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At least 865 records · Page 48

Polymer nanoparticles of N-vinylpyrrolidone loaded with an organic aminonitroxyl platinum (IV) complex. Characterization and investigation of their in vitro cytotoxicity

The conditions for obtaining stable aqueous solutions of a lipophilic aminonitroxyl platinum complex, namely, e-amine-d-(4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl)-a, f-bis(octanoato)-b, c-dichloroplatinum(IV), by means of its encapsulation into nanoparticles of copolymers of N-vinylpyrrolidone with triethylene glycol dimethacrylate with various monomer compositions and topologies were found. Aqueous solutions of the complex encapsulated into polymer particles were investigated by dynamic light scattering, the temperature dependence of nanostructure sizes was studied. Transmission electron microscopy established that the hybrid nanostructures are core—shell particles, in which the platinum complex forms small clusters (∼4 nm). The parameters of ESR spectra of aqueous dispersions indicate a high mobility of nitroxyl contained in hybrid nanostructures. Voltammetric measurements demonstrate a similarity of the redox reactions related to the free radical fragment of the aminonitroxyl Pt{sup IV} complex and of the 4-acetylamino-2,2,6,6-tetramethylpiperidine 1-oxyl radical. Polymer products containing the platinum complex were studied by IR spectroscopy, TGA, and DSC. The cytotoxicity index (IC{sub 50}) of the free and the encapsulated complex was determined for HeLa tumor cells. The cytotoxicity of the latter (IC{sub 50} 47–205 nmol L{sup −1}) depends on the monomeric composition of the nanoparticles and the incubation time.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Approaches for Tensile Testing of Braided Composites

For angleply composites, lamina tension and compression strengths are commonly determined by applying classical lamination theory to test data obtained from testing of angleply composite specimens. For textile composites such as 2D triaxial braids, analysis is more complex and standard test methods do not always yield reliable strength measurements. This paper describes recent research focused on development of more reliable tensile test methods for braided composites and presents preliminary data for various approaches. The materials investigated in this work have 0deg+/-60 2D triaxial braid architecture with nearly equal fiber volume fraction in each of the three fiber directions. Flat composite panels are fabricated by resin transfer molding (RTM) using six layers of the braided preform aligned along the 0deg fiber direction. Various epoxy resins are used as matrix materials. Single layer panels are also fabricated in order to examine local variations in deformation related to the braid architecture. Specimens are cut from these panels in the shape of standard straight-sided coupons, an alternative bowtie geometry, and an alternative notched geometry. Axial tensile properties are measured using specimens loaded along the 0deg fiber direction. Transverse tensile properties are measured using specimens loaded perpendicular to the 0deg fibers. Composite tubes are also fabricated by RTM. These tubes are tested by internal pressurization using a soft rubbery material sealed between the inside diameter of the tube and the load fixtures. The ends of the tube are unconstrained, so the primary load is in the hoop direction. Tubes are fabricated with the 0deg fibers aligned along the tube axis by overbraiding the preform on a mandrel. Since the loading is in the hoop direction, testing of the overbraided tube provides a measure of transverse tensile strength. Previous work has indicated that straight-sided coupons yield a transverse tensile strength that is much lower than the expected material strength because of premature edge-initiated failure. Full-field strain measured during transverse tensile tests clearly showed accumulation of edge damage prior to failure. In the current work, high speed video and testing of single layer specimens are used to investigate potential failure mechanisms in more detail. High speed video clearly shows the edge initiation in six layer transverse tensile test coupons. Specimens with the bowtie geometry and the notched geometry minimize this edge effect and yield significantly higher transverse tensile strength values compared to the straight-sided coupons. However, bowtie and notched specimens geometries are not ideal because of the non-uniform stress and strain fields in the region of failure. Testing of tubes using internal pressurization eliminates edge-initiated failure and provides a more uniform state of stress and strain. Preliminary results indicate that bowtie, notched, and tube specimens yield comparable values for transverse tensile strength and that these values are much higher than the strength measured using a straight-sided coupon.

Roberts, Gary D.↗

Bioinspired mineralizing microenvironments generated by liquid-liquid phase coexistence

Biominerals such as bones, teeth and shells exhibit improved mechanical properties and intricate morphologies not seen in nonbiologically-produced minerals of ostensibly the same composition. These remarkable properties of biogenic minerals are thought to arise due to precise local control over the mineral deposition process, including organic and inorganic inclusions. Understanding how Biology controls the local reaction environment during formation of these materials to control their composition, structure, and properties is a grand challenge that promises to enable new routes to high-performance materials. This project developed multi-compartment bioinspired microreactors as artificial mineralizing vesicles, and used them to understand and control formation of inorganic/organic composite solid materials. A major emphasis was on developing all-aqueous emulsions in which each droplet was a structured microreactor with two or more adjacent phases. This approach provided local control over reaction environment including availability of inclusions such as polypeptides and metal ions, while being sufficiently simple to produce large populations of essentially identical multiphase reactor droplets simultaneously within a batch. Organic/inorganic composite materials could be produced with very high organic content that stabilized the inorganic portions as amorphous materials (e.g., amorphous calcium carbonate) by preventing the typical conversion to more thermodynamically crystalline forms (e.g., calcite). These stabilized amorphous composites could be stored indefinitely and converted to crystalline forms later by removal of the organic inclusions via, for example, heating. Compositional gradients in the organic and inorganic components were embedded during synthesis due to the evolution of the reaction microenvironment, and despite the complexity of this process it occurred similarly across the population of reactive droplets and was hence encoded into the population of resulting composite particles. The approach developed here allows pre-structuring of reactive microenvironments to control the spatiotemporal reaction environment, which is an important step towards rational design and on-demand production of complex functional materials with desired composition, optical properties, and mechanical response.

36 MATERIALS SCIENCE↗

Thermal-Mechanical Analysis of an Additive Manufacturing Ceramic Heat Exchanger for High-Temperature Recuperator in a sCO2 Power System

Supercritical CO2 (sCO2) Brayton power cycle can be configured in a closed-loop power system and has a potentially high cycle efficiency. Compactness and high efficiency of a sCO2 power block make the sCO2 Brayton cycle a versatile power cycle in broad applications. While many heat sources are of sufficient intensity to produce high temperature working fluids to achieve high cycle efficiency, the thermal-mechanical stability of traditional materials (e.g., steels and nickel-based superalloys) used in construction of heat exchangers and turbine components limits the operating conditions and thus thermodynamic efficiency of the system. This effort seeks to establish the viability of ceramic heat exchanger technologies for the most extreme operating conditions envisioned for power generation and other high temperature processes. Heat exchangers constructed from ultra-high temperature ceramics, a class of extreme environment materials featuring melting points (Tmp.) above 3000 degrees C, is particularly appealing for sCO2 Brayton cycles given their ultra-low creep rates and very high retained strength at low homologous temperatures (i.e., T < 0.5 Tmp., or at least 1500 degrees C). To translate these materials properties to ultra-high temperature heat exchangers, innovations are required in ceramic manufacturing techniques to realize the complex architectures featured in compact heat exchangers with high power density. With appropriate processing, ZrB2-SiC based compositions can be sintered to near full density and shaped into complex topologies via ceramic additive manufacturing methods. This paper analyzes heat exchanger designs and explores thermal-mechanical implications of the operating environment. Thermal flow, heat transfer, and conjugate mechanical analyses provide insights into benefits and risks associated with the design approach.

additive manufacturing↗

Numerical framework for integrated additive manufacturing-compression molding (AM-CM) of thermoplastic composites

Additive manufacturing-compression molding (AM-CM) has emerged as a transformative technology in advanced composite manufacturing. Additive manufacturing (AM) offers high design flexibility and the ability to produce complex geometries with precisely aligned fibers in the preferred orientation. Compression molding (CM) enhances composite materials by providing excellent dimensional stability, reduced porosity, high production rates, and a smooth surface finish. Despite these advantages, extensive integrated analysis is required to optimize processing conditions for improved fiber orientation distribution (FOD) and porosity control. Here, this study develops a comprehensive numerical model to simulate the AM-CM manufacturing process. The model isolates the effects of both the AM and CM phases while also capturing their integration. Additionally, it accounts for heat transfer, temperature-dependent viscosity, and fiber orientation in the extruded fiber-filled polymer, accurately representing material behavior during processing. This approach enables the analysis of interactions between deposited beads of complex strand shapes and their interface regions after full compression. Moreover, the model predicts key parameters such as polymer flowability, fiber orientation, and temperature evolution in AM-CM parts. By optimizing processing conditions, it facilitates a controlled and predictable microstructure.

36 MATERIALS SCIENCE↗

Laboratory investigations of impact-generated plasma

The characteristics of plasma that was produced in laboratory by hypervelocity impacts were investigated to demonstrate the feasibility of generation of magnetic fields by meteoritic impacts and to explain the presence of paleomagnetic fields on the lunar surface. The impact-generated magnetic fields were found to exhibit spatial and temporal complexity that depended on the impact angle, the velocity, and the projectile/target composition. The results suggest that crater-related paleomagnetism associated with this mechanism should exhibit similar complexity with spatial wavelengths on the order of a fraction of the crater radius.

Crawford, David A.↗

An analysis of delamination in angle-ply fiber-reinforced composites

A study of the mechanics and failure modes of delamination initiated from a surface flaw in angle-ply fiber-reinforced composites is presented. The analysis employs a hybrid-stress finite-element method including a crack-tip singular element with its field variables expressed by Muskhelishvili's complex stress functions. Solutions are obtained for the delaminated composites with various laminate parameters. The results elucidate unique and important characteristics of delamination crack-tip response and interlaminar stress transfer mechanisms. Of particular interest are the mixed-mode stress-intensity factors associated with the delamination crack. The influence of ply orientation on KI and KII and their effects on subsequent crack extension are discussed.

Wang, S. S.↗

Automated Fiber Placement of Composite Wind Tunnel Blades: Process Planning and Manufacturing

The ability to accurately manufacture large complex shapes in a consistent and repeatable manner has led to Automated Fiber Placement (AFP) being the predominant mode of manufacturing for large composite aerospace structures today. Currently, AFP is being considered for medium- and small-scale parts. Composite wind tunnel blades have traditionally been fabricated by hand layup for pre-impregnated or dry fabrics with resin infusion. Though well proven, the traditional fabrication method is laborious and tedious, and hence expensive. The project described in this paper used the Integral Structural Assembly of Advanced Composites (ISAAC) facility at the NASA Langley Research Center to build a manufacturing demonstration unit (MDU) with a shape representative of a wind tunnel blade. This MDU is used to discuss tooling, process planning, and fabrication. Additionally, details of the generic manufacturing workflow are presented.

Harik, Ramy↗

One Step Closer to Mars with Aquaponics: Cultivating Citizen Science in K12 Schools

The Microbial Ecology and Biogeochemistry Research Laboratory at NASA Ames Research Center focuses primarily on the nutrient cycling and diversity of complex microbial communities. NASA is interested in the composition and functioning of microbial mat communities as these processes fundamentally shape the form and function of these analogs for the earliest forms of life on Earth (3.6 billion years ago), and likely will on other planets as well. Aquaponics systems are supported by microbial communities who perform many complex ecosystem services, including cycling nitrogen. Microbes are integral to the stability and productivity of aquaponics systems, which are analogous to microbial communities in food production systems that are essential for building efficient life support systems for long-distance space travel. Students at Meadow Park Middle School created 10 parallel aquaponics systems and took temporal microbial samples to characterize whether any macro-ecology variables impacted or changed the microbial diversity of these systems. Students additionally created a website so that other classrooms can pursue similar projects in their own schools (https://go.nasa.gov/2uJhxmF). Our lab at NASA Ames has sequenced water samples from each of the 10 tanks at 3 timepoints using a MinION sequencer. MPMS students will be involved in the analysis of the bioinformatics data generated through this collaboration. Our ongoing collaboration aims to collect and analyze data in the classroom setting that has utility for research scientists, while involving students as collaborators in the research process.

Kolattukudy, Maria↗

The Equilibrium Response of Climate and Composition to Lightning

Climate change can affect atmospheric composition through perturbation of natural processes, leading to complex feedbacks. The primary atmospheric oxidants OH and ozone are very sensitive to emissions of nitrogen oxides (NO x ) from lightning, and therefore so are the subsequent chemical perturbations to long-lived greenhouse gases (e.g., methane) and aerosol chemistry and physics. Meanwhile, cloud electrification responds to both meteorology and composition (aerosol particles). Key to understanding the ultimate impact of lightning on air quality and climate is the long-term methane feedback. Here, we present simulations from the GISS ModelE2.1 chemistry-climate model in which we isolate the response of Earth’s radiative budget and composition to lightning NO x in the present day and at the end of this century by allowing the model to re-equilibrate following removal of the source. Whereas lightning initially contributes to surface ozone enhancements, longer-term responses amplified by the methane lifetime feedback reduce surface ozone on multi-decadal time scales in the northern midlatitudes. Lightning consequently contributes a strong negative radiative effect in the present day (-0.5 W m -2 ), stronger than that estimated for the anthropogenic NOx source. In addition to influencing tropospheric composition, we find significant changes in stratospheric dynamics and composition. We test the sensitivity of our results to multiple parameterizations for global lightning activity.

Lightning↗

Additive manufacturing of continuous carbon fiber-reinforced SiC ceramic composite with multiple fiber bundles by an extrusion-based technique

Due to the high cost, complex preparation process and difficulty in structural design, the traditional methods for carbon fiber-reinforced SiC ceramic composite preparation have great limitations. This paper presents a technique for the additive manufacturing multiple continuous carbon fiber bundle-reinforced SiC ceramic composite with core-shell structure using an extrusion-based technique. A conventional nozzle system was modified to print simultaneously a water-based SiC paste with continuous carbon fibers. Different levels of binder contents were investigated to optimize the stickiness, viscosity, thixotropy and viscoelasticity of the paste. After sintering, SiC whiskers were generated on the surface of fiber, which is conjectured to be due to the reaction between SiO and carbon fiber at high temperature. The continuous carbon fiber-reinforced SiC ceramic composite exhibited non-brittle fracture. In conclusion, the flexural strength of the additively manufactured Cf/SiC composites improved from 162 MPa with no fiber bundles to a maximum of 219 MPa with three fiber bundles.

36 MATERIALS SCIENCE↗

Studies of Lubricating Materials in Vacuum

Lubricating materials for use in a vacuum environment have been the subject of a series of experimental investigations. Evaporation properties were evaluated for solid polymeric compositions. Friction and wear studies explored the behavior during sliding contact for series of polymeric compositions, binary alloys containing soft film-forming phases, complex alloys with film-forming materials, and a burnished MoS2 film. Friction and wear experiments were conducted at 10(exp-9)mm Hg with a 3/16-inch-radius-hemisphere rider specimen sliding on the flat surface of a rotating 2-1/2-inch-diameter disk specimen with materials that had low rates of evaporation. The influence of fillers in polytetrafluoroethylene (PTFE) on decomposition during vacuum friction studies was determined with a mass spectrometer. A real advantage in reducing decomposition and improving friction wear properties is gained by adding fillers (e.g., copper) that improve thermal conductivity through the composite materials. A polyimide and an epoxy-MoS2 composition material were found to have better friction and wear properties than PTFE compositions. A series of alloys (cast binary as well as more complex alloys) that contained microinclusions of potential film-forming material was studied. These materials replaced the normal surface oxides as they were worn away on sliding contact. Iron sulfide, nickel oxide, and tin are typical film-forming materials employed and were demonstrated to be effective in inhibiting surface welding and reducing friction. A burnished MoS2 film applied to type 440-C stainless steel in argon with a rotating soft wire brush had good endurance properties but somewhat higher friction than commercially available bonded films. An oil film applied to the burnished MoS2 markedly reduced its endurance life.

WEAR↗

Identification of Porphyrin-Silica Composite Nanoparticles using Atmospheric Solids Analysis Probe Mass Spectrometry

Porphyrins are critical pigments involved in biological energy transduction processes. Their abilities to absorb light, then convert it to energy, have raised the interest of using porphyrin nanoparticles as photosensitizers in photodynamic therapy. A current study showed that self- assembled porphyrin-silica composite nanoparticles can selectively destroy tumor cells, but detection of the cellular uptake of porphyrin-silica composite nanoparticles was limited to imaging microscopy. In this work, we developed a novel method to rapidly identify porphyrin-silica composite nanoparticles using Atmospheric Solids Analysis Probe-Mass Spectrometry (ASAP-MS). ASAP-MS can directly analyze complex mixtures without the need for sample preparation. Porphyrin-silica composite nanoparticles were vaporized using heated nitrogen desolvation gas, and their thermo-profiles were examined to identify distinct mass- to-charge (M/Z) signatures. HeLa cells were incubated in growth media containing the nanoparticles, and after sufficient washing to remove residual nanoparticles, the cell suspension was loaded onto the end of ASAP glass capillary probe. Upon heating, HeLa cells were degraded and porphyrin-silica composite nanoparticles were released. Vaporized nanoparticles were ionized and detected by MS. Furthermore, the cellular uptake of porphyrin-silica composite nanoparticles was identified using this ASAP-MS method.

36 MATERIALS SCIENCE↗

Swelling-Induced Symmetry Breaking: A Versatile Approach to the Scalable Production of Colloidal Particles with a Janus Structure

Janus particles are widely sought for applications related to colloidal assembly, stabilization of emulsions, and development of active colloids, among others. Here we report a versatile route to the fabrication of well-controlled Janus particles by simply breaking the symmetry of spherical particles with swelling. When a polystyrene (PS) sphere covered by a rigid shell made of silica or polydopamine is exposed to a good solvent for PS, a gradually increased pressure will be created inside the shell. If the pressure becomes high enough to poke a hole in the shell, the spherical symmetry will break while pushing out the swollen PS through the opening to generate a Janus particle comprised of two distinct components. One of the components is made of PS and its size is controlled by the extent of swelling. The other component is comprised of the rigid shell and remaining PS, with its overall diameter determined by the original PS sphere and the rigid shell. This solution-based route holds promises for the scalable production of complex Janus particles with a variety of compositions and in large quantities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pertechnetate/perrhenate–capped Zr/Hf–Dihydroxide Dimers: Elucidating Zr–TcO 4 Co–Mobility in the Nuclear Fuel Cycle

Spent nuclear fuel contains heavy element fission products that must be separated for effective reprocessing for a safe and sustainable nuclear fuel cycle. 93 Zr and 99 Tc are high-yield fission products that co-transport in liquid-liquid extraction processes. Here we seek atomic-level information of this co-extraction process, as well as fundamental knowledge about Zr IV (and Hf IV ) aqueous speciation in the presence of topology-directing ligands such as pertechnetate (TcO 4 – ) and non-radioactive surrogate perrhenate (ReO 4 – ). In this context, we show that the flat tetrameric oxyhydroxyl-cluster [M IV 4 (OH) 8 (H 2 O) 16 ] 8+ (and related polymers) is dissociated by perrhenate/pertechnetate to yield isostructural dimers, M 2 (OH) 2 (XO 4 – ) 6 (H 2 O) 6 • 3H 2 O (M=Zr/Hf IV ; X=Re/Tc VII ), elucidated by single-crystal X-ray diffraction. We used these model compounds to understand the pervasive 93 Zr- 99 Tc coextraction with further speciation studies in water, nitric acid, and tetrabutylphosphate (TBP) -kerosene; where the latter two media are relevant to nuclear fuel reprocessing. SAXS (small angle X-ray scattering), compositional evaluation, and where experimentally feasible, ESI-MS (electrospray ionization mass spectrometry) showed that perrhenate/pertechnetate influence Zr/Hf IV -speciation in water. Here, in Zr-XO 4 solvent extraction studies to simulate fuel reprocessing, we provide evidence that TcO 4 – enhances extraction of Zr IV , and compositional analysis of the extracted metal-complexes (Zr-ReO 4 study) is consistent with the crystallized Zr IV 2 (OH) 2 (Re VII O 4 – ) 6 (H 2 O) 6 •dimer.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Submicron Sodium Banding in Cultured Planktic Foraminifera Shells

The calcite shells, or tests, of foraminifera provide a window into Earth history because they are well preserved in marine sediments and contain useful geochemical proxies for paleoceanography. Previous observations of diurnal heterogeneity in proxies like Mg/Ca demonstrate a complex relationship between environmental conditions and test composition. The definitive causes for this diurnal banding and the potential impact for proxy interpretation in systems other than Mg/Ca have yet to be determined. Here we use time-of-flight secondary ion mass spectrometry (ToF-SIMS), a chemical and isotope mapping technique with a spatial resolution of 300 nm, to show that Na banding is a consistent feature in the tests of cultured Orbulina universa, a species of planktic foraminifer. This banding occurs in two distinct forms: (1) sharp Na bands associated with embedded organic sheets and (2) regular, thicker, but lower-amplitude Na bands that are found throughout the test. In Orbulina bilobata, a morphotype of O. universa that develops a second partial spherical chamber attached to the primary sphere, we use the first type of banding to show that a second organic sheet is used as a template to form this second chamber. Thus, sodium banding links test geochemistry with foraminiferal growth models, allowing us to explain the pattern and timing of chamber formation as well as a specific type of geochemical banding in foraminifera. Furthermore, the magnitude, timing, and coherency between Na and Mg bands can help constrain mechanistic explanations for geochemical banding in foraminifera in general.

paleoclimate, Foraminifera, biomineralization, pal↗

Deep reinforcement learning for optimal control of induction welding process

Optimizing induction welding (IW) process parameters for the application of joining thermoplastic composites is challenging as it requires achieving complex spatiotemporal thermal characteristics along the weld-line to obtain desired weld quality. We formulate an optimal control problem which captures these requirements and seeks to optimize the IW coil speed using a fast-acting dynamic IW process model. We develop a novel Deep Reinforcement Learning (DRL) framework to solve this computationally challenging control problem and demonstrate via simulation study that the learned DRL feedback control policy results in better spatiotemporal thermal characteristics as compared to the current state-of-the-art.

36 MATERIALS SCIENCE↗

Organic colloid composition in variable-redox porewaters within a mountainous floodplain

Redox gradients, often driven by changes in sediment moisture levels in porous, heterogeneous groundwater systems, create dynamic conditions that may promote the production and transport of colloids within natural waters. While much research has focused on the inorganic composition of colloids, the organic composition remains less well understood. Organic matter (OM) in colloids may associate with minerals, complex metal ions, and serve as an electron donor for microbial respiration; therefore, its composition is of high interest. We examined the composition of porewater OM along a redox gradient in a riparian soil located along the Slate River in Crested Butte, Colorado, USA as a function of depth (90, 130, 200, and 350 cm below ground surface). All depths were oxic to suboxic, except 200 cm, where the products of iron and sulfate reduction were observed concomitant with an increase in dissolved and/or colloidal OM, pH, alkalinity, and conductivity. We investigated the composition of porewater using correlated scanning transmission X-ray microscopy and transmission electron microscopy. We observed a change in the OM chemistry from carboxylate-rich at the 200 cm depth (where it was also enmeshed with non-crystalline iron) to phenol- and substituted-aromatic-rich at other depths. Radiocarbon dating revealed carbon in porewater at 200 cm was younger than depths above and below. Soil porewater can flow down into the underlaying gravel bed during baseflow conditions, thus we speculate whether riparian porewater could transport iron- and carboxylate-rich organic colloids into surrounding surface waters through the gravel bed conduit.

Alpine floodplain↗