Multi-scale chemo-mechanical evolution during crystallization of mixed conducting SrTi[subscript 0.6
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Buckner, Haley B.↗
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Results for “in situ crystallization”
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Heterolytic Scission of Hydrogen Within a Crystalline Frustrated Lewis Pair
We report the heterolysis of molecular hydrogen under ambient conditions by the crystalline frustrated Lewis pair (FLP) 1-{2-[bis(pentafluorophenyl)boryl]phenyl}-2,2,6,6-tetramethylpiperidine (KCAT). The gas–solid reaction provides an approach to prepare the solvent-free, polycrystalline ion pair KCATH2 through a single crystal to single crystal transformation. The crystal lattice of KCATH2 increases in size relative to the parent KCAT by approximately 2%. Microscopy was used to follow the transformation of the highly colored red/orange KCAT to the colorless KCATH2 over a period of 2 h at 300 K under a flow of H2 gas. There is no evidence of crystal decrepitation during hydrogen uptake. Inelastic neutron scattering employed over a temperature range from 4–200 K did not provide evidence for the formation of polarized H2 in a precursor complex within the crystal at low temperatures and high pressures. However, at 300 K, the INS spectrum of KCAT transformed to the INS spectrum of KCATH2. Calculations suggest that the driving force is more favorable in the solid state compared to the solution or gas phase, but the addition of H2 into the KCAT crystal is unfavorable. Ab Initio methods were used to calculate the INS spectra of KCAT, KCATH2, and a possible precursor complex of H2 in the pocket between the B and N of crystalline KCAT. Ex-situ NMR showed that the transformation from KCAT to KCATH2 is quantitative and our results suggest that the hydrogen heterolysis process occurs via H2 diffusion into the FLP crystal with a rate-limiting movement of H2 from inactive positions to reactive sites.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A Ligand-Directed Nitrophenol Carbonate for Transient in situ Bioconjugation and Drug Delivery
Here we report the first use of ligand-directed proximity accelerated bioconjugation chemistry in the tandem delivery and release of a therapeutic payload. To do this, we designed a nitrophenol carbonate for ligand-directed in situ bioconjugation of a prodrug payload to a protein. The transient nature of our conjugation chemistry renders the protein a depot for timedependent release of active drug following hydrolysis and selfimmolation. In our model system, using an immunostimulant prodrug, biotin ligand, and avidin protein, we observe release of bioavailable immunostimulant both spectroscopically and with an immune cell line over 48 h. Avidin co-crystalized with the nitrophenolate directing group verified the binding pose of the ligand and offered insight into the mechanism of in situ bioconjugation. Overall, this scaffold warrants further investigation for the time-dependent delivery of therapeutics and use in protein ligand pairs beyond biotin and avidin used for this work.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ice Supersaturation Variability in Cirrus Clouds: Role of Vertical Wind Speeds and Deposition Coefficients
Abstract Aircraft measurements reveal ice supersaturation statistics in cirrus (ISSs) with broad maxima around ice saturation and pronounced variance. In this study, processes shaping ISSs in midlatitude and tropical upper tropospheric conditions are systematically investigated. Water vapor deposition and sublimation of size‐resolved ice crystal populations are simulated in an air parcel framework. Mesoscale temperature fluctuations (MTFs) due to gravity waves force the temporal evolution of supersaturation. Various levels of background wave forcing and cirrus thickness are distinguished in stochastic ensemble simulations. Kinetic limitations to ice mass growth are brought about by supersaturation‐dependent deposition coefficients that represent efficient and inefficient growth modes as a function of ice crystal size. The simulations identify a wide range of deposition coefficients in cirrus, but most values stay above 0.01 such that kinetic limitations to water uptake remain moderate. Supersaturation quenching times are long, typically 0.5–2 hr. The wave forcing thus causes a remarkably large variability in ISSs and cirrus microphysical properties except in the thickest cirrus, producing ensemble‐mean ISSs in line with in‐situ measurements. ISS variance is controlled by MTFs and increases with decreasing cirrus integral radii. In comparison, the impact of ice crystal growth rates on ISSs is small. These results contribute to efforts directed at identifying and solving issues associated with ice‐supersaturated areas and non‐equilibrium cirrus physics in global models.
Meteorology & Atmospheric Sciences↗
Mechanism of the wurtzite to rocksalt phase transformation in cadmium sulfide single crystals shock compressed along the 𝑐-axis to elastic impact stresses of ∼ 5 GPa
Cadmium sulfide (CdS), which exhibits a wurzite (WZ) to rocksalt (RS) phase transformation at elevated stresses, is an ideal system to address the role of deformation on phase transformation mechanisms and kinetics. CdS has been shown to have very different elastic-inelastic behavior for shock propagation along the WZ 𝑐- and 𝑎-axes, and also exhibits significant differences in the time scale for the phase transformation when shocked along these different axes. As an important first step in examining the role of deformation in shock-induced phase transformations, here we present in situ, time-resolved x-ray diffraction (XRD) measurements in single-event, shock wave experiments on CdS single crystals shocked along the WZ 𝑐-axis to elastic impact stresses near or above ∼ 5 GPa, where a marked increase in the kinetics of this transformation has been reported. The XRD measurements are compared with forward diffraction simulations to evaluate different proposed phase transformation mechanisms and are shown to be consistent with a shearing mechanism that results in the RS [001] direction being aligned with the original WZ 𝑐-axis and the RS [110] direction being aligned with the original WZ 𝑎-axis. In order to reproduce all observed RS diffraction spots the forward diffraction simulations required three different RS crystalline domains, each with a [110] direction aligned with one of the three original WZ 𝑎-axes, and a significant mosaicity, particularly about the RS [001] direction (the direction of shock propagation). In conclusion, this large mosaicity is likely due to variations in the possible shearing mechanisms that connect the WZ and RS structures, which can create crystallites with up to ∼ ±10° of relative rotations about the RS [001] direction, as well as further rotation of these crystallites as they grow, merge, and coalesce.
Crystal structure↗
The Structural Properties of Vapor Deposited Water Ice and Astrophysical Implications
Films of vapor deposited water ice at low temperature (T<30 K) show a number of interesting structural changes during a gradual warmup. We would like to talk about the structure of the low temperature high density amorphous form of water ice, the process of crystallization, and some recent work on the morphological changes of water ice films at high temperature. The studies of the high density amorphous form are from in-situ electron microscopy as well as numerical simulations of molecular dynamics and have lead to new insights into the physical distinction between this high density amorphous form and the low density amorphous form. For the process of crystallization, we propose a model that describes the crystallization of water ice from the amorphous phase to cubic ice in terms of the nucleation of small domains in the ice. This model agrees well with the behavior of water ice in our electron microscopy studies and finds that pure water above the glass transition is a strong liquid. In more recent work, we have concentrated on temperatures above the crystallization temperature and we find interesting morphological changes related to the decrease in viscosity of the amorphous component in the cubic crystalline regime. Given enough time, we would like to put these results in an astrophysical context and discuss some observed features of the frost on interstellar grains and the bulk ice in comets.
Jenniskens, P.↗
X-ray diffraction and in situ pressurization of dentine apatite reveals nanocrystal modulus stiffening upon carbonate removal
Bone-like materials comprise carbonated-hydroxyapatite nanocrystals (c-Ap) embedding a fibrillar collagen matrix. The mineral particles stiffen the nanocomposite by tight attachment to the protein fibrils creating a high strength and toughness material. The nanometer dimensions of c-Ap crystals make it very challenging to measure their mechanical properties. Mineral in bony tissues such as dentine contains 2~6 wt.% carbonate with possibly different elastic properties as compared with crystalline hydroxyapatite. Here we determine strain in biogenic apatite nanocrystals by directly measuring atomic deformation in pig dentine before and after removing carbonate. Transmission electron microscopy revealed the platy 3D morphology while atom probe tomography revealed carbon inside the calcium rich domains. High-energy X-ray diffraction in combination with in situ hydrostatic pressurization quantified reversible c-Ap deformations. Additionally, crystal strains differed between annealed and ashed (decarbonated) samples, following 1 or 10 h heating at 250 °C or 550 °C respectively. Measured bulk moduli (K) and a-/c-lattice deformation ratios (η) were used to generate synthetic K syn and ηsyn identifying the most likely elastic constants C 33 and C 13 for c-Ap. These were then used to calculate the nanoparticle elastic moduli. For ashed samples, we find an average E 11 =107 GPa and E 33 =128 GPa corresponding to ~5% and ~17% stiffening of the a-/c-axes of the nanocrystals as compared with the biogenic nanocrystals in annealed samples. Ashed samples exhibit ~10% lower Poisson's ratios as compared with the 0.25~0.36 range of carbonated apatite. Carbonate in c-Ap may therefore serve for tuning local deformability within bony tissues.
36 MATERIALS SCIENCE↗
Highly Oriented Organic Ferroelectric Films with Single-Crystal-Level Properties from Restrained Crystallization
Device applications often require thin film growth with quasi-two-dimensional morphology and crystallization which are not always compatible. In this work, we exploit the method of low-temperature deposition followed by restrained crystallization (LDRC) in the growth of crystalline organic molecular thin films, which tend to grow three-dimensionally with random orientations. We demonstrate that, for 2-methylbenzimidazole (MBI), a molecular ferroelectric that tends to crystalize in spherulites, the quasi-two-dimensional films can be grown using LDRC with highly oriented polar axes and single-crystal-level ferroelectric properties. The crystallization process was shown to occur during the post-deposition annealing process using the in situ electrical measurements. The limited diffusion, low nucleation density, and low activation energy was found critical for the formation of the plate-shaped quasi-two-dimensional films. These results mark an important step in elucidating the LDRC as an effective and general approach for fabricating films with balanced crystallinity and morphology which are critical for applications.
36 MATERIALS SCIENCE↗
Understanding the Effect of Sample Geometry on Temperature Distribution during Optical Floating Zone Crystal Growth in Vacuum Environment through Heat Transfer Modeling
Optical floating zone furnaces (OFZ) have had a transformative impact on fundamental science due to their ability to rapidly produce large single crystals of a wide variety of complex materials. However, a quantitative understanding of the OFZ growth environment is generally lacking due to the difficulty of measuring the local sample temperatures during OFZ growth, as well as to the general lack of information about the temperature-dependent physical parameters needed to model heat transfer. To overcome these challenges, we apply a physics-based heat transfer model, parametrized by measurements from synchrotron experiments and a machine-learning (ML) algorithm, to simulate the temperature distributions of samples heated in an OFZ furnace in a vacuum environment. This model is used to quantitatively understand how the sample maximum temperature and temperature gradient (key parameters that influence the success of crystal growth) are affected by the rod size, rod shape, and heat-zone position on the rod. The results of this study can be applied to make informed decisions on how crystal growth parameters can be tuned to modify temperature profiles and to optimize crystal growth outcomes even when data on internal sample temperature profiles (e.g., those obtained through in situ synchrotron experiments) are not accessible.
36 MATERIALS SCIENCE↗
Synthesis, Stability, and Magnetic Properties of Antiperovskite Co 3 PdN
Experimental synthesis and characterization of theoretically predicted compounds are important steps in the materials discovery pipeline. Here, we report on the synthesis of Co 3 PdN, which was recently predicted to be a stable magnetic antiperovskite. The Co 3 PdN thin films were grown by reactive sputtering and were confirmed to form in an antiperovskite crystal structure. The thermal stability of the compound is demonstrated up to 600 K by in situ X-ray diffraction, though the phase persists at slightly higher temperatures (700 K) in an air-free magnetometer. Both ab initio calculations and magnetization measurements find Co 3 PdN to be ferromagnetic with an experimentally determined Curie temperature of T C = 560 ± 5 K. The saturation magnetization of 1.2 μ B /Co found in the experiment is slightly lower than the 1.7 μ B /Co value expected by theory. A narrow magnetic hysteresis loop with a coercive field of 100 Oe at low temperature suggests that Co 3 PdN might be useful in electronic applications requiring fast switching of the magnetization vector. While prior prediction of Co 3 PdN showed a gapped electronic band structure for each spin channel, we show that this was due to incomplete sampling of Brillouin zone paths and that band crossings exist along R-X|M and X|M-R paths. The metallic nature of Co 3 PdN is further confirmed by temperature-dependent transport measurements, which also show a considerable anomalous Hall effect. Altogether, this work represents an appreciable step toward understanding the synthesis, structure, stability, and properties of a new magnetic material.
14 SOLAR ENERGY↗
Active-Site Determination and Mechanistic Insights in a MOF-Supported Polymerization Catalyst
The structural elucidation of catalyst active sites in heterogeneous catalysts when supported by traditional metal oxides remains a challenge despite the advanced characterization techniques that have been developed. The catalyst-deposition-site nonuniformity in metal oxides inhibits clear structural characterization through bulk spectroscopic methods and rules out the use of single-crystal X-ray diffraction. However, for metal-organic framework (MOF)-supported catalysts, the crystallinity and uniform structures of the underlying support enhance our ability to identify the precatalyst and catalytically active sites and open the door to using single-crystal X-ray diffraction coupled with spectroscopy under reaction conditions. Additionally, the use of in situ X-ray absorption spectroscopy identifies the catalytically active site in diethylaluminum chloride (DEAC)-pretreated Cr-SIM-NU-1000 to be a Cr-ethyl when used for ethylene polymerization. Further kinetic experiments elucidate the effects of ethylene pressure, temperature, catalyst loading, and cocatalyst loading, furthering mechanistic knowledge and helping to deconvolute the structure-function relationship.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Quantification of Metabolic Products from Microbial Hosts in Complex Media Using Optically Diffracting Hydrogels
In this work, we herein describe a highly versatile platform approach for the in situ and real-time screening of microbial biocatalysts for enhanced production of bioproducts using photonic crystal hydrogels. This approach was demonstrated by preparing optically diffracting films based on polymerized N-isopropylacrylamide that contracted in the presence of alcohols and organic acids. The hydrogel films were prepared in a microwell plate format, which allows for high-throughput screening, and characterized optically using a microwell plate reader. While demonstrating the ability to detect a broad range of relevant alcohols and organic acids, we showed that the response of the films correlated strongly with the octanol-water partition coefficient (log P) of the analyte. Differences in the secretion of ethanol and succinic acid from strains of Zymomonas mobilis and Actinobacillus succinogenes, respectively, were further detected via optical characterization of the films. These differences, which in some cases were as low as ~3 g/L, were confirmed by high-performance liquid chromatography, thereby demonstrating the sensitivity of this approach. Our findings highlight the potential utility of this multiplexed approach for the detection of small organic analytes in complex biological media, which overcomes a major challenge in conventional optical sensing methods.
09 BIOMASS FUELS↗
Nanoscale observations of Fe(ii)-induced ferrihydrite transformation
Because of its sorption properties, transformation of the nanomineral ferrihydrite (Fh) into more stable lepidocrocite (Lp) or goethite (Gt) has important impacts on the fate of metals, nutrients, and contaminants in soils/sediments. Although it is well known that the transformation rate is greatly accelerated under suboxic conditions by aqueous Fe(II), the enabling mass transfer process remains an ongoing debate among various mechanisms including dissolution/reprecipitation, solid-state recrystallization, and particle-mediated growth. In this paper, using electron microscopy, we examine the mineralogical evolution of 2-line Fh to Lp/Gt catalyzed by Fe(II) under strict anoxic conditions, including evaluation of Cl–SO 4 –HCO 3 anion effects. Emergence of Lp/Gt crystallites at the nanoscale was observed at ~20 min of reaction, earlier than previously reported. Lp is the first phase to nucleate in Cl-rich solutions without HCO 3 – ; whereas Lp and Gt concomitantly nucleate in SO 4 2– -rich solutions, and also when co-solute HCO 3 – is added. Lp crystallites nucleate as quasi-2D nanosheets one-unit-cell thick that contour the Fh surface; in contrast, rod-shaped (in Cl/SO 4 ) or acicular needle-shaped (in HCO 3 ) Gt crystals nucleate and grow radially outward from the Fh aggregates. Stages of transformation monitored by in situ μ-XRD coupled with aqueous Fe(II) uptake/release measurements are correlated with a short initial sorption stage followed by the onset of Lp/Gt growth that then progresses to Lp loss in favor of Gt. Microscopy data overwhelmingly support dissolution/reprecipitation as the underlying mechanism, including direct evidence for classical ion-by-ion Lp/Gt growth and Lp dissolution. The collective findings imply that the iron mass transfer through solution to distal Lp/Gt growth fronts is a critical enabling process facilitating rapid transformation.
54 ENVIRONMENTAL SCIENCES↗
The Orthogonal In-Situ Machining of Single and Polycrystalline Aluminum and Copper, Volume 1
Metal cutting is a unique deformation process characterized by large strains, exceptionally high strain rates and few constraints to the deformation. These factors, along with the difficulty of directly measuring the shear angle, make chip formation difficult to model and understand. One technique for skirting the difficulty of post mortem chip measurement is to perform a cutting experiment dynamically in a scanning electron microscope. The performance of the in-situ experiment with full instrumentation allows for component force measurement, orientation measurement (on a round single crystal disk) and a timing device, all superimposed below the deformation on the TV monitor and recorded for future viewing. This allows the sher angle to be directly measured for the screen along with the other needed information.
Cohen, P. H.↗
What if chondritic porous interplanetary dust particles are not the real McCoy
To select a target comet for a Comet Nucleus Sample Return Mission (CNSRM) it is necessary to have an experimental data base to evaluate the extent of diversity and similarity of comets. For example, the physical properties (e.g., low density) of chondritic porous (CP) interplanetary dust particles (IDPs) are believed to resemble these properties of cometary dust although it is yet to be demonstrated that the porous structure of CP IDPs is inherent to presolar dust particles stored in comet nuclei. Porous structures of IDPs could conceivably form during sublimation at the surface of active comet nuclei. Porous structures are also obtained during annealing of amorphous Mg-SiO smokes which initially forms porous aggregates of olivine + platey tridymite and which, upon continued annealing, react to fluffy enstatite aggregates. It is therefore uncertain that CP IDPs are entirely composed of unmetamorphosed presolar dust. Conceivably, new minerals and textures may form in situ in nuclei of active comets as a function of their individual thermal history. Unmetamorphosed comet dust is probably structurally amorphous. Thermal annealing of this dust can produce ultra fine-grained minerals and this ultrafine grain size of CP IDPs should be considered in assessments of aqueous alterations that could affect presolar dust in comet nuclei between 200 and 400 K. Devitrification and hydration may occur in situ in ice-dust mixtures and the mantle of active comet nuclei. Devitrification, or uncontrolled crystallization, of amorphous precursor dust can produce a range of chemical compositions of ultrafine-grained minerals and (non-equilibrium) mineral assemblages and textures in dust contained in comet nuclei as a function of period and trajectory of orbit and number of perihelion passages (not considering internal heating). Thus, experimental data on relevant processes and reaction rates between 200 and 400 K are needed in order to evaluate comet selection, penetration depth for sampling device and curation of samples for CNSRM.
Rietmeijer, Frans J. M.↗
Measurements of Trace Gases Using a Tunable Diode Laser
This report is the final report for "Measurements of Trace Gases Using a Tunable Diode Laser." The tasks outlined in the proposal are listed below with a brief comment. The publications and the conference presentations are listed. Finally, the important publications are attached. The Cooperative Agreement made possible a research effort to produce high- precision and high-accuracy in-situ measurements of carbon monoxide, methane and nitrous oxide on the WB-57 during the CRYSTAL-FACE and pre-AVE field campaigns and to analyze these measurements. These measurements of CO and CH4 were of utmost importance to studies of the radiative effects of clouds. Some important results of the CRYSTAL-FACE program were contained in two scientific papers (attached). This Cooperative Agreement allowed the participation of the Argus instrument in the program and the analysis of the data.
Jost, Hans-Juerg↗
In situ temperature synthesis and characterization of ferroelectric PZN-4.5PT nanoparticles’ thin films using synchrotron light source
Despite the excellent properties of Pb(Zn 1/3 Nb 2/3 )O 3 -4.5PbTiO 3 (PZN-4.5PT) single crystals, the greatest difficulty for their application on electronic devices is to make them to thin layers related to the difficulty to make them as ceramic materials. In this paper, we use the combined USAXS/SAXS/WAXS instrument at 9ID beamline at APS-ANL for in situ characterization of PZN-4.5PT inorganic perovskite nanoparticles thin films deposited on nanotextured silicon to understand the phase transitions and determine the observed microcrystals' structure. Here, the sample was annealed from ambient to 1000°C. The results revealed structure changes in the nanoparticles' thin films which could be explained by the new phase that can be assigned to the Pb 3 (PO 4 )2-based component. The peak at 31° indicates the presence of the rhombohedral phase perovskites assigned to the nanoparticles. WAXS characterization permitted to identification of many transitions during thermal annealing like dehydration or dihydroxylation of phosphorus gel -OH bonds and internal water.
36 MATERIALS SCIENCE↗
Tailoring the structure and electrochemical performance of sodium titanate anodes by post-synthesis heating
Sodium titanate anodes synthesized via “chimie-douce” methods generally require a post-synthesis dehydration step. Their crystal structures are sensitive to the heating conditions such as temperature, resulting in distinct sodium storage performance. Herein, using in situ and ex situ high-temperature X-ray diffraction, we studied in detail the structural changes of Na 0.74 Ti 1.815 $\square$ 0.185 O 4 ·1.27H 2 O (NTO) under various heating conditions. Electrochemical characterization revealed that NTOs heated at lower temperatures with layered structures deliver larger capacities than those heated at high temperatures with tunnel structures. Heat treatment at moderate temperatures greatly improves the capacity retention of NTO, especially stabilizing the high voltage processes that are major contributors to the capacity fading, because of the modified crystal structure and surface chemistry. As a result, our findings suggest that post-synthesis heating is a simple and effective strategy to tailor the crystal structure, surface chemistry, and electrochemical properties of sodium titanate anodes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗