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At least 811 records · Page 45

In situ mechanical reinforcement of polymer hydrogels via metal-coordinated crosslink mineralization

Biological organic-inorganic materials remain a popular source of inspiration for bioinspired materials design and engineering. Inspired by the self-assembling metal-reinforced mussel holdfast threads, we tested if metal-coordinate polymer networks can be utilized as simple composite scaffolds for direct in situ crosslink mineralization. Starting with aqueous solutions of polymers end-functionalized with metal-coordinating ligands of catechol or histidine, here we show that inter-molecular metal-ion coordination complexes can serve as mineral nucleation sites, whereby significant mechanical reinforcement is achieved upon nanoscale particle growth directly at the metal-coordinate network crosslink sites.

36 MATERIALS SCIENCE↗

Mars rover sample return mission utilizing in situ production of the return propellants

This paper presents an unmanned Mars sample return mission that utilizes propellants manufactured in situ from the Martian atmosphere for the return trip. A key goal of the mission is to demonstrate the considerable benefits that can be realized through the use of indigenous resources and to test the viability of this approach as a precursor to manned missions to Mars. Two in situ propellant combinations, methane/oxygen and carbon monoxide/oxygen, are compared to imported terrestrial hydrogen/oxygen within a single mission architecture, using a single Earth launch vehicle. The mission is assumed to be launched from Earth in 2003. Upon reaching Mars, the landing vehicle aerobrakes, deploys a small satellite, and lands on the Martian surface. Once on the ground, the propellant production unit is activated, and the product gases are liquefied and stored in the empty tanks of the Earth Return Vehicle (ERV). Power for these activities is provided by a dynamic isotope power system. A semiautonomous rover, powered by the indigenous propellants, gathers between 25 and 30 kg of soil and rock samples which are loaded aboard the ERV for return to Earth. After a surface stay time of approximately 1.5 years, the ERV leaves Mars for the return voyage to Earth. When the vehicle reaches the vicinity of Earth, the sample return capsule detaches, and is captured and circularized in LEO via aerobraking maneuvers.

Bruckner, A. P.↗

SO2 over Central China: Measurements, Numerical Simulations and the Tropospheric Sulfur Budget

SO2 in central China was measured in situ from an aircraft and remotely using the Ozone Monitoring Instrument (OMI) from the Aura satellite; results were used to develop a numerical tool for evaluating the tropospheric sulfur budget - sources, sinks, transformation and transport. In April 2008, measured ambient SO2 concentrations decreased from approx.7 ppbv near the surface to approx. 1 ppbv at 1800 m altitude (an effective scale height of approx.800 m), but distinct SO2 plumes were observed between 1800 and 4500 m, the aircraft's ceiling. These free tropospheric plumes play a major role in the export of SO2 and in the accuracy of OMI retrievals. The mean SO2 column contents from aircraft measurements (0.73 DU, Dobson Units) and operational OMI SO2 products (0.63+/-0.26 DU) were close. The OMI retrievals were well correlated with in situ measurements (r = 0.84), but showed low bias (slope = 0.54). A new OMI retrieval algorithm was tested and showed improved agreement and bias (r = 0.87, slope = 0.86). The Community Multiscale Air Quality (CMAQ) model was used to simulate sulfur chemistry, exhibiting reasonable agreement (r = 0.62, slope = 1.33) with in situ SO2 columns. The mean CMAQ SO2 loading over central and eastern China was 54 kT, approx.30% more than the estimate from OMI SO2 products, 42 kT. These numerical simulations, constrained by observations, indicate that ",50% (35 to 61 %) of the anthropogenic sulfur emissions were transported downwind, and the overall lifetime of tropospheric SO2 was 38+/-7 h.

He, Hao↗

BioNutrients-2: Improvements to the BioNutrients-1 Nutrient Production System

The BioNutrients (BN) project aims to develop an on-demand biological production system capable of rapid and safe delivery of multiple nutrients in single-use production packs for long-duration missions. The general concept of this system is to develop edible engineered microorganisms that produce nutrients for human consumption following long-term storage, revival, and growth. BN-1 is a five-year flight project currently on the International Space Station (ISS). It is testing the long-term storage of various microorganisms for the biomanufacturing of space-relevant compounds and validating the performance of the first generation of production packs. The BN-2 project expands the BN-1 flight project scope by introducing novel products, broadening the range of microbial food sources, and improving upon production pack hardware. We are optimizing the biomanufacturing platform for in situ production of yogurt and kefir on the ISS. BN-2 also will test engineered microorganisms, including a probiotic strain, to produce carotenoids or follistatin. To improve the feasibility of this technology for mission use, we transitioned from a hard-shell pack to a second-generation fluorinated ethylene propylene (FEP) bag. The single-use FEP bioreactor facilitates growth of target organisms in a contaminant free environment, while reducing mass and volume compared to the BN-1 hardware. These bioreactors will be employed for production of additional space-relevant products in the BN-2 project. On-orbit testing of FEP production packs will enable optimization of the platform for eventual flight use by the crew.

Natalie Ball↗

Bimetallic Channel Wall Nozzle Development and Hot-Fire Testing Using Additively Manufactured Laser Wire Direct Closeout Technology

NASA has been developing and advancing regeneratively-cooled channel wall nozzle technology for liquid rocket engines to reduce cost and schedules associated with fabrication. One of the primary methods being advanced is Laser Wire Direct Closeout (LWDC). LWDC was developed to provide an additively manufactured laser deposited closeout of the coolant channels that also forms the structural jacket in-situ. This technique has been previously demonstrated through process development and hot-fire testing on a series of subscale nozzles at NASA Marshall Space Flight Center. The hot-fire test articles were fabricated using monolithic alloys to simplify the fabrication process. Ongoing research is being conducted to further expand use of this process for increased scale and bimetallic or multi-alloy options. The use of multi-alloys is desired to fully optimize the combination of materials in the radial and axial directions to reduce overall weight of the nozzle and allow for higher thermal and structural margins on the channel wall nozzle. NASA recently completed process development and hot-fire testing of a series of channel wall nozzles that incorporate a copper-alloy as the hotwall liner material and a superalloy and combination thereof for the structural jacket using the LWDC technique. The fabrication process was further advanced by using a multi-alloy axial joint using explosive bonding integrating a copper-alloy at the forward end of the nozzle hotwall and a stainless-alloy for the remaining length. A third alloy was then used for the channel closeout using the LWDC process. This paper will describe the process development using the LWDC process for channel closeout utilizing the multi-alloys, hardware design and results from hot-fire testing on subscale multi-alloy LWDC channel cooled nozzles.

Gradl, Paul↗

Accident tolerant fuel test 2c (ATF-2C) irradiation test report

A fully prototypic testing platform for testing new accident tolerant fuel (ATF) designs for light water reactors has been established in the center flux trap of Idaho National Laboratory’s advanced test reactor (ATR). The irradiation experiment named ATF-2C has completed its four cycles of prototypic steady state irradiation. Irradiation conditions have been maintained via the loop 2a pressurized water coolant loop and have been monitored through in-situ instrumentation during each cycle. Power and burnup histories of each of the 18 fueled test pins has been calculated.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Development of Fixtures and Methods to Assess the Durability of Balance of Systems Components

The degradation of photovoltaic (PV) balance of systems (BoS) components is not well studied, but the consequences include offline modules, strings, and inverters; system shutdown; arc faults; and fires. A utility provider experienced a ~30% failure rate in their power transfer chain, originally attributed to branch connectors. Field-failed specimen assemblies were, therefore, examined, consisting of cable connector, branch connector, and discrete fuse components. In this study, unused field-vintage specimens are examined using a benchtop prototype fixture to identify the most influential environmental stressors on BoS components as well as the effect of external mechanical perturbation. The prototype fixture was used to develop a perturbation capability for future use in the combined-accelerated stress testing chamber. The benchtop experiments were also used to develop the in-situ data acquisition of specimen current, voltage, and temperature. A significant increase in operating temperature (~100 °C from ~40 °C) and a different failure mode (arcing at the metal pins rather than overheating of the fuse filament) were observed promptly once periodic mechanical perturbation was applied. The current at failure was decreased from 35 A (measured for static specimens, with failure occurring in the fuses) to 15 A (for tests with mechanical perturbation, with failure at the male/female metal pin connection). After initial examination using X-ray computed tomography, the external plastic was machined away from failed specimens to allow for failure analysis, including the extraction of the internal convolute springs for morphological examination (optical and electron microscopy). Chemical composition analysis included energy-dispersive X-ray spectroscopy, differential scanning calorimetry, and Fourier transform infrared spectroscopy.

14 SOLAR ENERGY↗

Exploring Coupled Extreme Environments via In-situ Transmission Electron Microscopy

In-situ transmission electron microscopy (TEM) provides an avenue to explore time-dependent nanoscale material changes induced by a wide range of environmental conditions that govern material performance and degradation. The In-situ Ion Irradiation TEM (I 3 TEM) at Sandia National Laboratories is a JEOL 2100 microscope that has been highly modified with an array of hardware and software that makes it particularly well suited to explore fundamental mechanisms that arise from coupled extreme conditions. Here, examples pertaining to multibeam ion irradiation, rapid thermal cycling, and nanomechanical testing on the I 3 TEM are highlighted, along with prospective advancements in the field of in-situ microscopy.

47 OTHER INSTRUMENTATION↗

Hydraulic fracturing experiments at 1500 m depth in a deep mine: Highlights from the kISMET project

In support of the U.S. DOE SubTER Crosscut initiative, we established a field test facility in a deep mine and designed and carried out in situ hydraulic fracturing experiments relevant to enhanced geothermal systems (EGS) in crystalline rock to characterize the stress field, understand the effects of rock fabric on fracturing, and gain experience in monitoring using geophysical methods. The project also included pre- and post-fracturing simulation and analysis, and laboratory measurements and experiments. The kISMET (permeability (k) and Induced Seismicity Management for Energy Technologies) site was established in the West Access Drift of the Sanford Underground Research Facility (SURF) 4757 ft (1450 m) below ground (on the 4850 ft level (4850L)) in phyllite of the Precambrian Poorman Formation. We drilled and continuously cored five near-vertical boreholes in a line on 3 m (10 ft) spacing, deviating the two outermost boreholes slightly to create a five-spot pattern around the test borehole centered in the test volume 40 m below the drift invert (floor) at a total depth of ~1490 m (4890 ft). Laboratory measurements of core from the center test borehole showed P-wave velocity heterogeneity along each core indicating strong, fine-scale (~1 cm or smaller) changes in the mechanical properties of the rock. Field measurements of the stress field by hydraulic fracturing showed that the minimum horizontal stress at the kISMET site averages 21.7 MPa (3146 psi) trending approximately N-S (356 degrees azimuth) and plunging slightly NNW at 12°. The vertical and horizontal maximum stresses are similar in magnitude at 42-44 MPa (6090-6380 psi) for the depths of testing, which averaged approximately 1530 m (5030 ft). Hydraulic fractures were remarkably uniform suggesting core-scale and larger rock fabric did not play a role in controlling fracture orientation. Analytical solutions suggest that the fracture radius of the large fracture (stimulation test) was more than 6 m (20 ft), depending on the unknown amount of leak-off.

Oldenburg, C↗

Ni5Ga3 Catalysts for CO2 Reduction to Methanol: Exploring the Role of Ga Surface Oxidation/reductions on Catalytic Activity

Ad-Ni5Ga3/SiO2 catalyst, which is highly active and stable for thermal CO2 hydrogenation to methanol, was investigated to understand its surface dynamics during reaction conditions. The catalyst was prepared, tested and characterized using a multitude of techniques, including ex-situ XRD, TEM, H2-TPR, CO chemisorption and in-situ ETEM and APXPS. The formation of Ga2O3 upon air exposure was observed and the consequences on catalytic activity were investigated. Results revealed that upon air exposure Ga migrates from the subsurface region to the surface of the nanoparticles forming a Ga-oxide shell surrounding a metallic core. The oxide shell can be reduced completely at high temperatures and the temperature of the reduction activation treatment plays a crucial role on the catalytic activity. This air exposure-reduction procedure results in a redistribution of the Ga species in the surface/subsurface region, promoted by a higher Ga affinity for oxygen. XRD analysis of the post-reaction samples provide evidence for the partial transformation of a Ni5Ga3 intermetallic phase into a Ni-rich Ni3Ga phase. APXPS data indicate that the Ni-rich phase forms in the subsurface region. A Ga-rich phase exists on the surface, where the Ni/Ga ratio reaches 2/3 upon activation in hydrogen. At low reduction temperatures an amorphous Ga2O3 shell remains, indicating a promotion effect on methanol synthesis activity.

Ni-Ga, intermetallic, methanol synthesis, in-situ ↗

High-throughput additive manufacturing and characterization of refractory high entropy alloys

Refractory High Entropy Alloys (RHEAs) and Refractory Complex Concentrated Alloys (RCCAs) are high-temperature structural alloys ideally suited for use in harsh environments. While these alloys have shown promising structural properties at high temperatures that exceed the practical limits of conventional alloys, such as Ni-based superalloys, exploration of the complex phase-space of these materials remains a significant challenge. We report on a high-throughput alloy processing and characterization methodology, leveraging laser-based metal additive manufacturing (AM) and mechanical testing techniques, to enable rapid exploration of RHEAs/RCCAs. We utilized in situ alloying and compositional grading, unique to AM processing, to rapidly-produce RHEAs/RCCAs using readily available and inexpensive commercial elemental powders. We demonstrate this approach with the MoNbTaW alloy system, as a model material known for having exceptionally high strength at elevated temperature when processed using conventional methods (e.g., casting). Microstructure analysis, chemical composition, and strain rate dependent hardness of AM-processed material are presented and discussed in the context of understanding the structure-properties relationships of RHEAs/RCCAs.

36 MATERIALS SCIENCE↗

Optimization and understanding of ZnO nanoarray supported Cu-ZnO-Al 2 O 3 catalyst for enhanced CO 2 -methanol conversion at low temperature and pressure

Cu-ZnO-Al 2 O 3 is the most widely applied catalyst for CO 2 hydrogenation to methanol. However, it is still a challenge to produce methanol using this catalyst under low-temperature (<250 °C) and low-pressure (<10 bar) conditions with desirable yield and selectivity. In this work, by tuning the experimental processing parameters such as solvent, loading amount, and annealing temperature, highly improved ZnO nanoarray supported Cu-ZnO-Al 2 O 3 catalysts have been successfully demonstrated. Here, by using organic solvent (N,N-dimethylformamide (DMF), acetone, or isopropanol) for dip-coating loading process instead of deionized (DI) water, Cu-ZnO-Al 2 O 3 nanocatalysts was comparatively better dispersed on the nanorod array support with populated and abundant active sites, thus enhancing the methanol yield. With the control of the loading amount and annealing temperature, finely distributed Cu nanoparticles were obtained on the ZnO nanorod surfaces to enhance the interactions between Cu and ZnO nanorod surfaces. Further improvement of the catalyst performance is demonstrated by tuning the reaction space velocity. At 200 °C and 10 bar conditions, the optimized catalyst achieved a methanol yield of 6.46 mol h –1 kg –1 with 100 % selectivity. The good stability after prolonged testing of the catalysts demonstrates the potential practical implementation. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements under the 1 bar reveal that the CO 2 hydrogenation to methanol on the ZnO nanoarray supported Cu-ZnO-Al 2 O 3 catalyst follows the CO reaction pathway, due to the surface oxygen vacancies on ZnO nanorods which facilitate CO 2 dissociation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

In-situ synchrotron X-ray diffraction investigation on deformation behavior of Nb/NiTi composite during pre-straining process

The mechanisms responsible for deformation behavior in Nb/NiTi composite during pre-straining were investigated systematically using in-situ synchrotron X-ray diffraction, transmission electron microscopy and tensile test. It is shown that upon loading, the composite experiences elastic elongation and slight plastic deformation of B19', B2 and β-Nb phases, together with the forward stress-induced martensitic (SIM) transformation from B2 to B19'. Upon unloading, the deformation mechanisms of the composite mainly involve elastic recovery of B19', B2 and β-Nb phases, compression deformation of β-Nb phase and incomplete B19'→B2 reverse SIM transformation. In the tensile loading-unloading procedure, besides the inherent elastic deformation and SIM transformation, the (001) compound twins in B19' martensite can also be conducive to the elastic deformation occurring in B19'-phase of the composite. Therefore, this composite can exhibit a large recoverable strain after unloading owing to the elastic deformation, and the partially reversible and consecutive SIM transformation together with the (001) compound twins.

36 MATERIALS SCIENCE↗

3D-Printed Membranes with a Zwitterionic Hydrogel Coating for More Robust Oil–Water Separation

Three-dimensional (3D)-printed membranes via stereolithography (SLA) are promising in oil–water separation, which is the key in the purification of industrial oily wastewater. To achieve gravity-driven oil–water separation, the membrane material needs to be simultaneously hydrophilic/oleophobic. However, most of the state-of-the-art materials for SLA do not meet the requirement. While water-adsorbing hydrogel is simultaneously hydrophilic/oleophobic and there have been reports on 3D printing of hydrogels in biomedical applications, the hydrogel is too soft for membrane application. Here, we report a simple approach to tackle the issue: a hydrogel coating on SLA-based plastic membranes. The coating is fabricated, using [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide as the zwitterionic monomer and acrylamide as the comonomer, via in situ polymerization on SLA-based plastic membranes. The contact angle tests and Fourier transform infrared spectrum show that such a membrane readily adsorbs water and becomes simultaneously hydrophilic/oleophobic. The oil–water separation tests indicate that the water-adsorbed membrane is highly efficient in gravity-driven oil–water separation in 31 repeating cycles. Our results indicate the great potential of 3D-printed membranes in oil–water separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Activation of Ni–Fe Oxides for the Oxygen Evolution Reaction in Alkaline Media

The oxygen evolution reaction (OER) is essential to many key electrochemical devices, including H 2 O electrolyzers, CO 2 electrolyzers, and metal−air batteries. NiFe oxides have been historically identified as active for the OER, though they have been less studied in their more commercially relevant bulk oxide forms, such as NiFe 2 O 4 . Past works have demonstrated that the initial starting phase of Ni(Fe) precatalysts can influence their activation to the Ni(Fe)OOH active phase, including the rate and degree of conversion, pointing to the necessity of understanding activation protocols and in situ characteristics of catalyst materials at the device level. In this work, we investigate the characteristics of commercially relevant NiFe bulk oxides (NiFe 2 O 4 and a physical mixture of NiO and γ-Fe 2 O 3 ) during multiple activation procedures. Our results demonstrate that significant performance enhancement is observed for these bulk oxides regardless of the Fe incorporation in the initial form (i.e., atomically or macroscopically integrated), leading to significant performance enhancement (up to 30×) over time on stream. We hypothesize that this activation is due to the formation of NiFeOOH active sites on the surface, supported by in situ cyclic voltammetry and Raman spectroscopy results. We further show that not only the starting material but also the method of activation influences the number of Ni(Fe)OOH active sites formed and suggest that these sites can be quantified from the Ni 2+ to Ni 3+ redox transition using cyclic voltammetry. Broadly, this work demonstrates the necessity of in situ characterization of catalyst materials for cell-level design and testing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Location-Dependent Mechanical Property Evaluation on Additively Manufacture Materials

This report summarizes research activities conducted at Argonne National Laboratory in support of the development, qualification and certification of additively manufactured (AM) metallic components to allow for innovative reactor design and licensing for the Transformational Challenge Reactor (TCR). Focus is on the evaluation of high temperature mechanical properties including creep and fatigue of 316L stainless steel manufactured by the laser powder bed fusion process. Creep behavior of AM 316L stainless steel was evaluated for rods printed by either or a combination of both lasers of the dual-laser system of a Concept Laser-M2 printer to examine the consistency across the build plate. Creep tests were conducted at temperatures of 550, 575, 600, and 650°C and stresses between 175 and 300 MPa using ASTM standard-sized specimens. The effect of heat treatments at different temperatures on creep properties of AM 316L SS was examined to understand the processing-microstructure-property relationship. Fatigue properties of AM 316L SS were investigated for two print geometries (rod and plate) and in two build orientations of printed plates. Locations of specimens in the build were carefully tracked such that the testing data can be directly related to location-specific in situ data to establish links between printing process, post-printing treatment, microstructure and mechanical properties. The work is to support the development of a digital platform informed approach to AM component qualification and certification for nuclear applications.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Development of a satellite microwave radiometer to sense the surface temperature of the world oceans

A proposed S-band radiometer for determining the ocean surface temperature with an absolute accuracy of + or - 1 Kelvin and a resolution of + or - .1 Kelvin was placed under the Advanced Applications Flight Experiment for further development into Nimbus readiness state. The results of assessing the following are described: effects due to the state of the sea surface, effects caused by the intervening atmosphere, and effects associated with imperfections in the instrument itself. An extensive sea truth program is also described for correlation of aircraft test flight measurements or of satellite remote measurement to in-situ data. An improved radiometer design is a modified Dicke-switch type with temperature stabilized, microwave integrated circuit, front-end and with a pulsed injection-noise nulling system. The radiometer has a multimode rectangular horn antenna with very low ohmic losses and a beam efficiency of 98% or better.

Hidy, G. M.↗

New Polymer Coatings for Chemically Selective Mass Sensors

There is a current need to develop sensitive and chemically specific sensors for the detection of nitric acid for in-situ measurements in the atmosphere. Polymer coatings have been synthesized and tested for their sensitivity and selectivity to nitric acid. A primary requirement for these polymers is detectability down to the parts per trillion range. The results of studies using these polymers as coatings for quartz crystal microbalances (QCM) and surface acoustic wave (SAW) devices will be presented.

Sims, S. C.↗