successful detection of Bragg peaks is demonstrated for both low signal-to-noise data from theta-theta diffraction of nanoparticles and combinatorial x-ray diffraction data from a composition spread thin film. These datasets have different types of background signals which are effectively removed in the wavelet-based method, and the results demonstrate that the algorithm provides a robust method for automated peak detection.

X-ray fluorescence investigation of ordered intermetallic phases as electrocatalysts towards the oxidation of small organic molecules.

The composition of ordered intermetallic nanoparticles (PtBi and PtPb) has been quantitatively studied by in situ X-ray fluorescence (XRF) during active electrochemical control in solutions of supporting electrolyte and small organic molecules (SOMs). Because the Pt L(ß1,2) lines and the Bi L(α1,2) lines are only separated by 200 eV, an energy-dispersive detector and a multiple-channel analyzer (MCA) were used to record the major fluorescent emission lines from these two elements. The molar ratios of platinum to the less-noble elements (Bi, Pb) in the nanoparticles dramatically changed as a function of the applied upper limit potentials (E(ulp)) in cyclic voltammetric (CV) characterization. Similar to previous investigations for bulk intermetallic surfaces, the less-noble elements leached out from the surfaces of the intermetallic nanoparticles. For PtBi nanoparticles, the ratios of fluorescence intensities of Pt/Bi in the samples were 0.42, 0.96, and 1.36 for E(ulp)=+0.40, +0.80, and 1.20 V, respectively, while cycling the potential from -0.20 V to the E(ulp) value for 10 cycles. The leaching-out process of the less-noble elements occurred at more negative E(ulp) values than expected. After cycling to relatively positive E(ulp) values, nonuniform PtM (M=Bi of Pb) nanoparticles formed with a Pt-rich shell and intermetallic PtM core. When the supporting solutions contained active fuel molecules in addition to the intermetallic nanoparticles (formic acid for PtBi, formic acid and methanol for PtPb), kinetic stabilization effects were observed for E(ulp)=+0.80 V, in a way similar to the response of the bulk materials. It was of great importance to quantitatively explore the change in composition and structure of the intermetallic nanoparticles under active electrochemical control. More importantly, this approach represents a simple, universal, and multifunctional method for the study of multi-element nanoparticles as electrocatalysts. This is, to our knowledge, the first report of nondestructive, quantitative characterization of bimetallic or multi-elemental nanoparticles electrocatalysts under active electrochemical control.

Cosputtered composition-spread reproducibility established by high-throughput x-ray fluorescence.

We describe the characterization of sputtered yttria-zirconia composition spread thin films by x-ray fluorescence (XRF). We also discuss our automated analysis of the XRF data, which was collected in a high throughput experiment at the Cornell High Energy Synchrotron Source. The results indicate that both the composition reproducibility of the library deposition and the composition measurements have a precision of better than 1 atomic percent.

High energy x-ray diffraction/x-ray fluorescence spectroscopy for high-throughput analysis of composition spread thin films.

High-throughput crystallography is an important tool in materials research, particularly for the rapid assessment of structure-property relationships. We present a technique for simultaneous acquisition of diffraction images and fluorescence spectra on a continuous composition spread thin film using a 60 keV x-ray source. Subsequent noninteractive data processing provides maps of the diffraction profiles, thin film fiber texture, and composition. Even for highly textured films, our diffraction technique provides detection of diffraction from each family of Bragg reflections, which affords direct comparison of the measured profiles with powder patterns of known phases. These techniques are important for high throughput combinatorial studies as they provide structure and composition maps which may be correlated with performance trends within an inorganic library.

In situ x-ray reflectivity studies of dynamics and morphology during heteroepitaxial complex oxide thin film growth.

We present a method, based on refraction effects in continuous, stratified media, for quantitative analysis of specular x-ray reflectivity from interfaces with atomic-scale roughness. Roughness at interfaces has previously been incorporated into this framework via Fourier transform of a continuous height distribution, but this approach breaks down when roughness approaches the atomic scale and manifests discrete character. By modeling the overall roughness at interfaces as a convolution of discrete and continuous height distributions, we have extended the applicability of this reflectivity model to atomic-scale roughness. The parameterization of thickness and roughness enables quantitative analysis of time-resolved in situ reflectivity studies of thin film growth, modeling step-flow, layer-by-layer and three-dimensional growth within a single framework. We present the application of this model to the analysis of anti-Bragg growth oscillations measured in situ during heteroepitaxial growth of La(0.7)Sr(0.3)MnO(3) on [Formula: see text] SrTiO(3) at different temperatures and pressures, and discuss the evolution of surface morphology.

Calibration of the biotrainer pro activity monitor in children.

The unique physical and movement characteristics of children necessitate the development of accelerometer equations and cut points that are population specific. The purpose of this study is to develop an ecologically valid cut point for the Biotrainer Pro monitor that reflects a threshold for moderate-intensity physical activity in elementary school children. A sample of 30 children (ages 8-12) wore a Biotrainer monitor while completing a series of 7 movement tasks (calibration phase) and while participating in an organized group activity (cross-validation phase). Videotapes from each session were processed using a computerized direct-observation technique to provide a criterion measure of physical activity. Analyses involved the use of mixed-model regression and receiver operator characteristic (ROC) curves. The results indicated that a cut point of 4 counts/min provides the optimal balance between the related needs for sensitivity (accurately detecting activity) and specificity (limiting misclassification of activity as inactivity). Results with the cross-validation data demonstrated that this value yielded the best overall kappa (.58) and a high classification agreement (84%) for activity determination. The specificity of 93% demonstrates that the proposed cut point can accurately detect activity; however, the lower sensitivity value of 61% suggests that some minutes of activity might be incorrectly classified as inactivity. The cut point of 4 counts/min provides an ecologically valid cut point to capture physical activity in children using the Biotrainer Pro activity monitor.

Multiple time scales in diffraction measurements of diffusive surface relaxation.

We grew SrTiO3 on SrTiO3(001) by pulsed laser deposition, using x-ray scattering to monitor the growth in real time. The time-resolved small-angle scattering exhibits a well-defined length scale associated with the spacing between unit-cell high surface features. This length scale imposes a discrete spectrum of Fourier components and rate constants upon the diffusion equation solution, evident in multiple exponential relaxation of the "anti-Bragg" diffracted intensity. An Arrhenius analysis of measured rate constants confirms that they originate from a single activation energy.

Observed effects of a changing step-edge density on thin-film growth dynamics.

We grew SrTiO(3) on SrTiO(3)(001) by pulsed laser deposition, while observing x-ray diffraction at the (00(1/2)) position. The drop DeltaI in the x-ray intensity following a laser pulse contains information about plume-surface interactions. Kinematic theory predicts DeltaI/I = -4sigma(1 - sigma), so that DeltaI /I depends only on the amount of deposited material sigma. In contrast, we observed experimentally that |DeltaI /I| < 4sigma(1 - sigma) and that DeltaI /I depends on the phase of x-ray growth oscillations. The combined results suggest a fast smoothing mechanism that depends on surface step-edge density.