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At least 37 records · Page 2

Unveiling the Morphological and Physical Mechanism of Burn–in Loss Alleviation by Ternary Matrix Toward Stable and Efficient All–Polymer Solar Cells

All–polymer solar cells (All–PSCs) are considered the most promising candidate in achieving both efficient and stable organic photovoltaic devices, yet the field has rarely presented an in–depth understanding of corresponding device stability while efficiency is continuously boosted via the innovation of polymer acceptors. Herein, a ternary matrix is built for all–PSCs with optimized morphology, improved film ductility and importantly, boosted efficiency and better operational stability than its parental binary counterparts, as a platform to study the underlying mechanism. The target system PQM–Cl:PTQ10:PY–IT (0.8:0.2:1.2) exhibits an alleviated burn–in loss of morphology and efficiency under light soaking, which supports its promoted device lifetime. The comprehensive characterizations of fresh and light–soaked active layers lead to a clear illustration of opposite morphological and physical degradation direction of PQM–Cl and PTQ10, thus resulting in a delicate balance at the optimal ternary system. Specifically, the enlarging tendency of PQM–Cl and shrinking preference of PTQ10 in terms of phase separation leads to a stable morphology in their mixing phase; the hole transfer kinetics of PQM–Cl:PY–IT host is stabilized by incorporating PTQ10. Finally, this work succeeds in reaching a deep insight into all–PSC's stability promotion by a rational ternary design, which booms the prospect of gaining high–performance all–PSCs.

14 SOLAR ENERGY↗

Transmission electron microscopy of the rapid solidification microstructure evolution and solidification interface velocity determination in hypereutectic Al-20at.%Cu after laser melting

The evolution of rapid solidification (RS) microstructure and solidification interface velocity has been studied experimentally by in-situ transmission electron microscopy and postmortem characterization for hypereutectic Al-20at.%Cu (37 wt.%Cu) after laser melting. Four morphologically distinct regions formed via growth modes changing from θ-Al 2 Cu phase dendrites to eutectic cell growth, possibly α-Al dendrite growth (α-cell), banded growth, and α-Al plane front growth. Tendency for faceting and low capacity for solute trapping limited the θ-phase dendrite growth to solidification interface velocity v < 0.07 m/s. Consequently, formation of pro-eutectic micro-constituent was suppressed, and RS microstructure formation was dominated by eutectic, α-cell, and banded morphology grains for the Al-20at.%Cu alloy. Eutectic growth operated for interface velocity of 0.1 m/s ≤ v < 0.3 m/s, with a transition from regular lamellar, 2-λ and 1-λ mode to a dense irregular morphology dominated by α-phase at v = 0.3 m/s. Interface temperature calculations indicated feasibility of α-cell growth mode for 0.3 m/s ≤ v < 0.7 m/s. Banded growth occurred for 0.7 m/s ≤ v < 1.3 m/s. Plane front α-phase growth was evident for interface velocities v ≥ 1.3 m/s. Previous work on rapid solidification microstructure development in hypereutectic Al-Cu alloys reported a regime of α-cell growth subsequently to eutectic and prior to transition to banded growth for Al-19at.%Cu (36 wt.%Cu), while for Al-22at.%Cu (40 wt.%Cu) eutectic growth transitioned directly to α-plane front growth without emergence of a banded regime. Finally, based on the current study the disappearance of the banded growth regime occurs for a composition larger than 20at.%Cu.

36 MATERIALS SCIENCE↗

Nanotomographic observation and statistical analysis of overcharging induced cracks in LiCoO 2 single crystalline particles

Particle fracture represents an important mode of battery electrode degradation. Extensive cracking occurs in the layered oxide cathodes of lithium-ion rechargeable batteries when they are charged beyond safe operational voltages. In this paper, we analyze the morphology and distribution of cracks in over 100 overcharged LiCoO 2 (LCO) single-crystalline particles imaged via X-ray nanotomography. Herein, we observe a strong particle size dependence in both nucleation and growth of cracks, with percentage of cracked particles, crack size, and crack surface area per unit volume all increasing significantly with particle volume. Increasing the cutoff voltage above 4.6V is found to trigger much more pronounced crack growth, which we attribute to the large misfit stress caused by the H1-3 to O1 phase transition. This study offers valuable statistical insights into the fracture behavior of layered oxide cathodes and reveals the importance of particle size control on electromechanical degradation of battery electrodes.

25 ENERGY STORAGE↗

A compact design for an electric driven hydraulic gear machine capable of multiple quadrant operation

This paper presents an innovative design of an integrated electro-hydraulic (EH) flow generation unit able to operate in multiple quadrants. The proposed unit is composed of a hydraulic machine which can operate in either pumping or motoring mode, and an electric machine, which can operate as electric motor or generator. The adopted morphological integration of the two unit fulfills the goals of maximizing compactness, power to weight ratio, energy efficiency and quietness. Furthermore, the design results from a numerical optimization procedure that includes detailed simulation of both the electric machine and the hydraulic machine, using simulation tools previously developed by the authors, but combined for the first time in this work. After describing the optimization procedure, the paper focuses on the design integration aspects of the novel unit. A 9 kW prototype of the integrated unit was also fabricated and tested to verify its performance. Tests results show a measured overall energy efficiency up to 69%, demonstrating the potentials of the proposed concept, despite some limitations present in the first prototypes which could be addressed in future design refinements.

42 ENGINEERING↗

Shining a Light on Some Fundamental Research Opportunities in Semiconductor Photoelectrochemistry

Decades of research in semiconductor photoelectrochemistry have yielded a deep understanding of charge transfer, energetics, and stability at solid−liquid interfaces. Theoretical frameworks developed by Gerischer and contemporaries, together with extensive experimental validation, have clarified the key principles affecting the interfacial kinetics and energetics of semiconductor photoelectrodes. Nevertheless, significant opportunities remain for advances in fundamental understanding of semiconductor photoelectrochemistry. Exciting opportunities include exploiting advances in theory, synthesis, and instrumentation to determine the chemical identity and reactivity of surface states; exerting control of band-edge energetics through molecular-level surface modification processes; and systematically improving emerging photoelectrode protection strategies to enable long-term photoelectrode operation under both oxidative and reductive conditions. Advanced morphologies, such as nanowire and microwire arrays, present new pathways to combine efficient light absorption with effective charge collection and catalyst integration. Unique light−matter interactions during photoelectrochemical deposition of p-type semiconductors readily allow preparation at scale of complex 3D morphologies that are difficult, if not impossible, to access by other methods. Continued exploration of these avenues will expand the fundamental understanding of semiconductor−liquid interfaces and could additionally advance the realization of efficient, stable, and scalable systems for solar fuel generation and other emerging photoelectrochemical applications.

Bean, Paul J. L. [California Institute of Technolo↗

Alkali cation-induced cathodic corrosion in Cu electrocatalysts

The reconstruction of Cu catalysts during electrochemical reduction of CO 2 is a widely known but poorly understood phenomenon. Herein, we examine the structural evolution of Cu nanocubes under CO 2 reduction reaction and its relevant reaction conditions using identical location transmission electron microscopy, cyclic voltammetry, in situ X-ray absorption fine structure spectroscopy and ab initio molecular dynamics simulation. Our results suggest that Cu catalysts reconstruct via a hitherto unexplored yet critical pathway - alkali cation-induced cathodic corrosion, when the electrode potential is more negative than an onset value (e.g., –0.4 V RHE when using 0.1 M KHCO 3 ). Having alkali cations in the electrolyte is critical for such a process. Consequently, Cu catalysts will inevitably undergo surface reconstructions during a typical process of CO 2 reduction reaction, resulting in dynamic catalyst morphologies. While having these reconstructions does not necessarily preclude stable electrocatalytic reactions, they will indeed prohibit long-term selectivity and activity enhancement by controlling the morphology of Cu pre-catalysts. Alternatively, by operating Cu catalysts at less negative potentials in the CO electrochemical reduction, we show that Cu nanocubes can provide a much more stable selectivity advantage over spherical Cu nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Editors’ Choice—Examining Performance and Durability of Anion Exchange Membrane Fuel Cells with Novel Spirocyclic Anion Exchange Membranes

A series of spirocyclic copolymer membranes with varying ion exchange capacities (IECs) were investigated to probe the impact of polymer properties on in situ fuel cell performance and stability. In-situ electrochemical tests and post-mortem electron microscopy analysis of cross-sectioned membrane electrode assemblies (MEAs) have been combined with voltage loss breakdown analysis to evaluate the performance and degradation of different MEAs, and to probe the catalyst morphology and electrode structure at different stages of operation. Voltage loss breakdown results show that membrane degradation and kinetic losses played only a minor role in observed performance degradation and that performance losses were primarily related to increasing mass transport losses. From microscopy studies, carbon corrosion and Pt nanoparticle growth were identified at both the cathode and anode although more pronounced on the cathode resulting in significant structural changes. The membrane with the lowest IEC (1.3 mmolg −1 ) demonstrated the lowest peak power density ~ 1.16 W cm −2 , however, it showed the most stable performance (constant 0.6 A cm −2 hold) with ~ 5% degradation over 540 h. Isolation of performance losses and microscopic analysis of electrodes for anion exchange membrane fuel cells has not been reported previously, and these results help identify critical performance degradation concerns.

25 ENERGY STORAGE↗

Elucidate the Thermal Degradation Mechanism of Y6‐Based Organic Solar Cells by Establishing Structure‐Property Correlation

Abstract Organic solar cells (OSCs) achieved performance booming benefiting from the emerging of non‐fullerene acceptors, while inadequate device stability hampers their further application. At present, the prevalent belief attributes the inevitable thermal degradation of OSC device to morphological instability caused by excessive phase separation and crystallization in the active layer during device operation. However, it is inapplicable for state‐of‐art Y6‐based devices which strongly degrade before large‐scale morphology change. Herein, an alternative degradation mechanism is elucidated wherein molecular orientation change and demixing induced performance degradation in Y6‐based devices. Distinct from IT‐4F‐based counterpart, Y6‐based devices suffer severe thermal degradation dominated by open‐circuit voltage (V OC ) and fill factor (FF) losses. TheV OC loss is attributed to molecular orientation transition of polymer donors from edge‐on to face‐on, leading to a strong built‐in potential reduction and increase in non‐radiative loss due to energy level shifting. As forFFdecay, discontinuous acceptor phases result in electron mobility decrease by over orders of magnitude, originating from the increased molecular stacking and phase separation. This work reveals the thermal degradation mechanism for Y6‐based devices and correlates the photoelectric properties with morphology instability, which will offer guidance for improving the stability of high‐performance OSCs.

Chemistry↗

Morphological and chemical characteristics of oxide scales formed on δ-phase plutonium metal alloys II: 2.0 at% Ga

The focused ion-beam scanning electron microscopy (FIB-SEM) and three-dimensional (3D) microscopy were applied to characterize the subsurface morphological features of oxide scales formed on an ~2.0 at. % Ga plutonium (Pu) metal alloy. Using the FIB-SEM technique, a number of morphological features formed in the interior of the oxide scale from Pu metal’s environmental exposure were observed and identified. Auger electron spectroscopy (AES) was utilized to characterize the cross-sectional composition and chemistry of the oxide scale. The oxide scale formed during inert storage and operational environments was found to be highly variable in thickness and morphology, presenting some regions with a thin (<400 nm), dense oxide layer and others with a thick (>2 µm) scale with substantial lateral cracking. After subsequent exposure to dry air environment, the oxide scale became thicker (~4 µm) and slightly more porous. The changes following aging in a moist air environment were observed to be more severe, with the formation of a highly porous internal structure containing significant lateral and transverse cracking. In comparison to the scale formed on an ~3.5 at. % Ga-Pu metal alloy, the oxide morphology of the lower gallium alloy investigated here exhibited greater variation in thickness and a noteworthy dependence on the presence of water vapor, particularly in terms of the internal porosity formed during growth of the oxide.

36 MATERIALS SCIENCE↗

Pool boiling critical heat flux studies of accident tolerant fuel cladding materials

Pool boiling experiments have been performed at atmospheric pressure on potential accident tolerant fuel (ATF) cladding materials (Zirlo®, Cr coated Zirlo®, FeCrAl coated Zirlo®, and monolithic SiC) to evaluate the Critical Heat Flux (CHF) points. Corrosion resistant coatings of Cr and FeCrAl alloy were deposited on flat Zirlo® samples using cold spray technology. The as-prepared samples after uniform surface polishing were subjected to autoclave tests at 360 °C water and 18.6 MPa for 360 h to simulate prototypic corrosion of the ATF cladding materials in LWR normal operation. Surface characteristics potentially influencing CHF such as surface morphology, roughness, static contact angle, and surface chemistry were characterized using a suite of characterization methods including scanning electron microscopy, 3D optical profilometry, optical contact angle measurements, and x-ray photoelectron spectroscopy (XPS). Thermo-physical properties of the samples such as density, thermal conductivity, and heat capacity were measured by differential scanning calorimetry and laser flash thermal diffusivity measurement. FeCrAl coatings showed CHF values comparable to bare Zirlo® samples, while slightly lower CHF values were observed for Cr coated samples and bulk SiC flats (produced by chemical vapor deposition, CVD). As-deposited Cr coatings showed 67% higher CHF than the as-polished Cr coatings due to its higher surface roughness level. The autoclave testing for the prepared samples generally increased the CHF except for the surface polished Cr coatings. Similar CHF values of bare Zirlo®, FeCrAl coating, and CVD SiC samples were observed after autoclave test but there were negligible change CHF of Cr coatings. XPS studies indicated that the formation or deposition of a few monolayers of hydrophobic carbonaceous species on surface can affect CHF values. The trends in CHF data are discussed in terms of evolution of the surface characteristics of the ATF materials.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Plasma Surface Interactions: Predicting the Performance and Impact of Dynamic PFC Surfaces

The objective of this project is to develop, and integrate, high-performance simulation tools capable of predicting plasma-facing component (PFC) operating lifetime and the impact of the evolving surface morphology of tungsten-based PFCs on plasma contamination, including the dynamic recycling of fuel species and tritium retention, in future magnetic fusion devices. Establishing a fundamental physical understanding and developing predictive capabilities of plasma-surface interactions (PSI) requires simultaneously addressing complex and diverse physics occurring over a wide range of length (Angstroms to meters) and time (femtoseconds to years) scales, as well as integrating extensive physical processes across the plasma–surface interface. This requires development of not only detailed physics models and computational strategies at each scale, but also algorithms and methods to couple them effectively in a way that can be robustly validated. Deploying these tools requires the continued development and coupling of leadership-scale computational codes to describe the boundary plasma and the evolving PFC surface, as well as a host of simulations that bridge disparate scales to address complex physical and computational issues at the plasma–surface interface in multi-component materials systems for magnetic fusion energy development beyond ITER.

36 MATERIALS SCIENCE↗

Assessment of an E10 gasoline surrogate: Qualitative and quantitative comparisons of in-cylinder spray morphology

A minimum-component gasoline fuel surrogate that captures both chemical and physical behaviors of a full-distillate fuel is needed for high-fidelity CFD simulations. This study evaluates gasoline spray characteristics in a direct-injection spark-ignition engine under motored operation. Two fuels are compared; PACE-20, which is a 9-component surrogate formulation of RD5-87, is compared with its target fuel RD5-87, which is a full-boiling range research grade E10 gasoline. The spray morphologies of both fuels are recorded for a centrally-located direct-injection 8-hole spray subject to intake air cross-flow during the early part of the intake stroke. High-speed imaging recorded scattered light of the side and axial projections of the liquid spray. Quantitative metrics were developed and employed to facilitate comparison of spray morphologies as well as to identify the transition in spray morphology due to flash boiling. This paper builds on a previous study of RD5-87 where coolant temperature (20°C–100°C), in-cylinder pressure (40–110 kPa), engine speed (650–1950 rpm), and injection pressure (60–180 bar) were systematically changed to span operating conditions with and without flash boiling. Images of the PACE-20 morphology are selected for a sub-set of operating conditions from the previous study where distinctive morphology changes occurred. Visual inspection of the images and quantitative metrics demonstrate that the PACE-20 spray morphology is equivalent to that of the RD5-87 in most cases. The exception was for changes in the ambient-gas pressure where the flash-boiling transition occurred at ∼5 kPa higher in-cylinder pressure for PACE-20. Three empirical metrics, Merging Index, Asymmetry, and Flash Index are proposed here and they were found to be useful both as quantitative comparisons of the fuel morphologies, and for identifying the transition in spray morphology due to flash boiling.

Kim, Namho↗

PERFORMANCE CHARACTERIZATION OF THE DIRECT CONTACT MEMBRANE DISTILLATION MODULE OPERATED WITH HIGHLY CONCENTRATED SOLUTION

The experimental study was conducted to characterize the performance of the flat sheet Direct Contact Membrane Distillation. The length degradation was studied in a short and long module with and without spacers. The experimental study is validated using the predicted flux for a wide range of operating conditions using deionized water. Three different membranes are used in the parametric study for feed Reynolds number varied between 500 and 2000, and inlet feed temperature varied between 45°C and 80°C. PTFE membrane was shown to be more effective than the PVDF due to its higher permeability coefficient and higher hydrophobicity. Fouling study was conducted on the selected PTFE membrane with various feed Reynolds numbers between 500 and 2000 and feed inlet temperature between 50°C and 80°C. Membranes used in the fouling study were characterized using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) for the morphology and chemical composition of the fouling layer. 36 hours of operation with 10 wt% NaCl (100,000 ppm) at feed inlet temperatures 80°C and 60°C and fixed Reynolds 2000 demonstrated a drop in flux by 31% and 27%, respectively. Low flow rate and high temperature are favorable conditions for fouling formation and reduced permeate flux for highly concentrated solutions. The spacers improved the flux by 30.8% and 27.6% at the operating Reynolds numbers 2000 the short and long channel modules. This study helps to design and optimize DCMD modules for industrial-size desalination and water treatment applications.

Kim, Deliya↗

Oxide‐Based Solid‐State Batteries: A Perspective on Composite Cathode Architecture

Abstract The garnet‐type phase Li 7 La 3 Zr 2 O 12 (LLZO) attracts significant attention as an oxide solid electrolyte to enable safe and robust solid‐state batteries (SSBs) with potentially high energy density. However, while significant progress has been made in demonstrating compatibility with Li metal, integrating LLZO into composite cathodes remains a challenge. The current perspective focuses on the critical issues that need to be addressed to achieve the ultimate goal of an all‐solid‐state LLZO‐based battery that delivers safety, durability, and pack‐level performance characteristics that are unobtainable with state‐of‐the‐art Li‐ion batteries. This perspective complements existing reviews of solid/solid interfaces with more emphasis on understanding numerous homo‐ and heteroionic interfaces in a pure oxide‐based SSB and the various phenomena that accompany the evolution of the chemical, electrochemical, structural, morphological, and mechanical properties of those interfaces during processing and operation. Finally, the insights gained from a comprehensive literature survey of LLZO–cathode interfaces are used to guide efforts for the development of LLZO‐based SSBs.

25 ENERGY STORAGE↗

Temperature-Dependent Fracture Resistance of Silicon Nanopillars during Electrochemical Lithiation

During the lithation of silicon anodes, the solid-state diffusion of lithium into Li x Si follows the Arrhenius law, the resulting morphology and fracture behavior are determined by the silicon anode operation temperature. Here, we reveal the temperature dependence of the lithiation mechanics of crystalline silicon nanopillars (SiNPs) via microscopic observations of the anisotropic growth and fracture behavior. In this work, we fabricated 1D SiNP structures with various orientations ($\langle100\rangle, \langle110\rangle$, and $\langle111\rangle$) as working electrodes and operated them at temperatures ranging from –20 to 40 °C. The lithiation of crystalline silicon at low temperatures exhibited preferential volume expansion along $\langle110\rangle$ and decreased fracture resistance. Furthermore, low temperatures caused the catastrophic fracture of amorphous silicon after the second lithiation. Our findings demonstrate the importance of silicon anode temperature control to prevent mechanical fracture during the cycle of lithium-ion batteries in harsh environments (e.g., electric vehicles in winter).

25 ENERGY STORAGE↗

From binary to quinary: The rationale and development of GaInAsSbBi for mid- and long-wave infrared sensing applications

Given the added complexity in flux calibration and composition evaluation inherent to quinary alloy growth, what motivates compounding the challenges of III–V-Bi growth with the goal of producing a quinary alloy of GaInAsSbBi for mid- and long-wave infrared sensing applications? Each elemental constituent provides some additional design freedom to achieve the ultimate goal of producing a lattice-matched, bulk random alloy mid-wave infrared III–V material with smooth surface morphology and high optoelectronic quality to enable high performance elevated operating temperatures. Here, this paper reviews the evolution of Bi-containing semiconductor research, focusing on mid- and long-wave infrared materials and highlighting key research findings that motivated the decisions to accept the added complexity in going from binaries like InAs or InSb, to InAsBi, to InAsSbBi, and, finally, to GaInAsSbBi to meet the performance demands of advanced infrared sensing applications.

Webster, Preston T. [Air Force Research Laboratory↗

Operando Topography and Mechanical Property Mapping of CO 2 Reduction Gas-Diffusion Electrodes Operating at High Current Densities

Electrochemical atomic force microscopy (EC-AFM) enables measurement of electrode topography and mechanical properties during electrochemical reactions. However, for aqueous-based reactions that make gas products, such as CO 2 reduction and water splitting into CO/H 2 , current densities below 1 mA cm −2 have been necessary to prevent formation of bubbles at the electrode; such bubbles can stick to the AFM probe and prevent further AFM imaging. Here, we demonstrate a novel cell design with a gas-diffusion electrode (GDE) to exhaust the gas products, thereby enabling high current density EC-AFM measurements at 1, 10, and 100 mA cm −2 that are not disturbed by bubble formation at the electrode surface. These experiments revealed a stable morphological structure of Cu catalysts deposited on GDEs during high current density operation. Systematic spatially resolved maps of deformation and adhesion showed no signs of a gas-liquid interface between catalyst particles of the GDE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hierarchical porous metals with deterministic 3D morphology and shape via de-alloying of 3D printed alloys

The present disclosure relates to a method for forming a three dimensional, hierarchical, porous metal structure with deterministically controlled 3D multiscale pore architectures. The method may involve providing a feedstock able to be applied in an additive manufacturing process, and using an additive manufacturing process to produce a three dimensional (3D) structure using the feedstock. The method may involve further processing the 3D structure through at least a de-alloying operation to form a metallic 3D structure having an engineered, digitally controlled macropore morphology with integrated nanoporosity.

Qi, Zhen↗