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At least 1,063 records · Page 59

Recent developments in catalyst-related PEM fuel cell durability

Cost and durability remain the two major barriers to the widespread commercialization of polymer electrolyte membrane fuel cell (PEMFC)-based power systems, especially for the most impactful but challenging fuel cell electric vehicle (FCEV) application. Commercial FCEVs are now on the road; however, their PEMFC systems do not meet the cost targets established by the U.S. Department of Energy, primarily due to the high platinum loading needed on the cathode to achieve the requisite performance and lifetime. Furthermore, while the activities of a number of commercial Pt-based alloy cathode catalysts exceed the beginning-of-life (BOL) targets, these activities, and the overall cathode performance, degrade via a variety of mechanisms described herein. Degradation is mitigated in current FCEVs by utilizing a cathode catalyst with a lower BOL activity (e.g., much lower transition metal alloy content and larger BOL nanoparticle size), necessitating higher catalyst loadings, and through the utilization of system controls that avoid conditions known to exacerbate degradation processes, such as limiting the fuel cell stack voltage range. The design and development of active and robust materials and eliminating the need for vehicle mitigation strategies would greatly simplify the operating system, allowing for greater transient operation, avoiding large hybridization, and curtailing of fuel cell power. Although system mitigation strategies have provided the near-term pathway for FCEV commercialization, material-specific solutions are required to further reduce costs and improve operability and efficiency. Future material developments should focus on stabilization of the electrode structure and minimization of the catalyst particle susceptibility to dissolution caused by oxide formation and reduction over PEMFC cathode-relevant operating potentials plus minimization of support corrosion. Ex situ accelerated stress tests have provided insight into the processes responsible for material and performance degradation and will continue to provide useful information on the relative stability of materials and benchmarks for robust and stable materials-based solutions not requiring system mitigation strategies to achieve adequate lifetime.

25 ENERGY STORAGE↗

Sputtered carbon as a corrosion barrier for x-ray detector windows

Sputtered amorphous carbon thin films were explored as corrosion resistant coatings on aluminum thin films to be incorporated into x-ray detector windows. The requirements for this application include high corrosion resistance, low intrinsic stress, high strains at failure, and high x-ray transmission. Low temperature sputtering was used because of its compatibility with the rest of the window fabrication process. Corrosion resistance was tested by exposure of carbon coated and uncoated Al thin films to humidity. Substrate curvature and bulge testing measurements were used to determine intrinsic stress and ultimate strain at failure. The composition and bonding of the carbon films were further characterized by electron energy loss spectroscopy, Raman spectroscopy, and carbon, hydrogen, and nitrogen elemental analyses. Samples had low compressive stress (down to.08 GPa), a high strain at failure (3%), and a low fraction of sp{sup 3} carbon–carbon bonds (less than 5%). The high breaking strain and excellent x-ray transmission of these sputtered carbon films indicate that they will work well as corrosion barriers in this application.

36 MATERIALS SCIENCE↗

EVALUATION OF REQUIREMENTS FOR THE DWPF HIGHER CAPACITY CANISTER

The Defense Waste Processing Facility (DWPF) is considering the option to increase canister glass capacity by reducing the wall thickness of the current production canister. This design has been designated as the DWPF Higher Capacity Canister (HCC). A significant decrease in the number of canisters processed during the life of the facility would be achieved if the HCC were implemented leading to a reduced overall reduction in life cycle costs. Prior to implementation of the change, Savannah River National Laboratory (SRNL) was requested to conduct an evaluation of the potential impacts. The specific areas of interest included loading and deformation of the canister during the filling process. Additionally, the effect of the reduced wall thickness on corrosion and material compatibility needed to be addressed. Finally the integrity of the canister during decontamination and other handling steps needed to be determined. The initial request regarding canister fabrication was later addressed in an alternate study. A preliminary review of canister requirements and previous testing was conducted prior to determining the testing approach. Thermal and stress models were developed to predict the forces on the canister during the pouring and cooling process. The thermal model shows the HCC increasing and decreasing in temperature at a slightly faster rate than the original. The HCC is shown to have a 3°F ΔT between the internal and outer surfaces versus a 5°F ΔT for the original design. The stress model indicates strain values ranging from 1.9% to 2.9% for the standard canister and 2.5% to 3.1% for the HCC. These values are dependent on the glass level relative to the thickness transition between the top head and the canister wall. This information, along with field readings, was used to set up environmental test conditions for corrosion studies. Small 304-L canisters were filled with glass and subjected to accelerated environmental testing for 3 months. No evidence of stress corrosion cracking was indicated on either the canisters or U-bend coupons. Calculations and finite element modeling were used to determine forces over a range of handling conditions along with possible forces during decontamination. While expected reductions in some physical characteristics were found in the HCC, none were found to be significant when compared to the required values necessary to perform its intended function. Based on this study and a review of successful testing of thinner canisters at West Valley Demonstration Project (WVDP), the mechanical properties obtained with the thinner wall do not significantly undermine the ability of the canister to perform its intended function.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Relation of Engine Turbine-blade Life to Stress-rupture Properties of the Alloys, Stellite 21, Hastelloy B, Cast S-816, Forged S-816, X-40, Nimonic 80, Refractaloy 26, N-155, and Inconel X

An investigation was conducted to relate the engine performance of the heat-resistant alloys, Stellite 21, Hastelloy B, cast S-816, forged S-816, X-40, Nimonic 80, Refractory 26, N-155, and Iconel X to their stress-rupture properties. The engine test consisted of the repetition of a 20-minute cycle, 15 minutes at rated speed and approximately 5 minutes at idle. The results of the investigation indicated a direct correlation between stress-rupture life and blade life for the relatively low-strength alloys. The stress-rupture life and blade life for the relatively high-strength alloys did not correlate because of the effects of the vibratory stresses and the corrosive-gas atmosphere.

ALLOYS, HEAT-RESISTING↗

Analysis of critically refracted longitudinal waves

Fabrication processes, such as, welding, forging, and rolling can induce residual stresses in metals that will impact product performance and phenomena such as cracking and corrosion. To better manage residual stress tools are needed to map their distribution. The critically refracted ultrasonic longitudinal (LCR) wave is one such approach that has been used for residual stress characterization. It has been shown to be sensitive to stress and less sensitive to the effects of the texture of the material. Although the LCR wave is increasingly widely applied, the factors that influence the formation of the LCR beam are seldom discussed. This paper reports a numerical model used to investigate the transducers' parameters that can contribute to the directionality of the LCR wave and hence enable performance optimization when used for industrial applications. An orthogonal test method is used to study the transducer parameters which influence the LCR wave beams. This method provides a design tool that can be used to study and optimize multiple parameter experiments and it can identify which parameter or parameters are of most significance. The simulation of the sound field in a 2-D 'water-steel' model is obtained using a Spatial Fourier Analysis method. The effects of incident angle, standoff, the aperture and the center frequency of the transducer were studied. Results show that the aperture of the transducer, the center frequency and the incident angle are the most important factors in controlling the directivity of the resulting LCR wave fields.

42 ENGINEERING↗

Characterization of wellbore casing corrosion product as a permeable porous medium

Leakage along wellbores is of concern for a variety of applications, including sub-surface fluid storage facilities, geothermal wells, and CO 2 storage wells. We have investigated whether corroded casing is permeable to gas and can serve as a leakage pathway along wellbores. Three specimens were prepared from laboratory steel plates corroded using different mechanisms to reflect different possible field conditions and produce a variety of corrosion rates. Single-phase gas flow measurements were made under a range of gas pressures to investigate flow in both the viscous and visco-inertial flow regimes. Tests were conducted at different confining stresses (range from 3.45 to 13.79 MPa) following both loading and unloading paths. The gas flow test results imply corroded casing can serve as a significant leakage path along the axis of a wellbore. Transmissivity was discovered to be sensitive to the variation in confining stress suggesting that the corrosion product is deformable. Gas slip factors and the coefficients of inertial resistance of the corrosion product were comparable to those available in the literature for other porous media. Post-test examination of the corrosion product revealed it to be a heterogeneous, mesoporous material with mostly non-uniform slit type porosity. There was no discernable difference in the composition of corrosion product from specimens corroded by different mechanisms.

02 PETROLEUM↗

A review on molten sulfate salts induced hot corrosion

Hot corrosion has been extensively observed in various high temperature applications, which might cause large economic losses. Here, to deepen the insight and understanding of hot corrosion, we provide a detailed discussion on hot corrosion induced by molten sulfate salt, in which Na 2 SO 4 is the main chemical reactant. The hot corrosion is triggered and sustained by the negative solubility gradient of protective oxide from the oxide/salt interface to salt/gas interface. In this work, we reviewed several key factors, including temperature, gas composition, molten salt composition, alloy element and external stress, influencing the hot corrosion of alloy beneath the molten salt. The application of anti-corrosion coating seems to be the most effective and commercial mothed to mitigate hot corrosion. Therefore, the progress of the development of effective coatings, e.g., Ni-Cr coatings, aluminide coatings, silicide coatings and MCrAlY(X) coatings, has also been summarized.

36 MATERIALS SCIENCE↗

Fatigue-test acceleration with flight-by-flight loading and heating to simulate supersonic-transport operation

Possibilities for reducing fatigue-test time for supersonic-transport materials and structures were studied in tests with simulated flight-by-flight loading. In order to determine whether short-time tests were feasible, the results of accelerated tests (2 sec per flight) were compared with the results of real-time tests (96 min per flight). The effects of design mean stress, the stress range for ground-air-ground cycles, simulated thermal stress, the number of stress cycles in each flight, and salt corrosion were studied. The flight-by-flight stress sequences were applied to notched sheet specimens of Ti-8Al-1Mo-1V and Ti-6Al-4V titanium alloys. A linear cumulative-damage analysis accounted for large changes in stress range of the simulated flights but did not account for the differences between real-time and accelerated tests. The fatigue lives from accelerated tests were generally within a factor of two of the lives from real-time tests; thus, within the scope of the investigation, accelerated testing seems feasible.

Imig, L. A.↗

Liquid Salt Heat Exchanger Technology for VHTR Based Applications

The objective of this research is to evaluate performance of liquid salt fluids for use as a heat carrier for transferring high-temperature process heat from the very high-temperature reactor (VHTR) to chemical process plants. Currently, helium is being considered as the heat transfer fluid; however, the tube size requirements and the power associated with pumping helium may not be economical. Recent work on liquid salts has shown tremendous potential to transport high-temperature heat efficiently at low pressures over long distances. This project has two broad objectives: To investigate the compatibility of Incoloy 617 and coated and uncoated SiC ceramic composite with MgCl 2 -KCl molten salt to determine component lifetimes and aid in the design of heat exchangers and piping; and, To conduct the necessary research on the development of metallic and ceramic heat exchangers, which are needed for both the helium-to-salt side and salt-to-process side, with the goal of making these heat exchangers technologically viable. The research will consist of three separate tasks. The first task deals with material compatibility issues with liquid salt and the development of techniques for on-line measurement of corrosion products, which can be used to measure material loss in heat exchangers. Researchers will examine static corrosion of candidate materials in specific high-temperature heat transfer salt systems and develop an in situ electrochemical probe to measure metallic species concentrations dissolved in the liquid salt. The second task deals with the design of both the intermediate and process side heat exchanger systems. Researchers will optimize heat exchanger design and study issues related to corrosion, fabrication, and thermal stresses using commercial and in-house codes. The third task focuses integral testing of flowing liquid salts in a heat transfer/materials loop to determine potential issues of using the salts and to capture realistic behavior of the salts in a small scale prototype system. This includes investigations of plugging issues, heat transfer, pressure drop, and the corrosion and erosion of materials in the flowing system.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Thermal barrier coating life prediction model development

The objective of this program is to develop an integrated life prediction model accounting for all potential life-limiting Thermal Barrier Coating (TBC) degradation and failure modes including spallation resulting from cyclic thermal stress, oxidative degradation, hot corrosion, erosion, and foreign object damage (FOD). The mechanisms and relative importance of the various degradation and failure modes will be determined, and the methodology to predict predominant mode failure life in turbine airfoil application will be developed and verified. An empirically based correlative model relating coating life to parametrically expressed driving forces such as temperature and stress will be employed. The two-layer TBC system being investigated, designated PWA264, currently is in commercial aircraft revenue service. It consists of an inner low pressure chamber plasma-sprayed NiCoCrAlY metallic bond coat underlayer (4 to 6 mils) and an outer air plasma-sprayed 7 w/o Y2O3-ZrO2 (8 to 12 mils) ceramic top layer.

Demasi, J.↗

Distinct Mechanism of Anti-Corrosion and Swelling-Adhesion Modeling of Low-Dimensional Nylon-Fluoropolymer Composite Coatings

Compared to other polymers, composite coatings with fluoropolymers as the matrix have attracted considerable interest due to their mechanical performance, chemical stability, and low surface energy. Herein, we present an anticorrosion mechanism of fluoropolymer composite coatings achieved by dispersing varying amounts of polyamide 12 (PA-12) particles over a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix. The choice of PVDF-HFP as a coating matrix was driven by its superior processability and mechanical properties over Teflon, while PA-12 afforded swelling capacity, preventing electrolyte permeation, and inhibiting matrix stress crack propagation. The corrosion resistance of the coatings was assessed mainly by potentiodynamic polarization and impedance measurements while being immersed in a NaCl solution. Our electrochemical measurement findings showed that 0.75% w/w PA-12 in the PVDF-HFP matrix significantly enhanced corrosion protection even after 21 days of immersion. Microscopy, dielectric spectroscopy, surface analysis, and mechanical testing (American Society for Testing and Materials standards) corroborated the results. PVDF-HFP coatings containing a minimum percolation threshold of 0.75 wt % PA-12 with 1 mil thickness on mild steel exhibited a remarkable increase in resistance and film adhesion, and a notable corrosion rate decrease. Finite element analysis simulation with a bilinear traction-separation law confirmed the swelling mechanism and adhesion behavior. Finally, this study highlights the potential of nylon particle dispersion in PVDF-HFP matrices as a practical approach to developing advanced anticorrosion coatings with promising practical applications in various industries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bending-induced Symmetry Breaking of Lithiation in Germanium Nanowires

From signal transduction of living cells to oxidation and corrosion of metals, mechanical stress intimately couples with chemical reactions, regulating these biological and physiochemical processes. The coupled effect is particularly evident in electrochemical lithiation/delithiation cycling of high-capacity electrodes, such as silicon (Si), where on one hand lithiation-generated stress mediates lithiation kinetics, and on the other electrochemical reaction rate regulates stress generation and mechanical failure of the electrodes. Here we report for the first time the evidence on the controlled lithiation in germanium nanowires (GeNWs) through external bending. Contrary to the symmetric core-shell lithiation in free-standing GeNWs, we show bending GeNWs breaks the lithiation symmetry, speeding up lithaition at the tensile side while slowing down at the compressive side of the GeNWs. The bending-induced symmetry breaking of lithiation in GeNWs is further corroborated by chemomechanical modeling. In the light of the coupled effect between lithiation kinetics and mechanical stress in the electrochemical cycling, our findings shed light on strain/stress engineering of durable high-rate electrodes and energy harvesting through mechanical motion.

Environmental Molecular Sciences Laboratory↗

Magnetic Field Optimization of an In-Vacuum Undulator at NSLS-II Transactions on Applied Superconductivity

A 3.0 m long In-Vacuum Undulator (IVU) is employed at the National Synchrotron Light Source II (NSLS-II) for the Hard X-ray Nanoprobe (HXN) beamline providing structural and X-ray fluorescence imaging with world-leading spatial resolution. On July 1 st 2018 a gearbox shaft in the gap drive train assembly sheared due to corrosion fatigue caused by stress due to mechanical misalignment. Furthermore, the device was extracted from the storage ring and measured. The magnetic field measurements detected a degradation of the magnetic performance as well as a localized demagnetization of the magnetic modules of the first 3 upstream periods. We describe here the mechanical repairs and the magnetic phase shimming optimization implemented to restore the spectral performance of the device.

43 PARTICLE ACCELERATORS↗

Millimeter-Wave Thermal Analysis Development and Application to GEN IV Reactor Materials

New millimeter-wave thermal analysis instrumentation has been developed and studied for characterization of materials required for diverse fuel and structural needs in high temperature reactor environments such as the Next Generation Nuclear Plant (NGNP). A two-receiver 137 GHz system with orthogonal polarizations for anisotropic resolution of material properties has been implemented at MIT. The system was tested with graphite and silicon carbide specimens at temperatures up to 1300 ºC inside an electric furnace. The analytic and hardware basis for active millimeter-wave radiometry of reactor materials at high temperature has been established. Real-time, non contact measurement sensitivity to anisotropic surface emissivity and submillimeter surface displacement was demonstrated. The 137 GHz emissivity of reactor grade graphite (NBG17) from SGL Group was found to be low, ~ 5 %, in the 500 – 1200 °C range and increases by a factor of 2 to 4 with small linear grooves simulating fracturing. The low graphite emissivity would make millimeter-wave active radiometry a sensitive diagnostic of graphite changes due to environmentally induced stress fracturing, swelling, or corrosion. The silicon carbide tested from Ortek, Inc. was found to have a much higher emissivity at 137 GHz of ~90% Thin coatings of silicon carbide on reactor grade graphite supplied by SGL Group were found to be mostly transparent to millimeter-waves, increasing the 137 GHz emissivity of the coated reactor grade graphite to about ~14% at 1250 ºC.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Repair and Retuning of 3-m long In-Vacuum Undulator at NSLS-II

A 3.0 m long In-Vacuum Undulator (IVU) is employed at the National Synchrotron Light Source II (NSLS-II) for the Hard X-ray Nanoprobe (HXN) beamline providing structural and X-ray fluorescence imaging with world-leading spatial resolution. On July 1st 2018 a gearbox shaft in the gap drive train assembly sheared due to corrosion fatigue caused by stress due to mechanical misalignment. The device was extracted from the storage ring and measured. The magnetic field measurements detected a degradation of the magnetic performance as well as a localized demagnetization of the magnetic modules of the first 3 upstream periods. This paper describes the mechanical repairs and the magnetic phase shimming optimization implemented to restore the spectral performance of the device.

36 MATERIALS SCIENCE↗

Thermal barrier coating life prediction model development

The objective is to develop an integrated life prediction model accounting for all potential life-limiting thermal barrier coating (TBC) degradation and failure modes, including spallation resulting from cyclic thermal stress, oxidation degradation, hot corrosion, erosion and foreign object damage.

Demasi, J. T.↗