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At least 1,441 records · Page 80

Investigating the Effects of Lithium Deposition on the Abuse Response of Lithium-Ion Batteries

Li deposition at the graphitic anode is widely reported in literature as one of the leading causes of capacity fade in lithium-ion batteries (LIBs). Previous literature has linked Li deposition resulting from low-temperature ageing to diminished safety characteristics, however no current research has probed the effects of Li deposition on the abuse response of well-characterized cells. Using overtemperature testing, a relationship between increased concentrations of Li deposition and exacerbated abuse response in 1 Ah pouch cells has been established. A novel Li deposition technique is also investigated, where cells with n:p < 1 (anode-limiting) have been cycled at a high rate to exploit Li + diffusion limitations at the anode. Scanning Electron Microscopy of harvested anodes indicates substantial Li deposition in low n:p cells after 20 cycles, with intricate networks of Li(s) deposits which hinder Li + intercalation/deintercalation. Peak broadening and decreased amplitude of differential capacity plots further validates a loss of lithium inventory to Li + dissolution, and Powder X-ray Diffraction indicates Li + intercalation with staging in anode interstitial sites as the extent of Li deposition increases. A cradle-to-grave approach is leveraged on cell fabrication and testing to eliminate uncertainty involving the effects of cell additives on Li deposition and other degradation mechanisms.

25 ENERGY STORAGE↗

An Improved Thermal Conductivity Polyurethane Composite for a Space Borne 20KV Power Supply

This effort was designed to find a way to reduce the temperature rise of critical components of a 20KV High Voltage Power Supply (HVPS) by improving the overall thermal conductivity of the encapsulated modules. Three strategies were evaluated by developing complete procedures, preparing samples, and performing tests. The three strategies were: 1. Improve the thermal conductivity of the polyurethane encapsulant through the addition of thermally conductive powder while minimizing impact on other characteristics of the encapsulant. 2. Improve the thermal conductivity of the polyurethane encapsulated assembly by the addition of a slab of thermally conductive, electrically insulating material, which is to act as a heat spreader. 3. Employ a more thermally conductive substrate (Al203) with the existing encapsulation scheme. The materials were chosen based on the following criteria: high dielectric breakdown strength; high thermal conductivity, ease of manufacturing, high compliance, and other standard space qualified materials properties (low out-gassing, etc.). An optimized cure was determined by a statistical design of experiments for both filled and unfilled materials. The materials were characterized for the desired properties and a complete process was developed and tested. The thermal performance was substantially improved and the strategies may be used for space flight.

Pb free↗

L-PBF High-Throughput Data Pipeline Approach for Multi-modal Integration

Abstract Metal-based additive manufacturing requires active monitoring solutions for assessing part quality. Multiple sensors and data streams, however, generate large heterogeneous data sets that are impractical for manual assessment and characterization. In this work, an automated pipeline is developed that enables feature extraction from high-speed camera video and multi-modal data analysis. The framework removes the need for manual assessment through the utilization of deep learning techniques and training models in a weakly supervised paradigm. We demonstrate this pipeline’s capability over 700,000 high-speed camera frames. The pipeline successfully extracts melt pool and spatter geometries and links them to corresponding pyrometry, radiography, and processparameter information. 715 individual prints are examined to reveal melt pool areas that exceeds 0.07 mm 2 and pyrometry signal over a threshold (375 pyrometry units) were more likely to have defects. These automated processes enable massive throughput of characterization techniques.

36 MATERIALS SCIENCE↗

Optical effects of regolith processes on S asteroids as simulated by laser impulse alteration of ordinary chondrite

The spectral properties of some powdered chondrites and minerals altered by Isser impulse are studied in order to estimate possible optical effects of regolith processes (micrometeoritic bombardment). Gradual reduction of overall reflectance and spectral contrast, the increase of continuum slope, the increase of spectrally derived olivine/pyroxene ratio and Fs content of orthopyroxene with increasing alteration degree show that regolith processes could affect optical properties of surface material more heavily than has been previously appreciated. Ordinary chondrites (OC's) are known to account for 80 percent of observed meteorite falls, but so far no main belt parent bodies have been identified for these meteorites. S-asteroids resemble OC's spectrally, but are characterized by a steeper red continuum unlike that of OC's and their spectrally derived mineralogies are far outside OC range. Attempts were made to explain the spectral mismatch between OC's and S asteroids by some process, which alters optical properties of uppermost regolith. However, the spectral studies of shocked (black) OC's, gas-rich OC's, melted OC's and synthetic metal-rich regoliths derived from OC's demonstrate that such altered OC materials darken, but do not redden.

Moroz, L. V.↗

Mars Science Laboratory Sample Acquisition, Sample Processing and Handling: Subsystem Design and Test Challenges

The Sample Acquisition/Sample Processing and Handling subsystem for the Mars Science Laboratory is a highly-mechanized, Rover-based sampling system that acquires powdered rock and regolith samples from the Martian surface, sorts the samples into fine particles through sieving, and delivers small portions of the powder into two science instruments inside the Rover. SA/SPaH utilizes 17 actuated degrees-of-freedom to perform the functions needed to produce 5 sample pathways in support of the scientific investigation on Mars. Both hardware redundancy and functional redundancy are employed in configuring this sampling system so some functionality is retained even with the loss of a degree-of-freedom. Intentional dynamic environments are created to move sample while vibration isolators attenuate this environment at the sensitive instruments located near the dynamic sources. In addition to the typical flight hardware qualification test program, two additional types of testing are essential for this kind of sampling system: characterization of the intentionally-created dynamic environment and testing of the sample acquisition and processing hardware functions using Mars analog materials in a low pressure environment. The overall subsystem design and configuration are discussed along with some of the challenges, tradeoffs, and lessons learned in the areas of fault tolerance, intentional dynamic environments, and special testing

Jandura, Louise↗

Particle Size Analysis and Distribution

Scanning Electron Microscope (SEM) is a instrument used for examining samples at magnifications from 32 X to 500,000 X (for our instrument). The SEM is attached with an electron gun and is directed onto the sample. The sample then produces an image where it is read on the monitor. The electron gun is positioned at the top because it needs to shoot at the sample that is being tested. The electrons are then shot in a downward motion traveling through several lenses, such as the condenser lens for a more precise reading. Once the samples have been read by the instrument, it will show a picture that has a certain number of particles. Particle size distribution have many uses that are essential to life habits (health) or even conventional use for example construction. Here are just a few examples of how particle size analysis and distribution are being used even today. This Standard Reference Material (SRM) is primarily intended for use in the calibration of equipment used to measure particle size distributions (PSD) in the 9 μm to 30 μm range. A unit of SRM 1984 consists of a single bottle containing approximately 14 g of tungsten carbide/cobalt powder. Certified values: The PSD values at five mass percentiles were measured by scanning electron microscopy (SEM) and laser light scattering (LLS). The NIST certified PSD values by SEM are listed. These certified values were determined by the measurement of over 10 000 individual particles from three bottles. Comparing the certified NIST SRM 1984 tungsten carbide/cobalt powder with our results are almost identical. This is great because more accurate work can be done and proves that our laboratory is able to reproduce NIST results. In conclusion, the scanning electron microscope is used to capture the sampled element and display it to be counted. Without the use of particle distribution, it would be a difficult time to get necessities such as medicine, asthma pumps, constructing materials, or as simple as ink. Overall, our study is an experimental comparison of the techniques we have in house, which are LLS and SEM (combined with the NIH ImageJ software) using the NIST SRM-1984 as a common, well characterized sample so that we have an idea of how the results from the techniques compare.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Nanostructured Ni—Cd powders

Nanostructured powders of the Ni—Cd system containing 0–50 mol.% Cd obtained by co-reduction of metal salts from aqueous solutions by hydrazine were studied by X-ray diffraction, optical emission spectroscopy and electron microscopy. The reduction leads to formation of polycrystalline particles of 100–350 nm size, consisting of 10–20 nm crystallites. Phase composition of the powders is substantially different from that predicted by equilibrium on the phase diagram. Instead of a two-phase area consisting of Ni—NiCd intermetallide, other phase states are observed. If the system contains up to 6% Cd, the XRD data indicates the presence of a single-phase solid solution with a face centred cubic (fcc)-structure. The increase in the Cd content to ~40% is accompanied by formation of the NiCd{sub 5} intermetallide phase, along with a solid solution. In the 40–50% Cd content range, the main phases are NiCd{sub 5}, as well as a fcc-phase containing up to 18% Cd and characterized by a strong broadening of the diffraction maxima caused by the presence of 2–3 nm crystallites. Furthermore, the system of such composition contains a previously unknown non-stoichiometric phase based on Ni{sub 3}Cd, having a similar to Cu{sub 3}Au structure. The results serve to clarify compositions of reduction products and the character of the structural-phase transformations of the intermediate hydroxides and metal products during the reduction process. Based on the obtained data, we proposed a formation scheme for the phases that are unconventional for the studied composition region of the Ni-Cd system. It has been concluded that the main factors determining formation of the reduction products are particle nanoscale dimensionality and occurrence of the reduction process far from equilibrium.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Node Distortions in UiO-66 Inform Negative Thermal Expansion Mechanisms: Kinetic Effects, Frustration, and Lattice Hysteresis

In metal–organic frameworks (MOFs) the interplay between the dynamics of individual components and how these are constrained by the extended lattice can yield unusual emergent phenomena. For the archetypal Zr-MOF, UiO-66, we explore the cooperative dynamics of a Zr-node transformation that gives rise to negative thermal expansion (NTE). Here, using in situ synchrotron X-ray scattering, with powder diffraction and pair distribution function (PDF) analyses, we identify lattice hysteresis and a thermal ramp-rate-dependence of the thermal expansion. Specifically, kinetic trapping of distorted node states formed at high temperature, leads to broad variability in the apparent thermal expansion which ranges from large positive to large negative thermal expansion with coefficients of thermal expansion (CTE) from +45 to –80 × 10 –6 K –1 . Time-resolved relaxation studies at selected temperatures suggest that when equilibrated UiO-66 is intrinsically NTE, with a CTE of –35 × 10 –6 K –1 . Kinetic trapping of the node-distorted state following high temperature activation has broad implications for characterization and applications of these Zr-MOFs; the nonequilibrium node state depends on the thermal history of the sample with quench vs slow cooling likely to impact gas binding, pore volume, and accessible catalytic sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laser Powder Bed Fusion Manufactured Alloys 625 and 282 and Properties Relevant to Advanced Nuclear Components

Under the Advanced Materials and Manufacturing Technologies program, two Ni-based alloys fabricated by laser powder bed fusion (LPBF) have been evaluated: γ′-strengthened Haynes 282 and solution-strengthened Inconel 625. Large printing defects were observed in the LPBF 282 alloy fabricated using a Renishaw AM250 machine, likely due to particle spattering during printing. Annealing at 1,180°C for 1 h followed by 4 h at 800°C in a high density of 50 nm γ′-strengthening precipitates as well as partial recrystallization resulted in a bimodal grain distribution. Creep testing performed at 750°C revealed lower creep life and ductility for the LPBF 282 compared with wrought 282. X-ray computed tomography combined with optical and scanning electron microscopy microstructural characterization revealed crack formation during creep testing, initiated either from printing defects or from creep cavitation at grain boundaries. Printing defects were the likely reason for the lower creep performance of LPBF 282 and could be suppressed by optimizing the build configuration. Printing 625 on an EOS M290 machine using the recommended EOS parameters resulted in a very low defect density. Superior creep strength at 725°C was observed for the as-printed LPBF 625 along the build direction when compared with wrought 625. No defect larger than ~50 µm could be detected by X-ray computed tomography in the as-printed conditions and after creep testing for 1,000 h at 725°C and 150 MPa. Small, needle-like δ-phase precipitates were observed after creep testing for 100 h at 725°C and 200 MPa. The rapid formation of the γ phase is directly related to the initial Nb and Mo segregation in the LPBF 625 cell walls, and its effect on the alloy’s high-temperature performance will be evaluated. Solution annealing was carried out at 1,150°C for 1 h and led to full recrystallization of the alloy. A decrease in strength and increase in ductility were observed after solution annealing, and the alloy recrystallization resulted in isotropic tensile properties at room temperature, contrary to what was observed for the as-printed LPBF 625.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Degradation science: Integrating modeling and experiments to predict localized corrosion processes (Annual Progress Report)

Additively manufactured (AM) eutectic high-entropy alloys (EHEAs), such as nano-lamellar AlCoCrFeNi 2.1 , have excellent strength, ductility, and wear resistance even at elevated temperatures, but their corrosion behavior in aggressive acids at different length scales remain poorly understood. This work investigates the corrosion behavior of laser powder bed–fused (L-PBF) AlCoCrFeNi 2.1 as a function of annealing temperatures, probing degradation mechanisms from nanoscopic to macroscopic length scales. The alloy is dual phase consisting of a ductile FCC L1 2 phase and a high-strength BCC B2 phase. Rapid solidification during L-PBF produces a far-from-equilibrium nano-lamellar structure with nearly homogeneous elemental distribution, which tends to evolve upon annealing toward Cr/Co/Fe-enriched FCC and Al/Ni-enriched B2. Three conditions were studied: as-printed, 600 °C/5 h, and 1000 °C/1 h, over which B2 lamellae coarsen, lamellar spacing increases, and elemental segregation becomes more prominent. Microstructure and chemistry were characterized by scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS), while in-situ electrochemical atomic force microscopy (EC-AFM) was used to link early (<5 h) local dissolution to microstructure after exposure in sulfuric acid. EC-AFM highlights preferential dissolution of the BCC/B2 phase where the surrounding matrix is Cr-depleted and directly quantifies the dissolution rates within individual phases, tracks the transition from early nano-scale attack to partial repassivation, to correlate height differences with current and impedance responses. To monitor longer-term behavior (up to 96 h), ex-situ AFM, SEM, and confocal imaging were combined with conventional bulk electrochemical tests, bridging nanoscale observations to micro/meso-scale damage morphologies. At the meso-scale, the deepest dissolution channels align with the build-direction lamellae and melt-pool boundaries, indicating that printing directionality guides the propagation of these localized corrosion sites. Annealing modifies corrosion by restructuring BCC/FCC phase fractions, lamellar spacing, and Cr/Al segregation, thereby changing the cathode/anode ratio and passive film stability. The results clarify how as-printed and annealed nano-lamellar architectures differ in their susceptibility to selective dissolution; how elemental segregation competes with residual stresses along the build direction. With these insights, future work will use CALPHAD-guided alloy modification to stabilize higher Cr contents in the B2 phase while retaining a dominant FCC+B2/BCC microstructure, with the goal of designing mechanically robust, corrosion-resistant EHEAs for safety-critical applications to leverage the LLNL’s broader national and global security mission.

36 MATERIALS SCIENCE↗

Uncertainty evaluation in reference material characterization by double isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS)

Double isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) is one of the most important measurement methods in the establishment of measurement standards for inorganic analysis. However, there is still no good consensus on approaches for uncertainty evaluation in double ID-ICP-MS. Particularly, approaches to treating the instrumental isotopic fractionation (IIF) phenomenon and correlation between uncertainty sources are diverse and often unclear in the literature. Here, an approach for uncertainty evaluation in double ID-ICP-MS measurements is described. Using three certified reference materials (CRMs), it is shown that the IIF effects cancel out and should not be included in the uncertainty budget. Further, a consistent way of considering correlated sources of uncertainty to prevent double counting of uncertainties is described in detail along with an example of measuring the mass fraction of magnesium in an oyster powder CRM.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Experiments and Models for Polymeric Microsphere Foams

The current project was performed under the direction of Dr. Byron Pipes as its lead investigator from January 2001 to August 2004. With the permission of the NASA, the project was transferred to Dr. Thein Kyu as the principle investigator for the period of September 2004 - June 2005. There were two major thrust areas in the original proposal; (1) experimental characterization and kinematics of foam structure formation and (2) determination of the mechanical, physical, and thermal properties, although these thrust areas were further sub- divided into 7 tasks. The present project has been directed primarily to elucidate kinematics of micro-foam formation (tasks 1 and 3) and to characterize micro-foam structures, since the control of the micro-structure of these foams is of paramount importance in determining their physical, mechanical and thermal properties. The first thrust area was accomplished in a timely manner; however, the second thrust area of foam properties (tasks 2,4-7) has yet to be completed because the area of kinematics of foam structure formation turned out to be extremely complex and thus consumed more time than what have been anticipated. As will be reported in what follows, the present studies have greatly enhances the in-depth understanding of mechanisms and kinematics of the micro-foam formation from solid powders. However, in order to implement all objectives of the second thrust areas regarding investigations of mechanical, physical, and thermal properties and establishment of the correlation of structure - properties of the foams, the project needs additional time and resources. The technical highlights of the accomplishment are summarized as follows. The present study represents a first approach to understanding the complexities that act together in the powder foaming process to achieve the successful inflation of polyimide microstructures. This type of study is novel as no prior work had dissected the fundamentals that govern the inflation process in this type of systems. The systematic approach to each of the different phenomena (i.e. morphological, diffusive, kinetic and dynamic) brings into context each of them in a way that allows separate understanding and analysis. Of the different phenomena studied, probably the one that gives a higher level of control over the inflation process has been shown to be the morphological aspects of the precursor particles. It is a major contribution of the present work to isolate and identify this phenomenon and highlight the features that with careful control during the synthesis of the precursor material can lead to a highly optimized and specialized final product (neat foam or microstructure). Some of these accomplishments have been presented in various national meetings and some of which are either published in refereed journals or still in various stages of publications. One of the presentations was selected for "Best of ANTEC 2004" Online Presentation Series of the Society of Plastics Engineers (SPE) (September 2004)

Pipes, R. Byrona↗

Processing and characterization of the homologous Zr x Ta 2 O 2x+5 series

In this study, Zr x Ta 2 O 2x+5 (ZTOx) was systematically studied to determine ideal solid-state synthesis and pressureless sintering conditions. For Zr 6 Ta 2 O 17 (ZTO6) and other compositions with values of x in ZTOx the optimal synthesis temperature of 1100 °C with 1 h dwell time was optimal. XRD phase analysis of the homologous series indicated that for ZTOx, x = 5, 6, 7, and 8 were within the phase stability field while x = 4 and x = 9 were outside the phase stability field. Unit cell lattice parameters changed anisotropically with Zr:Ta ratio with an overall <0.1% change in unit cell volume across the solid solution. Some Raman modes red shifted while others blue shifted, indicating competing tensile and compressive strains. Sintering of ZTOx required a progressively higher temperature as Zr-content increased despite the same starting powder grain sizes and synthesis temperature. Higher Vickers hardness for Zr-rich (12.7–12.8 GPa) than Ta-rich Zr x Ta 2 O 2x+5 (11.6–11.7 GPa) disappeared when accounting for different sintering temperatures. Indentation toughness was similar for all compositions (1.2–1.4 MPa m 1/2 ). Properties of Zr x Ta 2 O 2x+5 series indicate tunability of Zr:Ta composition ratio while maintaining the structure and room temperature mechanical properties comparable to Hf 6 Ta 2 O 17 and 8 mol% yttria stabilized zirconia ceramics.

36 MATERIALS SCIENCE↗

Calorimetric metal vapor adsorption energies for characterizing industrial catalyst support materials

Many important catalysts and electro-catalysts for energy and environmental technologies involve late transition metal atoms and nanoparticles dispersed across the surface of high-surface-area support materials, for example, oxide nanoparticles. The surface reactivity and long-term stability against deactivation of these materials depends strongly on the strength of bonding of the metal atom and nanoparticles to the support surface. Here, we introduce a novel calorimetry method that implements a LiTaO 3 crystal for heat detection and extends metal adsorption calorimetry to surfaces of nanomaterials that are deposited from liquid solutions, as is typical when preparing industrial catalyst supports. This allows one to measure the strength of metal atom bonding and the adhesion energy of metal nanoparticles to clean surfaces of technologically relevant catalyst supports. We demonstrate that here by measuring the heat of Ag vapor adsorption onto the clean surfaces of high-surface-area TiO 2 anatase powdered support materials (i.e., 5-nm-diameter nanoparticles). These heats of adsorption show a pulse-to-pulse standard deviation of only 9.3 kJ/mol (3.3%) for pulses containing only 1% of a monolayer of Ag vapor, with potential for a 5-fold reduction in noise if used with another metal evaporator. The calorimeter was also proven to work well measuring heats of Ag adsorption on calcium niobate(001) nanosheets deposited as thin films from liquid solution. Here, this calorimeter opens up the possibility of using metal adsorption calorimetry to screen catalyst support materials for the strengths with which they bind metal atoms and metal nanoparticles, offering new opportunities to discover better support materials or for basic scientific study of structure / function relationships with respect to metal / support bond energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation of non-local screening in K-edge XANES for Pr0.67Sr0.33MnO3 under high pressure

The electronic excitation of 3$d$ transition metal oxide depends on the hybridization between orbitals of different ions, and is related to the materials properties. In this work, we systematically study the effect of hydrostatic pressure up to similar to ~20 GPa on the crystal structure and electronic structure of Pr 0.67 Sr 0.33 MnO 3 powder, using Mn $K$-edge X-ray absorption near edge structure and X-ray diffraction at room temperature. With the increase of pressure, the energy position of non-local screened feature moves towards feature without screening due to the enhanced transition energy; however, the intensity (probability) of non-local screened feature increases with the pressure. Further study suggests that the pressure-induced antiferromagnetic phase, affecting hybridization between neighboring Mn ions with spin sensitivity, increase the probability of non-local charge transfer and corresponding intensity of non-local screened feature. The spin-sensitivity of non-local screening may be a useful parameter for characterization of material properties.

36 MATERIALS SCIENCE↗

Effects of charging rates on LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622)/graphite Li-ion cells

Enabling fast charging capability of lithium-ion battery is of great importance to widespread adoption of electric vehicles. Increasing the charging rates from state-of-the-art 2C (30 min) to 6C (10 min) requires deep understanding on the cell aging mechanism. Here, 400 mAh pouch cells are cycled at 1C, 4C and 6C charging rates with 1C discharging rate. Capacity fading, cathode structural changes, Li inventory loss, electrolyte composition changes and Li plating on graphite electrodes are thoroughly studied by various characterization techniques. The rapid capacity fading in cells at 6C charging rate is mainly due to Li inventory loss from cathode structure and metallic Li plating on graphite electrode at higher charging rate. Post-mortem analysis also revealed changes in electrolyte such as increased salt molarity and transesterification during fast charging.

25 ENERGY STORAGE↗

Using SIMS to decode noisy stratigraphic δ 13 C variations in Ediacaran carbonates

Carbonate carbon isotope (δ 13 C carb ) chemostratigraphy is a valuable tool in Precambrian stratigraphic correlation. The effectiveness of this tool rests on the assumption that δ 13 C carb data record global seawater signals. However, in some cases δ 13 C carb data exhibit rapid and noisy stratigraphic variations that may have been influenced by authigenic or diagenetic carbonate minerals. To assess the contribution of non-primary minerals towards bulk carbonate carbon isotope values, we acquired SIMS (secondary ion mass spectrometry) δ 13 C carb data, electron microscopic data, and CL (cathodoluminescence) microscopic data from two Ediacaran successions—the lower Member II of the Doushantuo Formation in South China and the Mooifontein Member of the Zaris Formation in southern Namibia. The Doushantuo samples came from a stratigraphic interval with noisy meter-scale δ 13 C carb variations of up to 10‰, whereas the Mooifontein Member is characterized by consistent δ13Ccarb values with limited meter-scale variations of less than ~4‰. Our data show that the meter-scale stratigraphic variations in δ 13 C carb are also mirrored in the SIMS data at μm-mm scales in both Doushantuo and Mooifontein samples. In the Doushantuo samples, SIMS δ 13 C carb values of authigenic calcite vary by up to 10‰ over μm-mm scales and can be either higher or lower than those of the co-existing dolomite matrix, which also appears to be affected by authigenic carbonate on the basis of petrographic observation. Bulk-sample δ 13 C carb values measured on powders microdrilled from the same SIMS specimens are within the range of SIMS δ 13 C carb values. Thus, we infer that bulk-sample δ 13 C carb values of Doushantuo samples represent mixtures of different carbonate components. The Doushantuo and Mooifontein SIMS δ 13 C carb data validate the traditional method of using chemostratigraphic consistency to evaluate authigenic/diagenetic alteration, but given that secondary phases may be 13 C-enriched relative to matrix carbonate, caution is warranted when taking maximum values to approximate primary chemostratigraphic trends.

58 GEOSCIENCES↗

Using powder XRD and pair distribution function to determine anisotropic atomic displacement parameters of orthorhombic tridymite and tetragonal cristobalite

Determination of the crystal structures of low-temperature tridymite and cristobalite using single-crystal XRD has been challenging because they generally occur as metastable fine-grained crystals in the geological environment. Therefore, using powder diffraction and scattering techniques is critical to study the low-temperature crystals. Synchrotron powder X-ray diffraction (XRD), pair distribution function (PDF) and transmission electron microscopy were used to investigate the structure of orthorhombic tridymite with C 222 1 symmetry and tetragonal cristobalite with P 4 1 2 1 2 symmetry, including their anisotropic atomic displacement parameters (ADPs). Rietveld refinement was used to determine the unit-cell parameters, fractional coordinates and isotropic atomic displacement parameters ( U iso ) of the tridymite and cristobalite. The PDF method was used to determine ADPs for each atom. The results suggest that the crystal structure with high quality ADP values can be obtained using the combined methods of XRD and PDF analyses. The method can be used for characterizing crystals that are not suitable for single-crystal XRD.

Lee, Seungyeol (ORCID:0000000201751389)↗