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At least 469 records · Page 26

INFLUENCE OF SUPPLEMENTARY ARGON GAS SHIELDING ON THE MICROSTRUCTURE AND MECHANICAL BEHAVIOR OF SS316L ADDITIVELY MANUFACTURED BY DIRECTED ENERGY DEPOSITION

The dissolution of atmospheric gases into parts additively manufactured by directed energy deposition (DED) has long been of concern, and stock shielding solutions have usually proven inadequate at fully removing atmospheric gases from weld beads. The objective of this work was to design a new supplementary argon gas shroud for a specific DED printer and evaluate its effect on microstructure and macroscopic properties of SS316L and the potential for printing more reactive metals such as Ti-6Al-4V. This was investigated by printing four SS316L sample blocks, two with and two without the shroud, each printed in two different orientations. These samples were subsequently evaluated with inert gas fusion (IGF), SEM/EDS imaging, and tensile tests. The shroud reduced oxygen content by 0.019-0.031%, and SEM imaging revealed fewer oxide inclusions. A more dramatic reduction of 0.13% oxygen and 0.171% nitrogen was observed by the inert gas fusion of Ti-6Al-4V samples. Overall, the results indicated the shroud was successful at reducing atmospheric gas uptake within the print region and may enable the printing of reactive metal powders in DED systems.

Helvie, Kyle↗

Revisions of ORNL 188 W Process Based on Nonradiological Experiments

Tungsten-188 is in widespread use in the 188 W(t 1/2 = 69 d)/ 188 Re(t 1/2 =16.9 h) biomedical generator. Oak Ridge National Laboratory (ORNL) has been providing this product to the world since 1999. At ORNL, 188 W is produced via irradiation in ORNL’s High Flux Isotope Reactor (HFIR). Enriched 186 W targets in the form of sintered metallic pellets or rings achieve a compact loading in the irradiation vessel, providing a high yield per unit target. The enrichment of the target is >90% 186 W and this isotope undergoes double neutron capture to produce the desired 188W product. While 188 W is produced by neutron bombardment, 191 Os(t 1/2 = 15.4 d) is simultaneously produced as a byproduct requiring separation from 188 W by post irradiation treatment. In the current processing pathway, the irradiated W metal pellets or rings are first converted into an oxide form of WO 3 by heating the irradiated W metal target at 750°C in a quartz reaction vessel inside a vertical furnace under a constant flow of air. During heating, W metal reacts with oxygen in the air to produce WO 3 , which is soluble in 6 M NaOH for later purification process. This oxidation process also converts 188 Os (the decay daughter of 188 W) and 191 Os (the irradiation produced byproduct) into OsO 4 , a highly volatile and toxic gas. The gaseous effluents driven from the quartz reaction vessel are passed through a scrubbing array to remove OsO 4 before the air is discharged from the process. This heterogeneous oxidation method simultaneously achieves two goals: 1). converting metal target to a soluble oxide form and 2). separating volatile OsO 4 away from the solid WO 3 product, although harmful 191 OsO 4 is unfavorable but being taken care of by the down road scrubbing array. In the past twenty years the existing OsO 4 scrubbing array served well in preventing OsO 4 from being released into the environment, until July of 2020 when a minor amount of 191 Os was found to have been released into the environment which resulted in a standby of building 4501 from July 2020 to February 2021.Since October 20 of 2020 a team of researchers from groups of RSTD and NEFD were organized to work for the following tasks: (1) Fully understand the root causes of the July incident of 191 Os release and create a redesigned 191 Os scrubbing array to eliminate the possibility of 191 Os release in future 188 W processes; (2) In Phase-1 tests, select a correct air (O 2 ) flow rate in 188 W process, that provides sufficient oxygen for the oxidation of tungsten metal, while still allowing sufficient resonance time for 191 Os removal by the scrubbers; (3) In Phase-2 tests, confirm the efficiency of the redesigned scrubbing array to absorb excessive amount of non-rad OsO 4 (generated from Os metal powder) at the selected air flow; (4) In Phase-3 tests, simulate the hot cell 188 W process by heating pressed non-rad W-Os pellets in a quartz vessel of new design and the new array under operation parameters selected in Phase-1 and -2; (5) Complete a new operation procedure for 188 W process in hot cell and a TM report as a summary of the Os Mitigation Project. This TM report summarizes the investigation on root causes from technical aspects in July 191 Os release and the correspondent improvement towards the redesigned 191 Os scrubbing system. The report presents the efforts made on selection of optimal operational parameter with the new scrubbing array and the quartz vessel of new design, based on experiment data obtained in Phase-1, -2 and -3 tests. Further renovations for 188 W process and additional improvement of W target treatment will also be discussed.

07 ISOTOPE AND RADIATION SOURCES↗

Irradiation of Advanced Cladding Specimens in the High Flux Isotope Reactor: Capsule Designs and Test Matrix

The Advanced Fuels Campaign (AFC) has initiated the Advanced Reactor Cladding (ARC) irradiation campaign to generate irradiation performance data for candidate fuel cladding concepts. The campaign includes a diverse set of ferritic/martensitic steels, oxide dispersion strengthened (ODS) alloys, FeCrAlbased alloys, coated materials, and welded cladding specimens produced through multiple US Department of Energy (DOE) programs and international collaborations. Three complementary experimental thrusts comprise the campaign: tensile testing (ARC Tensile) to rapidly screen candidate alloys, fracture toughness testing (ARC Fracture) to evaluate irradiation effects on crack resistance, and tubular weld testing (ARC Weld) to quantify irradiation-induced changes in the mechanical performance of end cap welds. This report documents the irradiation campaign design, including the selected materials, specimen types, irradiation matrix, and capsule designs for irradiation within the High Flux Isotope Reactor (HFIR). A total of 14 irradiation capsules were developed to achieve target irradiation temperatures between 300°C and 600°C and doses up to 30 dpa. Thermal analyses were performed using finite element methods to establish capsule geometries capable of achieving the desired specimen temperatures while accommodating differences in specimen geometry and material properties. The resulting capsule designs provide the basis for irradiation of the AFC-ARC experimental matrix and subsequent post-irradiation examination to assess the effects of neutron irradiation on advanced cladding materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Laser powder bed fusion of oxide dispersion-strengthened IN718 alloys: A complementary study on microstructure and mechanical properties

In this study, two new grades of oxide dispersion strengthened (ODS) Inconel 718 (IN718) alloys were designed by the thermochemical CALPHAD method and produced by laser powder bed fusion (LPBF) technique. Alloys designated as IN718-YF and IN718-YFH, that consist Y 2 O 3 –FeO and Y 2 O 3 –FeO–Hf, respectively, were fabricated with >99.9 % densification using optimized process parameters. CALPHAD calculations were highly consistent with experimental findings, highlighting the formation of Al-containing Y–Ti–O and Y–Hf–O nano-oxides in both alloy types. Texture analyzes revealed no significant texture development in as-built (AB) or heat-treated (HT) alloys. Heat treatment was applied at 1050 °C for 1 h to enhance nano-oxide density. Further, the nano-oxide number density remained similar in IN718-YF while it decreased in IN718-YFH alloy as a result of carbide formation after the heat treatment. Besides, formation of secondary γ' particles was observed in the IN718-YFH/HT alloy. Even though the yield strengths of IN718-YF and IN718-YFH alloys in both AB and HT conditions were similar, the ductility of IN718-YFH was ~50 % less in almost all conditions compared to the ductility of IN718-YF. This has been shown to be as a result of irregular shaped micron-sized Y-Hf-O oxides, martensite formation in AB condition, increased amount of carbides and existence of secondary γ' particles in HT condition in IN718-YFH. High density of stacking faults (SF) forming at the interface of the nano-oxides have been detected in IN718-YF alloys. Besides dislocation/nanoparticle interactions, SFs which are responsible for the delocalization of the deformation improve the ductility of IN718-YF alloys. Overall, high temperature mechanical tests exhibit that both alloys have higher strength with improved ductility compared to the standard IN718 alloys, indicating the contribution of the nano-oxides.

36 MATERIALS SCIENCE↗

Method for Evaluating Irradiation Effects on Flow Stress in Fe-9%Cr ODS Using TEM In Situ Cantilevers

Transmission electron microscopic (TEM) in situ mechanical testing has become a widely utilized tool for simultaneously measuring mechanical properties and understanding fundamental deformation mechanisms in irradiated and nuclear materials. Although tensile and compression specimen geometries are amongst the most common, opportunities remain for investigating alternative geometries that could provide unique insights into the plasticity of irradiated materials. This research demonstrates a new TEM in situ cantilever beam configuration. Cantilevers are produced from as-received and proton irradiated (1 dpa, 500°C) Fe-9%Cr oxide dispersion strengthened (ODS) steel. Flow stress is measured using a TEM in situ depth-sensing mechanical testing holder. A 200 MPa increase in flow stress is measured due to irradiation. Size effects arise when the intrinsic (i.e. microstructural) size approaches the extrinsic (i.e. external dimensions) size and can be described using a power law relationship as a function of the material microstructure and cantilever dimensions.

36 MATERIALS SCIENCE↗

Investigations on the Thermal Stability and Kinetics of Biolubricants Synthesized from Different Types of Vegetable Oils

Petroleum-based lubricants raise environmental concerns due to their non-biodegradability and toxicity, whereas biobased lubricants underperform owing to low thermal stability. This study examined and compared three vegetable oils, along with their chemically modified versions, to better understand their suitability as biolubricants. High oleic soybean oil (HOSOY), regular soybean oil (RSOY), and waste cooking oil (WCO) were subjected to chemical modification, where isopropyl groups were attached to the fatty acid chains of the oils to produce branched oils, i.e., b-HOSOY, b-RSOY, and b-WCO. The detailed kinetic study of each regular and modified sample was investigated using thermogravimetric analysis. The kinetic parameters, such as the activation energies, reaction rate, and pre-exponential factor, were generated via Friedman methods. The differential thermal gravimetric (DTG) analysis showed low volatilization at the onset temperature in each modified oil as compared with the unmodified samples under an oxidative environment. Furthermore, the comparative kinetic studies demonstrated the enhanced thermoxidative stability of the modified products relative to their unaltered counterparts. Among the tested oils, the b-RSOY showed an average activation energy of 325 kJ/mol, followed by the b-WCO: 300 kJ/mol and the b-HOSOY: 251 kJ/mol, indicating the most stable modified product under an oxidative environment. For all the samples, the pre-exponential factors were in good agreement with the activation energies, which validates that finding the pre-exponential components is crucial to the kinetic analysis.

Sarker, Majher I. (ORCID:0000000299509274)↗

How Selective Transport Layer Improves Efficiency and Durability of Proton Exchange Membrane Fuel Cells

In any electrochemical device, the separator or membrane allows specific ions to transport but blocks electrons and other chemical species, enabling the electrochemical energy to be harvested. However, small amounts of undesired species are known to permeate through the membrane, reducing overall system efficiency and lifetime. An emerging concept called the “Selective Transport Layer” preferentially allows only protons to pass through but reduces the permeance of other species by a meaningful degree. Here, in this study, we demonstrate that a 60 nm thick graphene oxide composite layer can be very effective in reducing gas and ion permeation, even for a gas as small as H 2 , while not noticeably increasing proton transport resistance. In electrode and membrane accelerated stability tests, we show that both electrode and membrane durability are improved by a factor of two. Microscopy and mathematic simulations confirm that the graphene oxide composite is effective in blocking transport of dissolved Pt 2+ . The improved durability and reduced H 2 fuel crossover are expected to substantially reduce initial and operating costs of the fuel cell system. How this technology may affect other membrane-based electrochemical devices is also discussed.

Ngo, Phuong Quynh [General Motors, Pontiac, MI (Un↗

Chemical Kinetics of the Autoxidation of Poly(ethylenimine) in CO 2 Sorbents

The oxidative degradation rates of a CO 2 sorbent composed of a mesoporous alumina impregnated with poly- (ethylenimine) (PEI) are measured under systematically varied conditions and a reaction rate law is created. Good agreement is shown between the rate of oxidation obtained via in situ calorimetric heat measurement during oxidative degradation reactions and the loss of CO 2 capture performance presented as amine efficiency (mol CO 2 /mol amine). PEI mass loss and elemental composition are tracked over the course of the reaction and used in conjunction with the oxidation rate measurements to shed insight into the oxidation reaction(s). These data, in combination with measurements of the heat of reaction, suggest a common reaction set across the range of temperatures, oxygen concentrations, and sorbent compositions tested. The data are consistent with the basic autoxidation scheme (BAS), the accepted mechanism of autoxidation of aliphatic polymers. We propose a lumped kinetic model to describe the oxidation reaction set and estimate an activation energy of 105 kJ/mol and an oxygen reaction order of 0.5–0.7 from the data accordingly. Furthermore, these parameters can be incorporated into process cycle models to estimate the material lifetime, a critical uncertainty in the deployment of DAC technologies.

36 MATERIALS SCIENCE↗

Lepidopteran mevalonate pathway optimization in Escherichia coli efficiently produces isoprenol analogs for next-generation biofuels

Terpenes constitute the largest class of natural products with over 55,000 compounds with versatile applications including drugs and biofuels. Introducing structural modifications to terpenes through metabolic engineering is an efficient and sustainable way to improve their properties. Here, in this study, we report the optimization of the lepidopteran mevalonate (LMVA) pathway towards the efficient production of isopentenyl pyrophosphate (IPP) analogs as terpene precursors. First, we linked the LMVA pathway to NudB, a promiscuous phosphatase, resulting in the production of the six-carbon analog of 3-methyl-3-buten-1-ol (isoprenol), 3-ethyl-3-buten-1-ol (C6-isoprenol). Using C6-isoprenol as the final product, we then engineered the LMVA pathway by redirecting its upstream portion from a thiolase-dependent pathway to a beta-oxidation pathway. The beta-oxidation LMVA pathway transforms valeric acid, a platform chemical that can be produced from biomass, into C6-isoprenol at a titer of 110.3 mg/L, improved from 5.5 mg/L by the thiolase LMVA pathway, which used propionic acid as a feedstock. Knockout of the E. coli endogenous thiolase genes further improved the C6-isoprenol titer to 390 mg/L, implying efficient production of homo isopentenyl pyrophosphate (HIPP). The beta-oxidation LMVA-NudB pathway also converts butanoic acid and hexanoic acid into isoprenol and isoprenol’s seven-carbon analog, 3-propyl-3-buten-1-ol (C7-isoprenol), respectively, suggesting the beta-oxidation LMVA pathway produces IPP and C7-IPP from the corresponding fatty acids. Fuel property tests revealed the longer chain isoprenol analogs have lower water solubilities, similar or higher energy densities, and comparable research octane number (RON) boosting effects to isopentenols. This work not only optimizes the LMVA pathway, setting the basis for homoterpene biosynthesis to expand terpene chemical space, but provides an efficient pathway to produce isoprenol analogs as next-generation biofuels from sustainable feedstocks.

59 BASIC BIOLOGICAL SCIENCES↗

Single-Step Nonthermal Plasma Synthesis of Water-Soluble and Near-Infrared-Emitting Si Quantum Dots for Bioimaging Applications

Here, we present a single-step nonthermal plasma method for the synthesis of near-infrared (NIR)-emitting and water-soluble Si quantum dots (QDs) for bioimaging applications. Oxygen gas and water vapor were introduced together with acrylic acid (AA) into the afterglow region of the synthesis plasma leading to the surface functionalization of the upstream synthesized Si QDs. The simultaneous surface oxidation and ligand grafting enabled solubility and colloidal stability of the Si QDs in water, as evidenced by strongly reduced hydrodynamic diameters. Aged Si QDs in water emitted NIR photoluminescence (PL) at around 830 nm. The PL quantum yield of the Si QDs in water increased over time from initially undetectable to ~30% after 8 days. Cell viability tests showed that >70% of 3T3 cells survived for 24 h at a concentration of 200 μg/mL of oxidized AA grafted Si QDs. The water solubility, NIR emission with a high quantum yield, and cell viability make the Si QDs promising for bioimaging applications.

36 MATERIALS SCIENCE↗

Battery Abuse Testing

Abuse tests are designed to determine the safe operating limits of HEV\PHEV energy storage devices. Testing is intended to achieve certain worst-case scenarios to yield quantitative data on cell\module\pack response, allowing for failure mode determination and guiding developers toward improved materials and designs. Standard abuse tests with defined start and end conditions are performed on all devices to provide comparison between technologies. New tests and protocols are developed and evaluated to more closely simulate real-world failure conditions. While robust mechanical models for vehicles and vehicle components exist, there is a gap for mechanical modeling of EV batteries. The challenge with developing a mechanical model for a battery is the heterogeneous nature of the materials and components (polymers, metals, metal oxides, liquids). This year saw the stand up of a new drop tower tester capable of providing dynamic mechanical test results.

25 ENERGY STORAGE↗

Kinetic Probes of the Origin of Activity in MOF-Based C–H Oxidation Catalysis

The development of homogeneous catalysis is enabled by the availability of a rich toolkit of kinetics experiments, such as the Hgdrop test, that differentiate catalytic activity at ligand-supported metal complexes from potential heterogeneous catalysts derived from decomposition of molecular species. Metal-organic frameworks (MOFs) have garnered significant attention as platforms for catalysis at site-isolated, interstitial catalyst sites. Unlike homogeneous catalysis, relatively few strategies have been advanced to evaluate the origin of catalytic activity in MOF-promoted reactions. Many of the MOFs that have been examined as potential catalysts are comprised of molecular constituents that represent viable catalysts in the absence of the extended MOF lattice, and thus interfacial sites and leached homogeneous species represent potential sources of catalyst activity. Here, we demonstrate that analysis of deuterium kinetic isotope effects (KIEs) and olefin epoxidation diastereoselectivity provides probes of the origin of catalytic activity in MOF-promoted oxidation reactions. These analyses support involvement of lattice-based Fe sites in the turnover-limiting step of C–H activation with Fe-MOF-74-based materials (i.e., the MOF functions as a bona fide catalyst) and evidence that Cu 2 -based MOF MIL-125-Cu 2 O 2 functions as a solid-state initiator for solution-phase oxidation chemistry and is not involved in the turnover limiting step (i.e., the MOF does not function as a catalyst for substrate functionalization). furthermore, we anticipate that the simple experiments described here will provide a valuable tool for clarifying the role of MOFs in C–H oxidation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MS25: Materials Science-Focused Benchmark Data Set for Machine Learning Interatomic Potentials

Here, we present MS25, a benchmark data set for evaluating machine learning interatomic potentials (MLIPs) across diverse materials-relevant systems including MgO surfaces, liquid water, zeolites, a catalytic Pt surface reaction, high-entropy alloys (HEAs), and disordered Zr-oxides. Five MLIP architectures (MACE, NequIP, Allegro, MTP, and Torch-ANI) are trained and tested, focusing not only on traditional metrics (energies, forces, and stresses) but also explicitly validating derived physical observables such as lattice constants, volumes, and reaction barriers. We find that most models reach comparable accuracy on standard error metrics across the simple systems, although equivariant MLIPs offer 1.5–2× improvements over nonequivariant MLIPs in energy and force error for structurally complex or compositionally disordered environments such as HEAs and Zr–O systems. Our analysis highlights that low errors in energy and force predictions do not guarantee reliable observables, emphasizing the necessity of explicit validation. We demonstrate limitations in cross-framework transferability, as models trained on one zeolite framework (CHA) fail to reliably generalize to predictions of structurally distinct frameworks (e.g., MFI). Size-extensive tests show some dependence on system size for MgO, resulting from forced periodicity. The HEA and Zr–O data sets are identified as challenging tests for future benchmarks and MLIP model architecture developments as they show significant differentiation in error between MLIP architectures and are still relatively difficult at 1000 training images. Moving forward, we recommend that benchmarking efforts shift their focus from marginal accuracy improvements in energy and force errors toward identifying and understanding model failure modes, rigorously assessing transferability, and evaluating how their errors affect observable predictions. For researchers looking to choose an MLIP architecture, we suggest selecting equivariant MLIP architectures if the complexity of the system is a challenge. For simple materials problems, auxiliary features such as integration with molecular dynamics engines, trade-offs between computational data set generation cost vs MLIP inference speed, and framework integration may play a more important decision factor than small differences in error metrics that are unlikely to matter for production-level research.

chemical structure↗

Experimental Characterization of Hygrothermal Aging: Competition Between Thermo-Oxidation and Hydrolysis Phenomena

Abstract In this work, we have presented a comparison between effects of accelerated thermo-oxidative, hydrolytic and hygrothermal aging on the mechanical and chemical properties of a polyurethane based (PUB) adhesive. The adhesive is a flexible adhesive which is extensively used in automobile industry as a glass sealant. During service life it gets exposed to the hygrothermal environment and the integrity of matrix interface is most vulnerable. This study focuses on weighing and comparing effects of different aging environments on material behavior; and it shows that hygrothermal aging environment results as a competition between two sub-aging phenomena i.e., thermo-oxidation and hydrolytic aging. Samples were exposed to 0%RH, 80%RH and submerged condition in distilled water. Uni-axial tensile tests, and cross-link density analysis by swelling test were carried out on as-received and aged samples. The aging process was conducted at three different temperatures (60°C, 80°C and 95°C) and for four different exposure durations of 1, 10, 30, and 90 days. This work confirms that the effect of hygrothermal aging is a result of competition between thermo-oxidation and hydrolytic aging environments. The total mechanical and environmental damage incurred by specimens is a collaborative effect of all exposure environments involved i.e., aging time, temperature, oxygen, water and humidity. The results are in agreement with the chemical test outcomes as well.

Shaafaey, Mamoon↗

Boosting the Oxygen Reduction Performance via Tuning the Synergy between Metal Core and Oxide Shell of Metal−Organic Frameworks‐Derived Co@CoO x

Abstract Co core@Co oxide shell (Co@CoO x ) catalysts represent a large family with promising oxygen reduction reaction (ORR) catalytic activity. However, inadequate understanding of Co@CoO x synergy prohibits further pursuit of catalytic performance enhancement. Herein, a Co zeolitic−imidazolate framework was converted into metallic Co, followed by controlled air treatment to form Co@CoO x . The composition and structure evolution as a function of air treatment temperature were studied thoroughly through conventional and synchrotron (both ex‐situ and in‐situ) characterizations, confirming the coexistence of CoO and Co 3 O 4 in the shell. The optimal catalyst showed an ORR half‐wave potential of 0.87 V (vs. RHE) in an alkaline half‐cell and delivered high discharge capacity in an aprotic Li−O 2 battery (7,124 mAh g Cat+C −1 ) and an aqueous Zn−air battery (694 mAh g Zn −1 ) with good performance retention after durability test. Modeling simulation and density functional theory calculation confirmed the charge donation from metal core to oxide shell and shed light on new insights of how metal@metal oxide synergy impacted the ORR via tuning the charge conductivity, oxygen affinity and intermediate transfer pathway. This work opens up a venue to boost ORR catalytic activity from an interfacial synergy perspective.

Wang, Hao↗

Long Term Assessment of Radiocesium in Deer, Fish, Soil, and Vegetation at the Savannah River Site

Throughout the Savannah River Site's (SRS) operational history, many radionuclides have been released into the environment. However, due to fallout from weapons testing, the amount released from SRS, its persistence in the environment, and the seclusion of the Site, radiocesium (Cs-137) is one of the most critical radionuclides in the SRS environment. The Effective half-life (Te) is the time it takes for a radionuclide in the environment to decrease by 50% of its initial amount. There are three means of radionuclide removal: Physical: Radioactive decay, sedimentation, and washout; Chemical: Changes in pH, oxidation state or adsorption; Biological: Changes in the food web or translocation. Effective half-life (T{sub e}) = log{sub e}2/λ{sub e} Where λ{sub e} is estimated from the slopes of loge-transformed Cs-137 activity concentrations regressed on year. The objective of this work was to calculate the effective half-life of Cs-137 in various biota at SRS and to perform an assessment of the changes in the effective half life over time. Compared to 2013 data, there is a slight increase in the effective half-lives for fish at most sampling locations. This effective half-life increase is an indication that the rate of Cs-137 loss is starting to plateau. The effective half-life of Cs-137 in SRS fish ranges from 4-11 years. The effective half-life of Cs-137 in soil at the Creek plantation is about 15 years. The effective half-life of Cs-137 in grassy vegetation at the Creek Plantation is about 14 years. The effective half-life of deer hunted on the SRS is about 15.5 years. After termination of all reactor activity by 1980, the Cs-137 activity began to drop drastically.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Measurement of Contact Resistivity In Symmetric Polycrystalline Si/SiO x /Monocrystalline Si Test Structures Using Variable Light Illumination

While different methods exist to determine the contact resistivity in semiconductor devices, these methods are limited to measurement of the majority carrier contacts. The measurement of p‐ or n‐type contacts on n‐ or p‐type crystalline silicon, respectively, is challenging due to the blocking diode formed by the p–n junction. In this article, we address this problem for tunneling oxide passivating contacts used in high‐efficiency Si solar cells. We propose a universal method to extract contact resistivity on symmetric test structures with polycrystalline silicon on SiO x (poly‐Si/SiO x ) passivating contacts under illumination, both for p–n and high–low‐junction passivated contacts. In this method, we demonstrate that the total contact resistance of each cell grid finger to the base wafer is governed by its effective contact area, defined by the transfer length extending from both sides of the finger. Therefore, the grid contact resistance of a poly‐Si contact depends on the ratio of the doped poly‐Si sheet resistance to the tunneling contact resistivity.

14 SOLAR ENERGY↗

Methane combustion over Ni/Ce x Zr 1-x O 2 catalysts: impact of ceria/zirconia ratio

In this work, a series of Ce x Zr 1–x O 2 (x=1, 0.83, 0.17, 0) supports and 2 wt.% Ni/Ce x Zr 1–x O 2 catalysts were synthesized and evaluated for CH 4 oxidation. The Ce x Zr 1–x O 2 supports showed moderate activity (T 50 =519-638°C) with CO by-product formation. Additionally, nickel incorporation onto Ce x Zr 1–x O 2 lowered the T 50 to 438–477°C and eliminated the formation of CO. The results indicated that moderate Zr doping improved the support oxygen storage capacity (OSC) and reducibility of the catalyst at low temperatures (H 2 -TPR) leading to an enhanced CH 4 combustion turnover frequency: Ni/ZrO 2 <Ni/Ce 0.17 Zr 0.83 O 2 <Ni/CeO 2 <Ni/Ce 0.83 Zr 0.17 O 2 . The apparent activation energies of Ni/Ce x Zr 1–x O 2 catalysts (87-92 kJ/mol) were much lower than the ones of Ce x Zr 1–x O 2 supports and Ni/quartz sand (111-120 kJ/mol) indicating that CH 4 oxidation is facilitated when Ni is deposited on Ce x Zr 1–x O 2 . Moreover, stability tests with H 2 O and CO 2 showed that Zr doping can improve the catalyst stability, while H 2 O had a stronger reversible inhibition effect than CO 2 for CH 4 combustion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗