Tungsten (W) films have many applications in the semiconducting industry for sensor technology. Deposition conditions can significantly impact the resulting W films in terms of the phases present (α-BCC or β-A12), microstructural grain orientation (texture), and residual strain. Tilt-A-Whirl methodology has been employed for the evaluation of a W film showing both texture and residual strain. Sin2(ψ) analysis of the film was performed to quantify the strongly tensile in-plane strain (+0.476%) with an estimated in-plane tensile stress of ~1.9 GPa. The 3D dataset was also evaluated qualitatively via 3D visualization. Visualization of 3D texture/strain data poses challenges due to peak broadening resulting from defocusing of the beam at high ψ tilt angles. To address this issue, principal component analysis (PCA) was employed to diagnose, model, and remove the broadening component from the diffraction data. Evaluation of the raw data and subsequent corrected data (after removal of defocusing effects) has been performed through projection of the data into a virtual 3D environment (via CAD2VR software) to qualitatively detect the impact of residual strain on the observed pole figure.
Luminescent lanthanide decanoate nanoparticles (LnC10NPs; Ln = Pr, Nd, Sm, Eu, Gd, Er) with spherical morphology (<100 nm) have been synthesizedviaa facile microwave (MWV) method using Ln(NO3)3·xH2O, ethanol/water, and decanoic acid. These hybrid nanomaterials adopt a lamellar structure consisting of inorganic Ln3+layers separated by a decanoate anion bilayer and exhibit liquid crystalline (LC) phases during melting. The particle size, crystalline structure, and LC behavior were characterized using transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and powder X-ray diffraction (ambient and heated). Thermal analysis indicated the formation of Smectic A LC phases by LnC10nanoparticles, with the smaller lanthanides (Ln = Sm, Gd, Er) displaying additional solid intermediate and Smectic C phases. The formation of LC phases by the smaller Ln3+suggests that these nanoscale materials have vastly different thermal properties than their bulk counterparts, which do not exhibit LC behavior. Photoluminescence spectroscopy revealed the LnC10NPs to be highly optically active, producing strong visible emissions that corresponded to expected electronic transitions by the various Ln3+ions. Under long-wave UV irradiation (λ= 365 nm), bright visible luminescence was observed for colloidal suspensions of Nd, Sm, Eu, Gd, and ErC10NPs. To the best of the authors’ knowledge, this is the first reported synthesis of nanoscale metal alkanoates, the first report of liquid crystalline behavior by any decanoate of lanthanides smaller than Nd, and the first observation of strong visible luminescence by non-vitrified lanthanide alkanoates.
Residual strain in electrodeposited Li films may affect safety and performance in Li metal battery anodes, so it is important to understand how to detect residual strain in electrodeposited Li and the conditions under which it arises. To explore this Li films, electrodeposited onto Cu metal substrates, were prepared under an applied pressure of either 10 or 1000 kPa and subsequently tested for the presence or absence of residual strain via sin(ψ) analysis. X-ray diffraction (XRD) analysis of Li films required preparation and examination within an inert environment; hence, a Be-dome sample holder was employed during XRD characterization. Results show that the Li film grown under 1000 kPa displayed a detectable presence of in-plane compressive strain (-0.066%), whereas the Li film grown under 10 kPa displayed no detectable in-plane strain. The underlying Cu substrate revealed an in-plane residual strain near zero. Texture analysis via pole figure determination was also performed for both Li and Cu and revealed a mild fiber texture for Li metal and a strong bi-axial texture of the Cu substrate. Experimental details concerning sample preparation, alignment, and analysis of the particularly air-sensitive Li films have also been detailed. This work shows that Li metal exhibits residual strain when electrodeposited under compressive stress and that XRD can be used to quantify that strain.
Advancements in computer technology have enabled three-dimensional (3D) reconstruction, data-stitching, and manipulation of 3D data obtained on X-ray imaging systems such as micro-computed tomography (μ-CT). Likewise, intuitive evaluation of these 3D datasets can be enhanced by recent advances in virtual reality (VR) hardware and software. Additionally, the generation, viewing, and manipulation of 3D X-ray diffraction datasets, such as pole figures employed for texture analysis, can also benefit from these advanced visualization techniques. We present newly-developed protocols for porting 3D data (as TIFF-stacks) into a Unity gaming software platform so that data may be toured, manipulated, and evaluated within a more-intuitive VR environment through the use of game-like controls and 3D headsets. We demonstrate this capability by rendering μ-CT data of a polymer dogbone test bar at various stages of in situ mechanical strain. An additional experiment is presented showing 3D XRD data collected on an aluminum test block with vias. These 3D XRD data for texture analysis (χ, φ, 2θ dimensions) enables the viewer to visually inspect 3D pole figures and detect the presence or absence of in-plane residual macrostrain. These two examples serve to illustrate the benefits of this new methodology for multidimensional analysis.
The success of geological carbon storage (GCS) depends on the sealing properties of caprocks, typically mudrocks, and their laminated variety – shales. In this study, we examined mineralogical changes in carbonate-rich Mancos Shale and corresponding changes in micro-mechanical properties following the reaction with carbon dioxide (CO2). Mineralogical changes of Mancos Shale depended on the pressure of CO2 during its exposure to the CO2-brine mixtures for up to 8 weeks. Dedolomitization was observed in the reactors pressurized with 100 psi of CO2, combined with the precipitation of gypsum. In the reactor pressurized with 2500 psi of CO2, the complete dissolution of calcite, partial dissolution of dolomite, and precipitation of magnesite and anhydrite were observed. Localized mechanical weakening was observed only for dolomite-muscovite-illite-rich laminae following whole shale puck alteration at 2500 psi of CO2, and a decrease of up to 50 ± 20% in scratch toughness was observed. The quartz-calcite-rich laminae did not exhibit a measurable difference in scratch toughness before and after reaction in CO2-rich brine. The predicted changes in mineralogy, porosity, density, and hardness of Mancos Shale are limited, according to the geochemical models describing alteration of shale by CO2-rich brine lasting for 5000 years. This study illustrates a coupled and localized chemical-mechanical response of caprock to the injection of CO2.
The powder-bed laser additive manufacturing (AM) process is widely used in the fabrication of three-dimensional metallic parts with intricate structures, where kinetically controlled diffusion and microstructure ripening can be hindered by fast melting and rapid solidification. Therefore, the microstructure and physical properties of parts made by this process will be significantly different from their counterparts produced by conventional methods. This work investigates the microstructure evolution for an AM fabricated AlSi10Mg part from its nonequilibrium state toward equilibrium state. Special attention is placed on silicon dissolution, precipitate formation, collapsing of a divorced eutectic cellular structure, and microstructure ripening in the thermal annealing process. These events alter the size, morphology, length scale, and distribution of the beta silicon phase in the primary aluminum, and changes associated with elastic properties and microhardness are reported. The relationship between residual stress and silicon dissolution due to changes in lattice spacing is also investigated and discussed.
X-ray fluorescence (XRF) has been employed as one of several orthogonal means of screening materials to prevent counterfeit and adulterated products from entering the product stream. We document the use of principal component analysis (PCA) of XRF data on compositionally similar and dissimilar stainless steels for the purpose of testing the feasibility of employing XRF spectra to parse and bin these alloys as the same or significantly different alloy materials. The results indicate that XRF spectra can separate and assign alloys via PCA, but that important corrections for detector drift and scaling must be performed in order to achieve valid results.
High-temperature X-ray diffraction with concurrent gas chromatography (GC) was used to study cobalt disulfide cathode pellets disassembled from thermal batteries. When CoS2 cathode materials were analyzed in an air environment, oxidation of the K(Br, Cl) salt phase in the cathode led to the formation of K2SO4 that subsequently reacted with the pyrite-type CoS2 phase leading to cathode decomposition between ∼260 and 450 °C. Independent thermal analysis experiments, i.e. simultaneous thermogravimetric analysis/differential scanning calorimetry/mass spectrometry (MS), augmented the diffraction results and support the overall picture of CoS2 decomposition. Both gas analysis measurements (i.e. GC and MS) from the independent experiments confirmed the formation of SO2 off-gas species during breakdown of the CoS2. In contrast, characterization of the same cathode material under inert conditions showed the presence of CoS2 throughout the entire temperature range of analysis.
The sequence of crystallization in a recrystallizable lithium silicate sealing glass-ceramic Li2O–SiO2–Al2O3–K2O–B2O3–P2O5–ZnO was analyzed by in situ high-temperature X-ray diffraction (HTXRD). Glass-ceramic specimens have been subjected to a two-stage heat-treatment schedule, including rapid cooling from sealing temperature to a first hold temperature 650°C, followed by heating to a second hold temperature of 810°C. Notable growth and saturation of Quartz was observed at 650°C (first hold). Cristobalite crystallized at the second hold temperature of 810°C, growing from the residual glass rather than converting from the Quartz. The coexistence of quartz and cristobalite resulted in a glass-ceramic having a near-linear thermal strain, as opposed to the highly nonlinear glass-ceramic where the cristobalite is the dominant silica crystalline phase. HTXRD was also performed to analyze the inversion and phase stability of the two types of fully crystallized glass-ceramics. While the inversion in cristobalite resembles the character of a first-order displacive phase transformation, i.e., step changes in lattice parameters and thermal hysteresis in the transition temperature, the inversion in quartz appears more diffuse and occurs over a much broader temperature range. Localized tensile stresses on quartz and possible solid-solution effects have been attributed to the transition behavior of quartz crystals embedded in the glass-ceramics.
Soil accumulation on photovoltaic (PV) modules presents a challenge to long-term performance prediction and lifetime estimates due to the inherent difficulty in quantifying small changes over an extended period. Low mass loadings of soil are a common occurrence but remain difficult to quantify. In order to more accurately describe the specific effects of sparse soil films on PV systems, we have expanded upon an earlier technique to measure the optical losses due to an artificially applied obscurant film. A synthetic soil analog was sprayed onto glass coupons at very brief intervals with a high-volume, low-pressure pneumatic sprayer. Light transmission through the grime film was evaluated using a quantum efficiency test stand and UV/vis spectroscopy. A 0.1-g/m 2 grime loading was determined to be the limit of mass measurement sensitivity, which is similar to some reports of daily soil accumulation. Predictable, linear decreases in transmission were observed for samples with a mass loading between 0.1 and 0.5 g/m2. A similar change was observed for soiled coupons from an outdoor monitoring station. Collected soil from the field coupons was analyzed to develop a compositional analog for indoor studies. Natural and synthetic soils produced similar decreases in transmission.