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Directly Observing Micelle Fusion and Growth in Solution by Liquid-Cell Transmission Electron Microscopy

Amphiphilic small molecules and polymers form commonplace nanoscale macromolecular compartments and bilayers, and as such are truly essential components in all cells and in many cellular processes. The nature of these architectures, including their formation, phase changes, and stimuli-response behaviors, is necessary for the most basic functions of life, and over the past half-century, these natural micellar structures have inspired a vast diversity of industrial products, from biomedicines to detergents, lubricants, and coatings. The importance of these materials and their ubiquity have made them the subject of intense investigation regarding their nanoscale dynamics with increasing interest in obtaining sufficient temporal and spatial resolution to directly observe nanoscale processes. However, the vast majority of experimental methods involve either bulk-averaging techniques including light, neutron, and X-ray scattering, or are static in nature including even the most advanced cryogenic transmission electron microscopy techniques. Here, we employ in situ liquid-cell transmission electron microscopy (LCTEM) to directly observe the evolution of individual amphiphilic block copolymer micellar nanoparticles in solution, in real time with nanometer spatial resolution. These observations, made on a proof-of-concept bioconjugate polymer amphiphile, revealed growth and evolution occurring by unimer addition processes and by particle-particle collision-and-fusion events. In conclusion, the experimental approach, combining direct LCTEM observation, quantitative analysis of LCTEM data, and correlated in silico simulations, provides a unique view of solvated soft matter nanoassemblies as they morph and evolve in time and space, enabling us to capture these phenomena in solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fabrication of Engineered Silica-Functionalized-Polyanilines Nanocomposites for Water Decontamination of Cadmium and Lead

In this study, two novel functionalized silica nanocomposites were synthesized via covalent bonding with nanopolyaniline (NPANI) and crosslinked nanopolyaniline (CrossNPANI) to produce [NSi-NPANI] and [NSi-CrossNPANI], respectively. The two nanocomposites were portrayed by SEM, FT-IR, HR-TEM, BET-surface and TGA. The HR-TEM images of [NSi-NPANI] and [NSi-CrossNPANI] confirmed the particle size in the range 14.28–21.43 and 26.19–35.71 nm, respectively and these two nanocomposites were successfully applied to remove divalent cadmium and lead from solutions. As compared to nanosilica [NSi] sorbent, the maximum capacity values of the two nanocomposites for divalent cadmium and lead were identified to increase from 100–250 µmole g{sup −1} (pH 1.0) to 750–800 µmole g{sup −1} (pH 7.0) and from 400–1050 µmole g{sup −1} (pH 1.0) to 650–1350 µmole g{sup −1} (pH 6.0), at the optimum conditions. The adsorption data were compared using two and three parameter equations based on Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, Redlish-Peterson and sips models. The kinetic study of [NSi-NPANI] and [NSi-CrossNPANI] revealed that the pseudo-second order kinetic was the best model to explain the kinetic data for cadmium(II) and lead(II). The free energy of sorption (ΔG{sup o}), enthalpy (ΔH{sup o}), and entropy (ΔS{sup o}) changes were calculated to portend the nature of adsorption. Adsorptive extraction of toxic lead and cadmium from tap water and wastewater was successfully accomplished with the range of percentage recovery values 98.5–100.0 and 91.9–93.0%, respectively.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

In-situ TEM study of the ion irradiation behavior of U 3 Si 2 and U 3 Si 5

We report that U 3 Si 2 and U 3 Si 5 are two important uranium silicide phases currently under extensive investigation as potential fuel forms or components for light water reactors (LWRs) to enhance accident tolerance. In this paper, their irradiation behaviors are studied by ion beam irradiations with various ion mass and energies, and their microstructure evolution is investigated by in-situ transmission electron microscopy (TEM). U 3 Si 2 can easily be amorphized by ion beam irradiations (by 1MeV Ar 2+ or Kr 2+ ) at room temperature with the critical amorphization dose less than 1 dpa. The critical amorphization temperatures of U 3 Si 2 irradiated by 1MeV Kr 2+ and 1MeV Ar 2+ ion are determined as 580±10K and 540±5K, respectively. In contrast, U 3 Si 5 remains crystalline up to 8 dpa at room temperature and is stable against ion irradiation-induced amorphization up to ~50 dpa by either 1MeV Kr 2+ or 150KeV Kr + at 623K. In conclusion, these results provide valuable experimental data to guide future irradiation experiments, support the relevant post irradiation examination, and serve as the experimental basis for the validation of advanced fuel performance models

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Tunable magnetic and magnetocaloric properties of La{sub 0.6}Sr{sub 0.4}MnO{sub 3} nanoparticles

Nanoparticles of La{sub 0.6}Sr{sub 0.4}MnO{sub 3} with different particle sizes are synthesized by the nitrate-complex auto-ignition method. The structural and magnetic properties of the samples are investigated by X-Ray diffraction (XRD), Fourier transform infra-red (FT-IR) spectroscopy, transmission electron microscopy (TEM), and DC magnetization measurements. The XRD study coupled with the Rietveld refinement shows that all samples crystallize in a rhombohedral structure with the space group of R-3 C. The FT-IR spectroscopy and TEM images indicate formation of the perovskite structure with the average sizes of 20, 40, and 100 nm for the samples sintered at 700, 800, and 1100 °C, respectively. The DC magnetization measurements confirm tuning of the magnetic properties due to the particle size effects, e.g., reduction in the ferromagnetic moment and increase in the surface spin disorder by decreasing the particle size. The magnetocaloric effect (MCE) study based on isothermal magnetization vs. filed measurements in all samples reveals a relatively large MCE around the Curie temperature of the samples. The peak around the Curie temperature gradually broadens with reduction of the particle size. The data obtained show that although variations in the magnetic entropy and adiabatic temperature decrease by lowering the particle size, variation in the relative cooling power values are the same for all samples. These results make this material a proper candidate in the magnetic refrigerator application above room temperature at moderate fields.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Room temperature ferromagnetism in epitaxial Cr{sub 2}O{sub 3} thin films grown on r-sapphire

We report on the epitaxial growth and magnetic properties of Cr{sub 2}O{sub 3} thin films grown on r-sapphire substrate using pulsed laser deposition. The X-ray diffraction (XRD) (2θ and Φ) and TEM characterization confirm that the films are grown epitaxially. The r-plane (011{sup ¯}2) of Cr{sub 2}O{sub 3} grows on r-plane of sapphire. The epitaxial relations can be written as [011{sup ¯}2] Cr{sub 2}O{sub 3} ‖ [011{sup ¯}2] Al{sub 2}O{sub 3} (out-of-plane) and [1{sup ¯}1{sup ¯}20] Cr{sub 2}O{sub 3} ‖ [1{sup ¯}1{sup ¯}20] Al{sub 2}O{sub 3} (in-plane). The as-deposited films showed ferromagnetic behavior up to 400 K but ferromagnetism almost vanishes with oxygen annealing. The Raman spectroscopy data together with strain measurements using high resolution XRD indicate that ferromagnetism in r-Cr{sub 2}O{sub 3} thin films is due to the strain caused by defects, such as oxygen vacancies.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Gasification Studies: Task 4 Topical Report, Utah Clean Coal Program

A key objective of the Task 4 activities has been to develop simulation tools to support development, troubleshooting and optimization of pressurized entrained-flow coal gasifiers. The overall gasifier models (Subtask 4.1) combine submodels for fluid flow (Subtask 4.2) and heat transfer (Subtask 4.3) with fundamental understanding of the chemical processes (Subtask 4.4) processes that take place as coal particles are converted to synthesis gas and slag. However, it is important to be able to compare predictions from the models against data obtained from actual operating coal gasifiers, and Subtask 4.6 aims to provide an accessible, non-proprietary system, which can be operated over a wide range of conditions to provide well-characterized data for model validation. Highlights of this work include: (1) Verification and validation activities performed with the Arches coal gasification simulation tool on experimental data from the CANMET gasifier (Subtask 4.1). (2) The simulation of multiphase reacting flows with coal particles including detailed gas-phase chemistry calculations using an extension of the one-dimensional turbulence model’s capability (Subtask 4.2). (3) The demonstration and implementation of the Reverse Monte Carlo ray tracing (RMCRT) radiation algorithm in the ARCHES code (Subtask 4.3). (4) Determination of steam and CO 2 gasification kinetics of bituminous coal chars at high temperature and elevated pressure under entrained-flow conditions (Subtask 4.4). In addition, attempts were made to gain insight into the chemical structure differences between young and mature coal soot, but both NMR and TEM characterization efforts were hampered by the highly reacted nature of the soot. (5) The development, operation, and demonstration of in-situ gas phase measurements from the University of Utah’s pilot-scale entrained-flow coal gasifier (EFG) (Subtask 4.6). This subtask aimed at acquiring predictable, consistent performance and characterizing the environment within the gasifier.

01 COAL, LIGNITE, AND PEAT↗

Kinetics of calcite precipitation by ureolytic bacteria under aerobic and anaerobic conditions

The kinetics of urea hydrolysis (ureolysis) and induced calcium carbonate(CaCO 3 ) precipitation for engineering use in the subsurface was investigated under aerobic conditions using Sporosarcina pasteurii (ATCC strain 11859) as well as Bacillus sphaericus strains 21776 and 21787. All bacterial strains showed ureolytic activity inducing CaCO 3 precipitation aerobically. Rate constants not normalized to biomass demonstrated slightly higher-rate coefficients for both ureolysis (k urea ) and CaCO 3 precipitation (k precip ) for B. sphaericus 21776 (k urea =0.10±0.03 h -1 , k precip =0.60±0.34 h -1 ) compared to S. pasteurii (k urea =0.07±0.02 h -1 , k precip =0.25±0.02 h -1 ), though these differences were not statistically significantly different. B. sphaericus 21787 showed little ureolytic activity but was still capable of inducing some CaCO 3 precipitation. Cell growth appeared to be inhibited during the period of CaCO 3 precipitation. Transmission electron microscopy (TEM) images suggest this is due to the encasement of cells and was reflected in lower k urea values observed in the presence of dissolved Ca. However, biomass regrowth could be observed after CaCO 3 precipitation ceased, which suggests that ureolysis-induced CaCO 3 precipitation is not necessarily lethal for the entire population. The kinetics of ureolysis and CaCO 3 precipitation with S. pasteurii was further analyzed under anaerobic conditions. Rate coefficients obtained in anaerobic environments were comparable to those under aerobic conditions; however, no cell growth was observed under anaerobic conditions with $NO_3^-,SO_4^{2-}$ or Fe 3+ as potential terminal electron acceptors. These data suggest that the initial rates of ureolysis and ureolysis-induced CaCO 3 precipitation are not significantly affected by the absence of oxygen but that long-term ureolytic activity might require the addition of suitable electron acceptors. Variations in the ureolytic capabilities and associated rates of CaCO 3 precipitation between strains must be fully considered in subsurface engineering strategies that utilize microbial amendments.

58 GEOSCIENCES↗

Coordinated Chemical and Isotopic Studies of GEMS in IDPS

Cometary IDPs contain a record of the building blocks of the solar system including presolar grains, molecular cloud material, and materials formed in the early solar nebula [1]. Following their accretion, these materials have remained relatively unaltered because of the lack of parent body hydrothermal alteration. We are using coordinated transmission electron microscope (TEM) and ion microprobe studies to establish the origins of the various components within cometary IDPs. Of particular interest is the nature and abundance of presolar silicates in these IDPs because astronomical observations suggest that crystalline and amorphous silicates are the dominant grain types produced in young main sequence stars and evolved O-rich stars [e.g. 2]. Amorphous silicates (in the form of GEMS grains) are a major component of cometary IDPs and so a major objective of this work is to elucidate their origins. In rare cases, GEMS grains have highly anomalous O isotopic compositions that establish their origins as circumstellar condensates [3]. Here we present data on a systematic study of the silicate components within a primitive IDP.

Keller, L. P.↗

Characterization of mechano-thermally synthesized Curie temperature-adjusted La{sub 0.8}Sr{sub 0.2}MnO{sub 3} nanoparticles coated with (3-aminopropyl) triethoxysilane

This research aimed to synthesize nanostructured strontium-doped lanthanum manganite, La{sub 0.8}Sr{sub 0.2}MnO{sub 3} (LSMO), with its Curie temperature (T{sub c}) adjusted to the therapeutic range, through a mechanothermal route. In order to investigate the effect of heat treatment temperature and duration on the resulting crystallite size, morphology, magnetic behavior and Curie temperature, the starting powder mixture was milled in a planetary ball mill before being subsequently heat treated at distinct temperatures for different time lengths. The composition, morphology, and magnetic behavior were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and vibrating sample magnetometer (VSM). In addition, magnetic properties were further investigated using an alternating current (AC) susceptometer and thermo-magnetic analyzer. 20 h of milling produced a crystallite size reduction leading to a decrease in the heat treatment temperature of LSMO synthesis to 800 °C. Moreover, SEM analysis has shown the morphology of a strong agglomeration of fine nanoparticles. HRTEM showed clear lattice fringes of high crystallinity. The mean crystallite and particle size of 20-hour milled sample heat treated at 1100 °C for 10 h are relatively 69 and 100 nm, respectively. The VSM data at room temperature, indicated a paramagnetic behavior for samples heat treated at 800 °C. However, by increasing heat treatment temperature to 1100 °C, LSMO indicates a ferromagnetic behavior with well-adjusted Curie temperature of 320 K, suitable for hyperthermia applications. Also, reentrant spin glass (RSG) behavior has been found in heat treated samples. The particles are coated with (3-aminopropyl) triethoxysilane (APTES) for biocompatibility purposes; Fourier transform infrared spectroscopy (FTIR) and thermo-gravimetric analysis (TGA) are used for further confirmation of APTES coating. - Highlights: • La{sub 0.8}Sr{sub 0.2}MnO{sub 3} nanoparticles were synthesized via a mechanothermal route. • We report a significant reduction in the heat treatment temperature. • The Curie temperature was tuned within the therapeutic range. • The particles were coated with (3-aminopropyl) triethoxysilane for biocompatibility purposes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The performance evaluation of direct detection electron energy-loss spectroscopy at 200 kV and 80 kV accelerating voltages

Direct electron detectors (DeDs) have been widely used for imaging studies because of their higher beam sensitivity, lower noise, improved pixel resolution, etc. However, there have been limited studies related to the performance in spectroscopic applications for the direct electron detection. Hereby, taking the advantage of the DeD installed on a high-performance electron energy-loss spectrometer, we systematically studied the performance of a DeD (Gatan's K2 IS) fitted on an aberration-corrected transmission electron microscope (TEM) equipped with an electron monochromator. Using SrTiO3 as the model system, the point spread function in the zero-loss region of the spectrum and the performance for core loss spectroscopy have been investigated under both 200 kV and 80 kV operating conditions. We demonstrate that the K2 detector can achieve an overall better performance at 200 kV than a charge coupled device (CCD) detector. At 80 kV, the K2 DeD is still better than a CCD, except for the relative broad tails of the zero-loss peak. The signal-to-noise ratio is very close for DeD and CCD under 80 kV. Based on our data obtained at different operating voltages, it is clear that DeD will benefit the microscopy community and boost the development of cutting-edge materials science studies by pushing the frontiers in electron energy-loss spectroscopy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

CO/H2 in Translucent Clouds

A thorough examination of techniques to improve the resolution of the FUSE spectrograph was undertaken. These involved co-adding time tagged data very carefully so as to remove any blurs caused by drift. In addition, data was binned by detector pulse height bin (to eliminate any positional vs. gain variations, e.g. "walk"). These techniques only resulted in an extremely modest increase in the spectral resolution, insufficient to allow the CO/H2 studies to be performed. The only remaining potential source of blur was defocus - implying the instrument was never properly focused on orbit. Private discussions with B.G. Anderson of the FUSE team resulted in my learning that this was in fact the case - the slidgrating distance was never optimized on orbit - resulting in a degradation of the peak performance of the instrument. Unfortunately, this was never publicized, even to myself, a member of the instrument tem and the spectrograph designer.

Green, James↗

Coordinated Microstructural and Isotopic Characterization of Diamond Inclusions within the Kenna Ureilite

Introduction: The origin of diamonds in ureilitic meteorites, a major family of ultramafic achondrites, has long been debated, with various formation mechanisms inferred, including: 1) shock conversion of preexisting graphite due to a hypervelocity impact on the ureilite parent body [e.g., 1]; 2) vapor deposition during condensation of the solar nebula [e.g., 2]; or 3) static transformation in the mantle of a large planetesimal (>1000 km in diameter) [e.g., 3]. The Kenna ureilite is a 10.9 kg stone that was found in Kansas in 1972 and is dominantly composed of olivine and pigeonite (68% and 22% modal abundance, respectively), together with minor metal and carbon-rich regions. Within the carbon-rich domains researchers have identified microdiamonds up to ~10 µm in size [4]. Methods: Due to the proximity of the extremely hard microdiamonds with soft graphite and moderately hard silicates, achieving an appropriately flat surface for electron backscatter diffraction (EBSD) analysis has proven challenging. We have, therefore, employed a Hitachi ArBlade 5000 broad beam Ar ion milling system to prepare a sample with an adequately uniform surface flatness across the various minerals. The ion milling dramatically im-proved indexing of the EBSD patterns and facilitated high-resolution microstructural analysis of the carbon-rich domains. After microstructural EBSD analyses using an Oxford Symmetry detector we collected coordinated hy-perspectral cathodoluminescence (CL) analyses using a Gatan Monarc system mounted on a JEOL 7900F field emission (FE) scanning electron microscope at NASA Johnson Space Center. A focused ion beam (FIB) foil was extracted from a region of interest and analyzed using a JEOL 2500 FE scanning transmission electron microscope (STEM). In situ carbon and nitrogen isotopic analyses were collected from diamond-bearing domains using a Cameca NanoSIMS 50L at NASA JSC. Results: The carbon rich regions occur as tabular domains between polygonal olivine and pigeonite, and are composed of aggregates of micrometer-scale diamond with intermediate graphite, oxides and metal grains. Within the microdiamonds, {111} twins are abundant, many of which form ragged lamellae consistent with mechanical twinning. The microdiamond assemblages appear to pseudomorph tabular graphite habits, which together with the abundant deformation twins, support a shock transformation mechanism for microdiamond formation within the Kenna meteorite. Further supporting this observation, the diamond laths show close alignment of <111> and <110> between domains, consistent with a solid-state transformation from graphite along <0001> and <1-210>, respec-tively [5]. A FIB foil was extracted from a region with mechanical twins, and high resolution STEM analyses reveal cross-cutting veins of graphite and oriented kamacite crystals together with additional sets of {111} nano-twins formed in at least three orientations. Isotopic analyses of C and N reveal sector zoning patterns [cf. 3] that are unre-lated to the diamond substructure identified by EBSD yet consistent with hyperspectral CL images. Conclusions: These data provide new constraints on microdiamond formation within ureilites. The microdia-monds exhibit orientation variants defined by aligned <111> and <110> axes consistent with inherited crystallo-graphic orientations from transformation of a single hexagonal graphite parent crystal [5]. Crosscutting the micro-diamonds are veins of graphite and kamacite, together with additional {111} nanotwins. Taken together these data suggest that microdiamonds from ureilites formed from a solid state, diffusionless transformation from graphite, likely associated with a major shock event, which was subject to subsequent reversion either during decompression or a later deformation event. The N and C isotopic sector zoning is unrelated to diamond microstructures and likely reflects inheritance from the parent graphite crystal.

Ureilite↗

Effect of Rice Husk Derived Nanosilica on the Structure, Properties and Biodegradability of Corn-Starch/LDPE Composites

Development of material with enhanced mechanical properties and biodegradability by the incorporation of synthesized inorganic nanostructured mesoporous silica from rice husk has been investigated. The produced nanosilica (≈ 25 nm and 213.045 m{sup 2}/g surface area) and nanosilica blended LDPE/starch composites were extensively characterised by SEM, FTIR, XRD, XRF, TEM, EDAX and TGA analysis. The low cost of production estimated, ensures its feasibility toward large scale application. The addition of nanosilica into the matrix led to the enhancement of Young’s modulus and stiffness by a value of 535.6 MPa and 32172.81 N/m respectively at 3% nanosilica content, thereby enhancing the initial rigidity and resistivity towards deformation making a better biodegradable substitute in terms of initial application range. The MFI and hardness value also increased with increase of silica content upto 1.5% and 2% respectively to 7.23 g/10 min and 42 (Shor D). Increase in nanofiller content improved the value of degradation rate constant (k) of the weight loss data plot in both vegetable waste and garden soil environment. The addition of 1.5% of nanosilica to a blend of 80% LDPE and 20% starch showed almost the same biodegradation rate as that without nanosilica but with superior mechanical properties and applicability range.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

3D Observation of GEMS by Electron Tomography

Amorphous silicates in chondritic porous interplanetary dust particles (CP-IDPs) coming from comets are dominated by glass with embedded metal and sulfides (GEMS). GEMS grains are submicron-sized rounded objects (typically 100-500) nm in diameter) with anaometer-sized (10-50 nm) Fe-Ni metal and sulfide grains embedded in an amorphous silicate matrix. Several formation processes for GEMS grains have been proposed so far, but these models are still being debated [2-5]. Bradley et al. proposed that GEMS grains are interstellar silicate dust that survived various metamorphism or alteration processes in the protoplanetary disk and that they are amorphiation products of crystalline silicates in the interstellar medium by sputter-deposition of cosmic ray irradiation, similar to space weathering [2,4]. This consideration is based on the observation of nano-sized crystals (approximately 10 nm) called relict grains in GEMS grains and their shapes are pseudomorphs to the host GEMS grains. On the other hand, Keller and Messenger proposed that most GEMS formed in the protoplanetary disk as condensates from high temperature gas [3,5]. This model is based on the fact that most GEMS grains have solar isotopic compositions and have extremely heterogeneous and non-solar elemental compositions. Keller and Messenger (2011) also reported that amorphous silicates in GEMS grains are surrounded by sulfide grains, which formed as sulfidization of metallic iron grains located on the GEMS surface. The previous studies were performed with 2D observation by using transmission electron microscopy (TEM) or scanning TEM (STEM). In order to understand the structure of GEMS grains described above more clearly, we observed 3D structure of GEMS grains by electron tomography using a TEM/STEM (JEM-2100F, JEOL) at Kyoto University. Electron tomography gives not only 3D structures but also gives higher spatial resolution (approximately a few nm) than that in conventional 2D image, which is restricted by sample thickness ) approx. or greater than 50 nm). Three cluster IDPs (L2036AA5 cluster4, L2009L8 cluster 13 and W726A2) were used for the observations. ID W726A2 was collected without silicon oil, which is ordinary used to collect IDPs, so this sample has no possibility of contaminations caused by silicon oil or solvent to rinse it [6]. The samples were embedded in epoxy risin and sliced into ultrathin sections (50-300 nm) using an ultramicotome. The sections were observed by BF-TEM and HAADF-STEM (high angle annular dark field-scanning TEM) modes. Images were obtained by rotating the sample tilt angle over a range of +/- 65 deg in 1 deg steps. The obtained images were reconstructed to slice images. Mineral phases in the slice images were estimated by comparing with a 2D elemental map obtained by an EDS (energy dispersive X-ray spectroscopy) system equipped in the TEM/STEM. Careful examination of the slice images confirmed that iron grains are embedded in the amorphous silicate matrix of the GEMS grains, but sulfide grains were mainly present on the surface of the amorphous silicate. These results are consistent with the model that GEMS grains formed as condensates [3,5], although more data are needed to conclude the origin of GEMS grains. The present study is the first successful example adapting the electron tomography to the IDPs. This type of analysis will be important for planetary material sciences in the future.

Matsuno, Junya↗

Interactions of cationic polystyrene nanoparticles with marine bivalve hemocytes in a physiological environment: Role of soluble hemolymph proteins

The bivalve Mytilus galloprovincialis has proven as a suitable model invertebrate for evaluating the potential impact of nanoparticles (NPs) in the marine environment. In particular, in mussels, the immune system represents a sensitive target for different types of NPs. In environmental conditions, both NP intrinsic properties and those of the receiving medium will affect particle behavior and consequent bioavailability/uptake/toxicity. However, the evaluation of the biological effects of NPs requires additional understanding of how, once within the organism, NPs interact at the molecular level with cells in a physiological environment. In mammalian systems, different NPs associate with serum soluble components, organized into a “protein corona”, which affects particle interactions with target cells. However, no information is available so far on the interactions of NPs with biological fluids of aquatic organisms. In this work, the influence of hemolymph serum (HS) on the in vitro effects of amino modified polystyrene NPs (PS-NH{sub 2}) on Mytilus hemocytes was investigated. Hemocytes were incubated with PS-NH{sub 2} suspensions in HS (1, 5 and 50 µg/mL) and the results were compared with those obtained in ASW medium. Cell functional parameters (lysosomal membrane stability, oxyradical production, phagocytosis) were evaluated, and morphological changes were investigated by TEM. The activation state of the signalling components involved in Mytilus immune response (p38 MAPK and PKC) was determined. The results show that in the presence of HS, PS-NH{sub 2} increased cellular damage and ROS production with respect to ASW medium. The effects were apparently mediated by disregulation of p38 MAPK signalling. The formation of a PS-NH{sub 2}-protein corona in HS was investigated by centrifugation, and 1D- gel electrophoresis and nano-HPLC-ESI-MS/MS. The results identified the Putative C1q domain containing protein (MgC1q6) as the only component of the PS-NH{sub 2} hard protein corona in Mytilus hemolymph. These data represent the first evidence for the formation of a NP bio-corona in aquatic organisms and underline the importance of the recognizable biological identity of NPs in physiological exposure medium when testing their potential impact environmental model organisms. Although the results obtained in vitro do not entirely reflect a realistic exposure scenario and the more complex formation of a bio-corona that is likely to occur in vivo, these data will contribute to a better understanding of the effects of NPs in marine invertebrates. - Highlights: • The effects of PS-NH2 NPs on Mytilus hemocytes were compared in serum-HS and ASW. • HS increased cellular/lysosomal damage, ROS production and p-p38MAPK levels. • NP-corona proteins in HS were isolated and identified by MS. • NP-protein coronas in biological fluids can affect NP impact in marine species.

60 APPLIED LIFE SCIENCES↗

Plutonium migration and phase evolution in irradiated U-Pu-Zr metallic fuels: An integrated EPMA-SEM-TEM study

Constituent redistribution is a defining feature of irradiated U-Pu-Zr metallic fuels, yet its mechanisms and effects on fuel performance are not sufficiently resolved to guide model development. Although decades of irradiation testing have established broad trends, a true mechanistic understanding of constituent redistribution has not been achieved. Here, in this study, we use electron probe microanalysis (EPMA), scanning electron microscopy (SEM), and transmission electron microscopy-based (TEM) selective area electron diffraction (SAED) on a EBR-II irradiated U-19 wt.% Pu-6 wt.% Zr fuel pin cross-section to correlate the composition, porosity, and crystallographic phases formed after irradiation. Constituent redistribution is thought to consist of three distinct zones, in which uranium and zirconium migrate while plutonium remains relatively unchanged. Our EPMA results resolve eight distinct compositional regions, and more importantly, show that plutonium redistributes alongside zirconium, contrary to historical assumptions. The distribution of fission products was highly asymmetric with a few large lanthanide precipitates observed at isolated sites on the pin periphery instead of a uniform distribution of smaller precipitates around the periphery. Using thermodynamic data from TAF-ID and the measured EPMA compositions, matrix phase fractions were predicted across the fuel radius. Phase predictions based on composition did not match TEM/SAED results, which revealed a much higher fraction of α−U phase than would be expected if phases were retained from reactor temperatures. These findings highlight the need for expanded SAED phase identification to capture post-irradiation and storage effects, as well as rigorous uncertainty quantification in fuel performance and phase diagram modeling to better constrain predictions from compositional data.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High Velocity Impact Performance of a Dual Layer Thermal Protection System for the Mars Sample Return Earth Entry Vehicle

The Mars Sample Return (MSR) Earth Entry Vehicle (EEV) is currently planned on being released from its Micro-Meteorite/Orbital Debri (MM/OD) shielding housing about two days before the Earth entry phase. This leaves the EEV exposed to incoming MM/OD impacts, potentially damaging the heat shield and compromising its Entry, Decent, and Landing (EDL) integrity. Currently, two materials are proposed to comprise the MSR-EEV heat shield, a dual layer material Heat-shield for Extreme Entry Environment Technology (HEEET) and Phenolic Impregnated Carbon Ablator (PICA). PICA has been well characterized for OD class impacts, ~7km/s high mass impacts, from previous testing done in the Orion program, but hasn't under-gone extensive MM impact testing. HEEET is a rela-tively new material with minimal prior testing in re-gards to High Velocity Impacts (HVI). In order to in-form selectability of a material, it is crucial to under-stand the material performance when faced with an HVI, directly affecting mission success probability.The current measure of a Thermal Protection Sys-tem's (TPS) performance against an HVI is evaluating a thermally sized material against its derived Balistic Limit Equation (BLE). A BLE is generated empirically from multiple shots of HVI testing, and is used as a first order method in evaluating TPS's performance against the expected MM/OD environment. This method has proved useful for previous uniform densi-ty TPS materials, but has never been validated against a dual layer recession material such as HEEET. Testing in the MSR program for FY19 has a re-quirement to assess the effects of a dual layer TPS by testing various thicknesses of HEEET's Recession Layer, seen in Figure 1. From this data, BLE's will be derived for the individual thickness ratio samples, as well as the material as a whole to evaluate if a heritage form of the BLE can capture the complex physics associated with a dual layer system. Crater morpholo-gy will also be assessed with post-test Non-Destructive Evaluation (NDE) methods such as CT scanning to visualize if a BLE can well predict the associated pene-tration depths, since a BLE assumes full disinigration of the impacting particle and is generally only used to size a spherical crater ? disregarding any shrapenel effects from a high density impactor.To inform this analysis, expected MM environ-ments from the Meteoroid Engineering Model (MEM) and analytical equations for mass flux of incoming MM were evaluated against the notional MSR-EEV trajectory [1]. Using those dispersions, a monte-carlo was run to determine the most probable particle pa-rameters, as well as the riskiest in terms of full bondline penetration. From these probabilities, a test matrix was designed to test against bounding cases for the various parameters of the BLE: projectile density, projectile mass, projectile velocity, and the impact angle.This presentation will discuss the performance of the dual layer TPS material HEEET against a wide range of impact kinetic energies and densitites, as well as the comparison of HEEET to PICA in terms of MM/OD performance and selectability criteria.

Libben, B. J.↗

Metalorganic chemical vapor deposition of ZnGeN 2 films on GaN: effects of cation stoichiometry on surface morphology and crystallinity

Novel optoelectronic device designs based on the heterostructures of III-N and II-IV-N 2 are promising to advance device performance significantly. For example, by utilizing InGaN-ZnGeN 2 quantum well (QW) structures instead of pure InGaN, the band structure engineering in the QW active region can lead to improved electron-hole wavefunction overlap, and thus enhance the radiative efficiency for photon generation. These novel heterostructures have great potential to address the current challenge of low quantum efficiency in InGaN QW based light emitting diodes emitting in green and beyond. The materials development of ZnGeN 2 is still at an early stage as compared to the much matured GaN material system. In an ideal octet rule preserving ordered structure of ZnGeN 2 , every N atom is coordinated by exactly two Zn and two Ge atoms. However, local violation of octet rule can be caused by non-ideal coordination of N by the cations. The disordered structure is thermodynamically less favorable but can still be achieved, for example, in kinetics-limited growth regime. The ordered ZnGeN 2 has a bandgap very close to that of GaN (~3.4 eV) and a lattice mismatch of <0.1% with GaN. Interestingly, the valence band of ZnGeN 2 has been predicted to be ~1 eV above that of GaN, which has inspired novel designs for high efficiency light emitters. In this work, we investigated the metalorganic chemical vapor deposition (MOCVD) of ZnGeN 2 films on GaN/c-sapphire templates. Diethylzinc (DEZn), germane (GeH4) and ammonia were used as the precursors for Zn, Ge and N, respectively. A systematic study was conducted to investigate the cation stoichiometry as a function of growth temperature (TG), total reactor pressure (P) and DEZn/GeH 4 molar flow rate ratio (RII/IV). Under the investigated growth window, the Zn/(Zn+Ge) composition in the films, determined from energy dispersive X-ray spectroscopy, decreased monotonically with increase in TG but increased with increase in P and RII/IV. Atom probe tomography data did not indicate the presence of any secondary phases such as Zn 3 N 2 or Ge 3 N 4 . The surface morphology and crystallinity of the grown films had strong correlation with the Zn/(Zn+Ge) composition. The scanning electron microscopy images showed that the near-stoichiometric films have planar surfaces whereas Zn-rich films had crystallites on their surface and the Zn-poor films had faceted surface. Scanning transmission electron microscopy (STEM) imaging revealed that the Zn-rich and Zn-poor films have columnar and filament-like morphology, respectively, whereas the near-stoichiometric films have continuous film-like cross-sectional morphology. TEM nano-diffraction patterns as well as X-ray diffraction 2θ-ω scan profiles indicate that the near stoichiometric films are single crystalline. Nano-diffraction pattern of the stoichiometric films resembled that of a disordered ZnGeN 2 structure. Room temperature Raman spectra of near-stoichiometric films showed only the phonon density of states like features of a cation disordered ZnGeN 2 . Cathodoluminescence and photoluminescence spectra measured at different temperatures had similar features with peak emission wavelength at ~ 2 eV. In conclusion, the stoichiometry of ZnGeN 2 films can be widely tuned by tuning the MOCVD growth parameters. The surface morphology and the crystallinity of the films were found to have strong correlation with the Zn/(Zn+Ge) composition. The stoichiometric ZnGeN 2 films grown on GaN were demonstrated with uniform surface morphology and high crystalline quality. The results from this work will provide pathway to implement ZnGeN 2 in device structures.

Karim, Md Rezaul↗