Search NASA⌕ Search

SEARCH · Search NASA

Results for “Crystal preferred orientation”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 91 records · Page 5

Anisotropic Tribological Properties of Silicon Carbide

The anisotropic friction, deformation and fracture behavior of single crystal silicon carbide surfaces were investigated in two categories. The categories were called adhesive and abrasive wear processes, respectively. In the adhesive wear process, the adhesion, friction and wear of silicon carbide were markedly dependent on crystallographic orientation. The force to reestablish the shearing fracture of adhesive bond at the interface between silicon carbide and metal was the lowest in the preferred orientation of silicon carbide slip system. The fracturing of silicon carbide occurred near the adhesive bond to metal and it was due to primary cleavages of both prismatic (10(-1)0) and basal (0001) planes.

Miyoshi, K.↗

Transmission Electron Microscopy of Magnetite Plaquettes in Orgueil

Magnetite sometimes takes the form of a plaquette - barrel-shaped stack of magnetite disks - in carbonaceous chondrites (CC) that show evidence of aqueous alteration. The asymmetric nature of the plaquettes caused Pizzarello and Groy to propose magnetite plaquettes as a naturally asymmetric mineral that can indroduce symmetry-breaking in organic molecules. Our previous synchrotron X-ray computed microtomography (SXRCT) and electron backscatter diffraction (EBSD) analyses of the magnetite plaquettes in fifteen CCs indicate that magnetite plaquettes are composed of nearly parallel discs, and the crystallographic orientations of the discs change around a rotational axis normal to the discs surfaces. In order to further investigate the nanostructures of magnetite plaquettes, we made two focused ion beam (FIB) sections of nine magnetite plaquettes from a thin section of CI Orgueil for transmission electron microscope (TEM) analysis. The X-ray spectrum imaging shows that the magnetite discs are purely iron oxide Fe3O4 (42.9 at% Fe and 57.1 at% O), which suggest that the plaquettes are of aqueous origin as it is difficult to form pure magnetite as a nebular condensate. The selected area electron diffraction (SAED) patterns acquired across the plaquettes show that the magnetite discs are single crystals. SEM and EBSD analyses suggest that the planar surfaces of the magnetite discs belong to the {100} planes of the cubic inverse spinel structure, which are supported by our TEM observations. Kerridge et al. suggested that the epitaxial relationship between magnetite plaquette and carbonate determines the magnetite face. However, according to our TEM observation, the association of magnetite with porous networks of phyllosilicate indicates that the epitaxial relationship with carbonate is not essential to the formation of magnetite plaquettes. It was difficult to determine the preferred rotational orientation of the plaquettes due to the symmetry of the cubic structure, however, we are able to observe small but consistent rotational orientation across several discs within a plaquette.

Chan, Q. H. S.↗

Water Storage and Transport Processes During Impact Experiments on Nominally Anhydrous Minerals

Water, in the form of structurally bound hydrogen in the crystal lattice of nominally anhydrous minerals (NAMs), strongly influences many important physical processes on terrestrial planets and planetary objects. Water enhances the rates of plastic deformation and controls the degree of partial melting in silicate rocks, which influences the generation of melt and therefore the nature of planetary volcanism. Water has also been experimentally demonstrated to influence the nature of lattice preferred orientation in deformed aggregates, and thus may be important in the interpretation of seismic anisotropy data collected from planetary bodies, such as from the current InSight mission on Mars. Therefore, much attention has been focused on characterizing the distribution and concentration of water in the planets and rocky bodies of our solar system.

Tielke, J.↗

High temperature neutron diffraction investigation of U 3 Si 2

The U-Si system is actively undergoing studies due to its promise as a component of an accident tolerant nuclear fuel. In this work, the crystal structure of the U 3 Si 2 compound in the U-Si system was investigated as a function of temperature from room temperature to 1298 K for a sample of approximately 42.02 at.% Si composition and 1373 K for a sample with approximately 42.10 at.% Si using high temperature time-of-flight neutron diffraction on the High-Pressure Preferred Orientation (HIPPO) diffractometer at Los Alamos Neutron Science Center (LANSCE). The simultaneous Rietveld refinement of five histograms from the five HIPPO detector backs (40°, 60°, 90°, 120°, and 145°) provided datasets for the lattice parameters, anisotropic atomic displacement parameters, and atomic positions as a function of temperature. To explore the possibility of a homogeneity range, two sample compositions were analyzed, a 40.02 at.% Si (near stoichiometric) and a potentially hyperstoichiometric (40.10 at.% Si) sample. While minor differences in the anisotropic atomic displacement parameters between the two samples were observed, over the entire investigated temperature range no additional phases were found indicative of a single phase sample and the ability of the U 3 Si 2 compound to accommodate nonstoichiometry, suggesting that the U 3 Si 2 compound is not a line compound confirming previous determinations. However, the differences observed in the average coefficient of linear thermal expansion identified between the two compositions warrant future investigation.

36 MATERIALS SCIENCE↗

Transient oxidation of single-crystal beta-NiAl

The transient oxidation of beta-NiAl in air at 800 C and 1100 C has been studied using electron microscopy. The oxide scale consists predominantly of metastable Al2O3 phases. Theta-Al2O3 is the major oxide phase within 10.0 hr of oxidation at 800 C and 0.1 hr at 1100 C. The scales form epitaxially on (001) sub beta and (012) sub beta specimens throughout the transient stage, whereas the degree of preferred oxide orientation decreases with oxidation time on (011) sub beta and (111) sub beta specimens. The orientation relationships reflect the small mismatch between parallel close-packed directions in the metal and in the cation sublattice of the oxides. The correlation of distinctive oxide surface morphologies with internal structural defects indicates the strong tendency of the Al2O3 scale to grow via short-circuit diffusion paths.

Doychak, J.↗

Fission yeast Duf89 and Duf8901 are cobalt/nickel-dependent phosphatase–pyrophosphatases that act via a covalent aspartyl–phosphate intermediate

Domain of Unknown Function 89 (DUF89) proteins are metal-dependent phosphohydrolases. Exemplary DUF89 enzymes differ in their metal and phosphosubstrate preferences. Here, we interrogated the activities and structures of two DUF89 paralogs from fission yeast—Duf89 and Duf8901. We find that Duf89 and Duf8901 are cobalt/nickel-dependent phosphohydrolases adept at hydrolyzing p-nitrophenylphosphate and PP i . Crystal structures of metal-free Duf89 and Co 2+ -bound Duf8901 disclosed two enzyme conformations that differed with respect to the position of a three-helix module, which is either oriented away from the active site in Duf89 or forms a lid over the active site in Duf8901. Lid closure results in a 16 Å movement of Duf8901 Asp195, vis-à-vis Asp199 in Duf89, that brings Asp195 into contact with an octahedrally coordinated cobalt. Reaction of Duf8901 with BeCl 2 and NaF in the presence of divalent cations Co 2+ , Ni 2+ , or Zn 2+ generated covalent Duf8901-(Asp248)–beryllium trifluoride (BeF 3 )•Co 2+ , Duf8901-(Asp248)–BeF 3 •Ni 2+ , or Duf8901-(Asp248)–BeF 3 •Zn 2+ adducts, the structures of which suggest a two-step catalytic mechanism via formation and hydrolysis of an enzyme-(aspartyl)–phosphate intermediate. Alanine mutations of Duf8901 Asp248, Asn249, Lys401, Asp286, and Asp195 that interact with BeF 3 •Co 2+ squelched p-nitrophenylphosphatase activity. A 1.8 Å structure of a Duf8901-(Asp248)–AlF 4 –OH 2 •Co 2+ transition-state mimetic suggests an associative mechanism in which Asp195 and Asp363 orient and activate the water nucleophile. Whereas deletion of the duf89 gene elicited a phenotype in which expression of phosphate homeostasis gene pho1 was derepressed, deleting duf8901 did not, thereby hinting that the DUF89 paralogs have distinct functional repertoires in vivo.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deciphering the evolution of flavin-dependent monooxygenase stereoselectivity using ancestral sequence reconstruction

Controlling the selectivity of a reaction is critical for target-oriented synthesis. Accessing complementary selectivity profiles enables divergent synthetic strategies, but is challenging to achieve in biocatalytic reactions given enzymes’ innate preferences of a single selectivity. Thus, it is critical to understand the structural features that control selectivity in biocatalytic reactions to achieve tunable selectivity. Here, we investigate the structural features that control the stereoselectivity in an oxidative dearomatization reaction that is key to making azaphilone natural products. Crystal structures of enantiocomplementary biocatalysts guided the development of multiple hypotheses centered on the structural features that control the stereochemical outcome of the reaction; however, in many cases, direct substitutions of active site residues in natural proteins led to inactive enzymes. Ancestral sequence reconstruction (ASR) and resurrection were employed as an alternative strategy to probe the impact of each residue on the stereochemical outcome of the dearomatization reaction. These studies suggest that two mechanisms are active in controlling the stereochemical outcome of the oxidative dearomatization reaction: one involving multiple active site residues in AzaH and the other dominated by a single Phe to Tyr switch in TropB and AfoD. Moreover, this study suggests that the flavin-dependent monooxygenases (FDMOs) adopt simple and flexible strategies to control stereoselectivity, which has led to stereocomplementary azaphilone natural products produced by fungi. This paradigm of combining ASR and resurrection with mutational and computational studies showcases sets of tools for understanding enzyme mechanisms and provides a solid foundation for future protein engineering efforts.

Science & Technology - Other Topics↗

Energy based fracture initiation criterion for strain-crystallizing rubber-like materials with pre-existing cracks

Fracture prediction is indispensable for polymers, like rubbers, which have a broad range of applications mainly due to their high extensibility. The phenomenon known as strain-induced crystallization further contributes to the fracture toughness of certain rubbers. Here in this study, a criterion based on internal bond energy, incorporating the effects of crystallization, is proposed to predict fracture initiation in rubber-like materials with pre-existing cracks. First, a multi-scale mechanical model is developed for characterizing the behavior of rubber when subjected to both uniaxial and biaxial deformation states. At the microscale, both the amorphous and crystalline chain segments are modeled as elastic in order to consider the energy contribution by the molecular bond distortions. This internal energy is considered along with the entropic and crystalline free energy for each chain. In the chain model, the effects of loading condition and the relative orientation of a chain on its crystallinity are taken into account. At the macroscopic scale, an existing crystallinity distribution function is adapted and a mixed finite element formulation with an augmented Lagrangian multiplier is utilized to impose the incompressibility constraint. A non-affine maximal advance path constraint based homogenization model is utilized for bridging the two scales. Its potential to account for anisotropy in the stretched network compels the model to be preferable due to its physical significance, for the purpose of fracture modeling. The rigidity of the crystallites is accounted for by proposing a crystallite distortion energy in addition to the critical bond dissociation energy, for fracture initiation to occur. The model is validated by comparison with existing experimental results for both crystallizing and non-crystallizing rubbers. In addition to its potential to predict the material behavior when subjected to uniaxial and biaxial loading, the capability of the model to quantitatively estimate the effect of crystallization on fracture initiation is also verified.

36 MATERIALS SCIENCE↗

Intermolecular correlations of liquid and glassy CS 2 studied by synchrotron radiation x-ray diffraction

How is the orientation of molecular liquids ordered on cooling? What are the basic structures of molecular glasses, e.g., close to the crystalline structure or some special structures such as icosahedral cluster? These are long-standing questions in liquid and glass physics. Here, we have constructed a novel cryostat to prepare simple molecular glasses by vapor deposition and performed in situ synchrotron radiation x-ray diffraction experiments. The glassy state of a simple molecule CS 2 , which cannot be vitrified by normal liquid quenching, was successfully prepared with this instrument, and its diffraction data were collected in a wide Q-range of 0.16–25.7 Å -1 with a high-energy diffractometer at BL04B2, SPring-8. The diffraction data of liquid CS 2 were also recorded in a wide temperature range of 160–300 K. These diffraction data were analyzed with molecular dynamics simulations and reverse Monte Carlo modelings to investigate orientational correlation. From the obtained 3D structure models, the orientational correlation between neighboring CS 2 molecules was investigated quantitatively as a function of temperature. At room temperature, the parallel and T-shaped arrangements are preferred for the nearest neighbor correlation. On cooling, these arrangements are developed gradually, and its rate became prominent below the melting temperature (162 K). In the glassy state, the slipped-parallel arrangement is dominant as well as the T-shaped arrangement. Both arrangements appear in the CS 2 crystal, indicating that the structure of glassy CS 2 is close to that of crystalline CS 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cryo neutron crystallography demonstrates influence of RNA 2'-OH orientation on conformation, sugar pucker and water structure

The ribose 2'-hydroxyl is the key chemical difference between RNA and DNA and primary source of their divergent structural and functional characteristics. Macromolecular X-ray diffraction experiments typically do not reveal the positions of hydrogen atoms. Thus, standard crystallography cannot determine 2'-OH orientation (H2'-C2'-O2'-HO2' torsion angle) and its potential roles in sculpting the RNA backbone and the expansive fold space. Here, we report the first neutron crystal structure of an RNA, the Escherichia coli rRNA Sarcin-Ricin Loop (SRL). 2'-OD orientations were established for all 27 residues and revealed O-D bonds pointing toward backbone (O3', 13 observations), nucleobase (11) or sugar (3). Most riboses in the SRL stem region show a 2'-OD backbone-orientation. GAGA-tetraloop riboses display a 2'-OD base-orientation. An atypical C2'-endo sugar pucker is strictly correlated with a 2'-OD sugar-orientation. Neutrons reveal the strong preference of the 2'-OH to donate in H-bonds and that 2'-OH orientation affects both backbone geometry and ribose pucker. We discuss 2'-OH and water molecule orientations in the SRL neutron structure and compare with results from a solution phase 10 μs MD simulation. We demonstrate that joint cryo-neutron/X-ray crystallography offers an all-in-one approach to determine the complete structural properties of RNA, i.e. geometry, conformation, protonation state and hydration structure.

59 BASIC BIOLOGICAL SCIENCES↗

Mesocrystalline Ordering and Phase Transformation of Iron Oxide Biominerals in the Ultrahard Teeth of Cryptochiton stelleri

Biological organisms naturally synthesize complex, hierarchical, multifunctional materials through mineralization processes at ambient conditions and under physiological pH. One such example is the ultrahard and wear-resistant radular teeth found in mollusks, which are used to scape against the rock to feed on algae. Herein, the biologically controlled structural development of the hard, outer magnetite-containing shell of the chitin teeth is revealed. Specifically, the formation of a series of mesocrystalline iron oxide phases, templated by chitin-binding proteins, is identified. The initial domains, consisting of ferrihydrite mesocrystals with a spherulite-like morphology, undergo a solid-state phase transformation to form magnetite while maintaining mesocrystallinity, likely via a shear-induced solid-state reaction, without any noticeable architectural changes. Subsequent growth via Ostwald ripening leads to nearly single-crystalline rod-like elements. In addition, an interpenetrating organic matrix is identified that, at early stages of tooth development, potentially contains iron-binding proteins that guide the self-assembly of the mesocrystalline mineral and influence the preferred orientation of the later-formed magnetite nanorods, which ultimately determines the mechanical behavior of the mature chiton teeth.

36 MATERIALS SCIENCE↗

Comparison of excess free energy at an interface according to the applied interpolation scheme for elasticity: A phase-field method

Phase-field modeling is an effective simulation technique for modeling microstructure evolution of elastically anisotropic systems. To introduce the elastic energy contribution in a phase field model, an interpolation scheme is used to define the mechanical properties within the phases and across the continuous interface. Several existing interpolation schemes introduce a potential excess elastic energy at the interface, which undesirable effect on microstructure evolution needs to be evaluated. In this study, we focused on three interpolation schemes including Khachaturyan’ scheme (KHS), Voigt–Taylor’s scheme (VTS), and Steinbach–Apel’s scheme (SAS). Comparisons of these schemes’ performances were performed in three configuration types using the MOOSE (Multiphysics Object-Oriented Simulation Environment) framework: bi-crystal, isotropic particle-matrix and anisotropic particle-matrix. The contribution of excess elastic energy on the interface energy as a function of interface width and the computational time to steady-state were evaluated in these three configurations. SAS introduces the lowest excess elastic energy contribution and the VTS has the biggest contribution amongst the considered schemes. Moreover, when modeling precipitation in an anisotropic elastic material, the SAS approach seems to predict more physical convex shapes during growth, making it preferable to KHS and VTS. Finally, as currently implemented, SAS requires the largest computational time and KHS requires the smallest time to reach steady-state amongst the considered schemes.

36 MATERIALS SCIENCE↗

Single Crystals of Vanadium Oxides as a Lens for Understanding Structural and Electronic Phase Transformations, Ion Transport, Chemo-Mechanical Coupling, and Electrothermal Neuronal Emulation

Vanadium oxides cystallize in a diverse array of structures and compositions arising from the redox versatility of vanadium, variable covalency of V−O bonds, and myriad coordination geometries. Their open frameworks present abundant interstitial sites that enable insertion of guest-ions. In such compounds, V3d electron and spin localization and disorder couple strongly to structural preferences. The rich structural diversity manifests as a “rugged” free energy landscape with multiple interconvertible polymorphs. Such a landscape sets up structural, electronic, and magnetic transitions that underpin the promise of these materials as ion-insertion battery electrodes; compact primitives for brain-inspired computing, and heterogeneous catalysts. Here, we examine the structural and compositional diversity, electronic instabilities, defect dynamics, structure transformations, mechanical properties, and surface structure of vanadium oxides using single crystals as a distinctive lens. Single crystals enable the measurement of structure−function correlations without the ensemble and orientational averaging inevitable in polycrystalline materials. Their well-defined surfaces further enable examination of facet-dependent reactivity toward molecular adsorbates, ion fluxes, and lattice (mis)matched solids. We provide a comprehensive account of vanadium-oxide single-crystal studies, from delineation of common structural motifs to single-crystal growth techniques, topochemical modification strategies, mechanisms underpinning electronic instabilities, and implementation as electrothermal neurons and battery electrode materials.

Ponis, John [Texas A&M University, College Station↗

Microstructure Evolution of U–Zr System in A Thermal Cycling Neutron Diffraction Experiment: Extruded U–10Zr (wt. %)

Microstructure evolution of 1073 K extruded U–10Zr (wt. %) fuel during thermal cycling (303–1073 K with a ~9 hour hold at 873 K during cooling) was investigated using in situ neutron diffraction. Analysis was performed using Rietveld texture and crystal structure refinements from time–of–flight neutron diffraction data, with a focus on the evolution of textures and lattice parameters as a function of temperature. The α–U phase exhibits lattice contraction with increasing temperature along the b lattice direction and lattice expansion in the other directions while the other phases exhibit lattice expansion with temperature in all directions. Contrary to the established phase diagram, the β–U phase is absent at the temperatures of the thermal cycling. (001) α and (110) γ plane normals are observed with a strong preferred orientation along the extrusion direction. Finally, the variant selection of (001) α ||(110) γ is observed for the first time.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Seismic Visibility of Eclogite in the Earth’s Upper Mantle—Implications From High Pressure‐Temperature Single‐Crystal Elastic Properties of Omphacite

Abstract Identifying and locating the geochemical and geophysical heterogeneities in the Earth’s interior is one of the most important and challenging tasks for the deep Earth scientists. Subducted oceanic crust metamorphizes into the dense eclogite in the upper mantle and is considered as a major cause of geochemical and geophysical heterogeneities in the deep Earth. In order to detect eclogitic materials inside the Earth, precise measurements of the high pressure‐temperature single‐crystal elasticity of major minerals in eclogite are thus exceedingly important. Omphacite, a Na,Al‐bearing clinopyroxene, constitutes up to 75 vol% of eclogite. In the present study, we performed the first high pressure‐temperature single‐crystal elasticity measurements of omphacite using Brillouin spectroscopy. Utilizing the finite‐strain approach, we obtained the following thermoelastic parameters for omphacite: K S0 ’ = 4.5(1), G 0 ’ = 1.53(5), ∂K S0 /∂ T = −0.029(5) GPa/K, ∂G 0 /∂ T = −0.013(5) GPa/K, with K S0 = 123(3) GPa, G 0 = 74(2) GPa, and ρ 0 = 3.34(1) g/cm 3 . We found that the seismic velocities of undeformed eclogite are similar to pyrolite at the depths of 200–300 and 410–500 km, thus eclogite is seismically invisible at these depths. Combined with the lattice‐preferred orientations of the omphacite in naturally deformed eclogites, we also modeled seismic anisotropy of eclogite at various pressure‐temperature conditions. A 10 km thick subducted eclogitic crust can result in ∼0.2 s shear wave splitting in the Earth’s upper mantle.

Hao, Ming↗

Endotaxial growth of CoSi2 within (111) oriented Si in a molecular beam epitaxy system

A new mode of growth is reported in which buried metallic layers can be fabricated within a single-crystal semiconductor through preferential subsurface growth on previously-grown 'seed' regions. The deposition of Co at 800 C at a rate of 0.01 nm/s on (111) Si substrates containing buried CoSi2 columns 40-100 nm below the Si surface results in the growth and coalescence of these subsurface columns. The formation of a CoSi2 layer on the Si surface is suppressed by this growth mode. It is proposed that the high diffusion rate of Co at 800 C, coupled with the high growth rate of CoSi2 at the subsurface columns, is responsible for this preferred 'endotaxial' growth mode. This growth technique was used to produce a continuous buried single-crystal layer of CoSi2 under a single-crystal Si capping layer.

George, T.↗

Influence of Nucleation Mechanisms on the Radiative Properties of Deep Convective Clouds and Subvisible Cirrus in CRYSTAL/FACE

During the past few years we have conducted work on several different topics, as reflected by our publications. As one of the Co-Project scientists for The Cirrus Regional Study of Tropical Anvils and Cirrus Layers - Florida Area Cirrus Experiment (CRYSTAL FACE) we worked to help design the mission and then conduct it in the field. Another major activity during the past two years has been to pull together various groups to formulate plans for follow on missions to CRYSTAL FACE. We organized a workshop at the University of Colorado during the summer of 2003 to assess the best locations for future missions. Working with a group of about 10 scientists from around the country we prepared a science-planning document (Tropical Composition, Cloud and Climate Coupling Experiment (TC(sup 4)) that outlined the rationale, locations, strategy to accomplish the goals, and possible payloads for a set of three tropical missions. We also prepared background materials for various NRAs being prepared at NASA Headquarters for missions in Costa Rica, Darwin and Guam. In conjunction with the group at NASA Ames we have helped build a new numerical model for deep convection and have applied that model to simulate the CRYSTAL data. Our goal in particular has been to better understand how convection distributes water vapor isotopes. CRYSTAL observations of water isotopes are very different from those suggested by previous workers who assumed the isotopes would obey Rayleigh fractionation. The water isotope study has several implications. First it is a check on the realism of the deep convection model. Second, the isotopes are a measure of the precipitation removal in the atmosphere. Hence they provide a constraint on a parameter that is difficult to otherwise measure. Finally it has been suggested that isotopes may be the key to unraveling the water transport into the stratosphere and upper troposphere. Such transport is critical both for the radiation balance and for stratospheric chemistry. Ours is the first model that is able to treat this transport. Our initial results have just been submitted to Geophys. Res. Lett (Smith et al., 2005). Essentially we are able to explain the vertical profiles of isotopes in the tropical tropopause transition layer. We are also able to account for stratospheric humidity and isotope abundances with this model. We have also been heavily involved in trying to improve our understanding of nitric acid condensation on ice. Gao et al (2004) have shown that water supersaturations above ice occur when the atmosphere is supersaturated with respect to nitric acid trihydrate. As one of the co-authors of that work, we suggested the mechanism that may explain why this is occurring. Essentially, ice does not like to grow near unit supersaturation, but does so because the water molecules can find sites on the ice surface to attach themselves to before they fly off the ice surface. This phenomena was well known in the 1960s when it was a source of debate about whether condensation and evaporation coefficients for ice would be the same. Evaporation does not require any molecular orientation, while condensation does, so it was possible that the coefficients would differ. They don't differ because the water molecules rapidly move across the surface and find places to attach. Nitric acid may be occupying these preferred sites and therefore the water molecules can't find a desirable place to attach. We anticipate that this research will be the subject of laboratory work during the coming few years. Another possibility that has been suggested is that cubic ice is forming in clouds. We have measured the vapor pressure of cubic ice, and plan to publish that result in the next few months. We have also been working on additional aspects of the condensation of nitric acid on ice. With Y. Kondo we studied the condensation of NOy on ice using the SOLVE data. Gamblin et al. have continued this work. The CRYSTAL NOy and HNO, groups have shown th their data can be fit using standard Langmuir isotherms as suggested in some, but not all, laboratory studies. We have found in the SOLVE data set that this is not the case. Moreover some laboratory studies show there are important kinetic effects that may be occurring in the atmosphere limiting the transfer of nitric acid to the ice. The SOLVE data seem consistent with these studies. We are currently re-analyzing the CRYSTAL data to look for these kinetic effects. There are a number of implications of these studies. One of the more interesting is that the nitric acid coating on ice can be used as a cloud clock to determine how long the cloud parcel has been in existence. We have also been involved with several laboratory studies. We have worked to improve the database on ice optical constants, which are critical for remote sensing. We have also studied the ways in which ice nucleates on clays. We suspect now that the standard theories used for depositional ice nucleation are completely incorrect. Further work will be needed to develop a new theory.

Toon, Owen B.↗

Shear-aligned large-area organic semiconductor crystals through extended π–π interaction

Small molecule-based organic semiconductors are of broad interest in organic field-effect transistors (OFETs) due to their potential for high crystallinity and electrical performance. The 2D molecule, TIPS-peri-pentacenopentacene (TIPS-PPP), which is the vertical extension of the 1D TIPS-pentacene (TIPS-PEN) molecule, offers a lower bandgap, higher aromaticity, and an enhanced π–π interaction with neighboring molecules in the solid state when compared to TIPS-PEN. However, an in-depth understanding of the relationship between the molecule structure, solid-state molecular packing, and the electronic properties has not been reported due to poor control over the TIPS-PPP crystallite size. In this work, we successfully engineered highly oriented large-area TIPS-PPP crystals through the solution shear coating technique. Additionally, compared with narrow ribbon-like TIPS-PEN crystals, TIPS-PPP crystals can grow centimeters long and over 500 μm wide. TIPS-PPP molecules are less susceptible to forming metastable polymorphs than TIPS-PEN molecules upon fast evaporation. The crystal structure of TIPS-PPP is also thermally stable at 250 °C. Notably, the anisotropic charge carrier mobility of TIPS-PPP crystals is resolved through fabricating bottom-gate top-contact devices, with a hole mobility of 3.1 cm 2 V -1 s -1 along the preferred packing direction. Further device optimization using top-gate bottom-contact devices improved the mobility up to 6.5 cm 2 V -1 s -1 , which is among the highest for pentacene-derivative-based organic semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗