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At least 649 records · Page 36

Rapid microwaves synthesis of CoSi{sub x}/CNTs as novel catalytic materials for hydrogenation of phthalic anhydride

CoSi{sub x}/CNTs catalysts with different CoSi{sub x} phases (CoSi, CoSi{sub 2}) have been rapidly synthesized via a microwave-assisted route and applied for the liquid phase hydrogenation of phthalic anhydride. The synthesized catalysts were analyzed and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy-energy dispersive X-ray spectroscopy, thermogravimetric/derivative thermogravimetric analysis. The reaction progress of cobalt silicides and the ratio of Co:Si were monitored at different microwave irradiation times by XRD, giving insight into the formation mechanism. Compared to the Co/CNTs catalyst, all the prepared CoSi{sub x}/CNTs catalysts exhibited excellent activity and good selectivity to phthalide under mild reaction conditions (180–220 °C and 4.0 MPa H{sub 2}). This novel methodology can be applied to the synthesis of other transition metal silicides such as FeSi, Ni{sub 2}Si, and Cu{sub 4}Si. - Graphical abstract: CoSi{sub x}/CNTs catalysts with different CoSi{sub x} phases (CoSi{sub 2}, CoSi) have been rapidly synthesized via microwave-assisted route, which involves the vaporization of CoCl{sub 2} and subsequent reaction of CoCl{sub 2} with Si. - Highlights: • CoSi{sub x}/CNTs catalysts have been rapid synthesized via microwave-assisted route. • The phases of CoSi{sub x} were controlled by varying microwave time and Co:Si ratio. • FeSi, Ni{sub 2}Si and Cu{sub 4}Si were also synthesized via microwave-assisted route. • CoSi{sub x}/CNTs catalysts can be applied in hydrogenation of phthalic anhydride.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Towards fully self-consistent optoelectronic simulation of planar devices

Photon recycling plays an important role in various optoelectronic devices, such as thin-film solar cells and intracavity double-diode structures presently studied for electroluminescent cooling. However, a complete description of photon recycling requires developing fully self-consistent simulation tools of photon and electronic charge transport in realistic device structures. In this paper, we describe a possible route towards such simulation tools in planar devices by combining the radiative transfer (RT) equation of photon transport with the drift-diffusion (DD) equations of electron and hole dynamics. We investigate the feasibility of the approach by selected proof-of-principle device studies. The results indicate that combining the RT and DD models not only yields the expected device characteristics, but also produces new insight into the pertinent local emission and absorption properties within the device structures. In particular, the model allows to accurately investigate how emission directivity and saturation affect the coupling coefficient in the double diode structures, showing that the main contribution to the coupling coefficient arises from the reflectivity of the top contact. For completeness, we also discuss how interference affects photon transport in resonant devices by an example calculation using the quantized fluctuational electrodynamics framework, paving way for self-consistent modeling tools that also account for wave-optical effects.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Formation of five-membered ring structures via reactions of o -benzyne

The formation of five-membered ring structures is important for the generation of curved and bowl-shaped polycyclic aromatic hydrocarbons (PAHs) under combustion conditions. Here, we report the identification of the indenyl (C 9 H 7 ) radical – the simplest aromatic hydrocarbon radical carrying an adjacent five- and six-membered ring, as the major product of the o-benzyne (o-C 6 H 4 ) reaction with propargyl (C 3 H 3 ). Because real flames exhibit a complex chemistry, elucidation of a specific reaction is very challenging. Instead, we studied the o-C 6 H 4 + C 3 H 3 reaction in a resistively heated microtubular SiC reactor at controlled conditions of 1150 K and a pressure near 10–20 Torr. To this end, the reactants o-benzyne and propargyl were pyrolytically generated from benzoyl chloride and propargyl bromide. We identified the reactants and the indenyl radical isomer-selectively utilizing photoion mass-selected threshold photoelectron spectroscopy (ms-TPES). In conclusion, the experimentally observed predominant formation of indenyl radicals finally confirms the theoretical predictions of Matsugi and Miyoshi [Phys. Chem. Chem. Phys. 14 (2012), 9722–9728] and highlights a versatile route for the formation of five-membered rings and curved PAHs via reactions of o-benzyne that favor the formation of multiring species over aliphatically substituted aromatic species.

Molecular-weight growth↗

Role of Bimetallic Interactions in the Enhancement of Catalytic CO 2 Reduction by a Macrocyclic Cobalt Catalyst

The use of two metal centers in a CO 2 reduction catalyst that work together synergistically, with similar or complementary functions, can potentially lead to a significant reduction in overpotential, enhance catalytic activity and/or selectivity, and/or enable access to cascade strategies where each metal center catalyzes a different step in the conversion of CO 2 to a fuel. Here, the bimetallic reactivity of two metal centers has been identified as the primary route for the reduction of CO 2 to CO promoted by the macrocycle, [Co(HMD)] 2+ (HMD = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene), based on the experimental characterization of all major steps of the proposed catalytic cycle using pulse radiolysis time-resolved IR (PR-TRIR) spectroscopy, corroborated by density functional theory (DFT) calculations and IR spectroelectrochemistry (IR-SEC). A bimetallic intermediate is formed in situ from two singly reduced [Co(HMD)] + species bridged by a CO 2 molecule, and the presence of a coordinating species, e.g., formate anion, appears to assist in the formation of such an intermediate. In this work, it has been demonstrated that this reactivity enables access to elementary steps with lower energy requirements, resulting in overall catalysis being kinetically more facile compared to the mononuclear pathway. A two-step approach that combines chemical reduction followed by PR-TRIR has been successfully used for probing the structure and reactivity of reactive intermediates involved in the advanced stages of a catalytic cycle, which are rarely interrogated using experimental techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical synthesis of multisegmented nanowires

Electrochemical deposition has emerged as a promising route for nanostructure fabrication in recent years due to the many inherent advantages it possesses. This study focuses on the synthesis of high-aspect-ratio multisegmented Au/Ni nanowires using template-directed sequential electrochemical deposition techniques. By selectively removing the Ni segments in the nanowires, high-yield of pure gold nanorods of predetermined lengths was obtained. Alternatively, the sacrificial Ni segments in the nanowires can be galvanically displaced with Bi and Te to form barbells structures with Bi{sub x}Te{sub y} nanotubes attached to neighbouring gold segments. Detailed studies on the nanostructures obtained were carried out using various microscopy, diffraction and probebased techniques for structural, morphological and chemical characterizations.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Comparing GGA, GGA+ U , and meta-GGA functionals for redox-dependent binding at open metal sites in metal–organic frameworks

Metal–organic frameworks (MOFs) with open metal sites have been widely investigated for the selective adsorption of small molecules via redox mechanisms where charge transfer can take place between the binding site and the adsorbate of interest. Quantum-chemical screening methods based on density functional theory have emerged as a promising route to accelerate the discovery of MOFs with enhanced binding affinities toward various adsorbates. However, the success of this approach is linked to the accuracy of the underlying density functional approximations (DFAs). In this work, we compare commonly used generalized gradient approximation (GGA), GGA+U, and meta-GGA exchange-correlation functionals in modeling redox-dependent binding at open metal sites in MOFs using O 2 and N 2 as representative small molecules. We find that the self-interaction error inherent to the widely used Perdew, Burke, and Ernzerhof (PBE) GGA predicts metal sites that are artificially redox-active, as evidenced by their strong binding affinities, short metal–adsorbate bond distances, and large degree of charge transfer. The incorporation of metal-specific, empirical Hubbard U corrections based on the transition metal oxide literature systematically reduces the redox activity of the open metal sites, often improving agreement with experiment. Additionally, the binding behavior shifts from strong chemisorption to weaker physisorption as a function of U. The M06-L meta-GGA typically predicts binding energies between those of PBE-D3(BJ) and PBE-D3(BJ)+U when using empirically derived U values from the transition metal oxide literature. Despite the strong sensitivity of the binding affinities toward a given DFA, the GGA, GGA+U, and meta-GGA approaches often yield the same qualitative trends and structure–property relationships.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of High Surface Area VS2 for Nitrogen Reduction

Ammonia synthesis from dinitrogen provides a critical chemical feedstock to agriculture worldwide. The dominant process for ammonia synthesis is the Haber-Bosch process, which is fossil-fuel dependent and energy intensive. The electrochemical nitrogen reduction reaction (NRR) could provide a more environmentally friendly route to industrial ammonia synthesis. We have worked to realize electrochemical NRR by developing transition metal dichalcogenide NRR catalysts. In the first part of this presentation, a VS2-based NRR electrocatalyst, which has shown promising activity and selectivity, will be presented. The synthesis of this VS2-based catalyst is straightforward and results in few-layer VS2 or VSx, (x < 2) nanoflakes. Additionally, the proposed mechanism of NRR on VS2 will be discussed, and we will discuss DFT simulation of NRR on VS2 and MoS2 as well as planned in-situ Raman experiments to probe this mechanism. In the second part of this presentation, we will share several lessons learned during our early NRR research including important points of electrochemical cell design and experimental controls to reduce environmental ammonia contamination of experiments. Finally, we will address areas of opportunity for electrochemical NRR.

dichalcogenide↗

Automated Conflict Resolution, Arrival Management and Weather Avoidance for ATM

The paper describes a unified solution to three types of separation assurance problems that occur in en-route airspace: separation conflicts, arrival sequencing, and weather-cell avoidance. Algorithms for solving these problems play a key role in the design of future air traffic management systems such as NextGen. Because these problems can arise simultaneously in any combination, it is necessary to develop integrated algorithms for solving them. A unified and comprehensive solution to these problems provides the foundation for a future air traffic management system that requires a high level of automation in separation assurance. The paper describes the three algorithms developed for solving each problem and then shows how they are used sequentially to solve any combination of these problems. The first algorithm resolves loss-of-separation conflicts and is an evolution of an algorithm described in an earlier paper. The new version generates multiple resolutions for each conflict and then selects the one giving the least delay. Two new algorithms, one for sequencing and merging of arrival traffic, referred to as the Arrival Manager, and the other for weather-cell avoidance are the major focus of the paper. Because these three problems constitute a substantial fraction of the workload of en-route controllers, integrated algorithms to solve them is a basic requirement for automated separation assurance. The paper also reviews the Advanced Airspace Concept, a proposed design for a ground-based system that postulates redundant systems for separation assurance in order to achieve both high levels of safety and airspace capacity. It is proposed that automated separation assurance be introduced operationally in several steps, each step reducing controller workload further while increasing airspace capacity. A fast time simulation was used to determine performance statistics of the algorithm at up to 3 times current traffic levels.

Erzberger, H.↗

Additive manufactured bipolar plate for high-efficiency hydrogen production in proton exchange membrane electrolyzer cells

Additive manufacturing (AM) technology is capable of fast and low-cost prototyping from complex 3D digital models. To take advantage of this technology, a stainless steel (SS) plate with parallel flow field served as a combination of a cathode bipolar plate and a current distributor; it was fabricated using selective laser melting (SLM) techniques and investigated in a proton exchange membrane electrolyzer cell (PEMEC) in-situ for the first time. The experimental results show that the PEMEC with an AM SS cathode bipolar plate can achieve an excellent performance for hydrogen production for a voltage of 1.779 V and a current density of 2.0 A/cm 2 . The AM SS cathode bipolar plate was also characterized by SEM and EDS, and the results show a uniform elemental distribution across the plate with very limited oxidization. As a result, this research demonstrates that AM method could be a route to aid cost-effective and rapid development of PEMECs.

08 HYDROGEN↗

Mechanistic Studies of Continuous Partial Methane Oxidation on Cu−Zeolites Using Kinetic and Spectroscopic Methods

Abstract Over the past few decades, a significant amount of research effort has focused on investigating the active site requirements and reaction mechanisms for partial methane oxidation (PMO) to methanol over copper–exchanged zeolites during stoichiometric and stepwise chemical looping routes. More recently, research efforts have expanded to include investigating the PMO reaction in a continuous catalytic regime, primarily focusing on determining the influence of catalyst composition on Cu speciation and structure and, in turn, on PMO rate and selectivity. The structures of candidate Cu active sites are commonly studied using a combination of ex situ and in situ spectroscopic approaches. In this perspective, we critically examine the prior literature on catalytic PMO over Cu–zeolites to identify key knowledge gaps that remain in our understanding as motivation for future research efforts. We identify opportunities for future research to address these gaps by adapting analogous interrogation techniques that have been successfully used to elucidate the active site requirements and mechanistic details of another catalytic redox reaction cycle on Cu–zeolites, the selective catalytic reduction (SCR) of nitrogen oxides (NO x ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Overcoming barriers to medium-chain fatty alcohol production

Medium-chain fatty alcohols ( mc FaOHs) are aliphatic primary alcohols containing six to twelve carbons that are widely used in materials, pharmaceuticals, and cosmetics. Microbial biosynthesis has been touted as a route to less-abundant chain-length molecules and as a sustainable alternative to current petrochemical processes. Several metabolic engineering strategies for producing mc FaOHs have been demonstrated in the literature, yet processes continue to suffer from poor selectivity and mc FaOH toxicity, leading to reduced titers, rates, and yields of the desired compounds. Here, this opinion examines the current state of microbial mc FaOH biosynthesis, summarizing engineering efforts to tailor selectivity and improve product tolerance by implementing engineering strategies that circumvent or overcome mc FaOH toxicity.

59 BASIC BIOLOGICAL SCIENCES↗

Memory Effect on the Synthesis of Perovskite-Type Li-Ion Conductor Li x La 2/3– x /3 TiO 3 (LLTO)

The structural chemistry of the solid ion-conducting Li x La 2/3–x/3 TiO 3 (LLTO) is rich with various polymorphs related to atomic segregation. Here, we explored the LLTO reaction pathway from various structurally related precursors (La 2 LiO 3 H, Li 2 TiO 3 , and Li 4 Ti 5 O 12 ), focusing on the effects of LLTO-like structural motifs in precursors using a combination of experimental and computational techniques. Density functional theory (DFT) calculations revealed that the failure of syntheses to produce LLTO below 1300 °C is due to the presence of multiple competing low-energy phases that result in competitive byproduct formation. In all syntheses where T = 1300 °C, LLTO was the sole product; however, varying phase fractions of I4/mcm and P4/nbm polymorphs and double-perovskite P4/mmm can be obtained depending on the synthesis route. This is an unusual result as at 1300 °C, LLTO should only be the ideal cubic Pm-3m perovskite structure, yet there appears to be a memory effect from the different precursors resulting in the unique phase selectivity and stabilization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Decomposition of methane diluted with inert gas in an RF discharge cell

Decomposition of methane using non-thermal plasmas is an attractive route for producing hydrogen-rich gases and valuable carbon nanomaterials. Understanding how plasma discharge modes influence methane decomposition in optimizing plasma-assisted chemical conversion remains unexplored. This study explores the coupling between the discharge structure and product selectivity in RF capacitively coupled discharges operating in methane/inert gas mixtures in the pressure range of 2–3 torr. Under our experimental conditions the discharge exhibits mode transitions from uniform to striated in Ar and Kr and from diffuse to contracted in Ar and Kr with <5% CH 4 . The discharges in He and Ne remained uniform under our operating conditions, and their mixtures with CH 4 remained diffuse. A 0-d model for Ar/CH 4 discharge established a threshold for contraction while also asserting the importance of Ar$^{*}_{\textrm{m}}$ in the dissociation and ionization processes. The highest degree of methane decomposition, >99.7% with the main products of acetylene and graphitized solid carbon was achieved in the contracted discharge mode for both Kr or Ar with ⩽5% CH 4 . We demonstrate that contraction can play a crucial role in the effective decomposition of methane with value-added products and that both the electronic and thermal properties of plasma gas are responsible for this effect.

RF plasma↗

An Evaluation of the Network Simulators in Large-Scale Distributed Simulations

This is a survey paper about the state-of-the-art in large-scale network simulation. Networks for the smart grids are characterized by millions of sensor nodes exchanging information about the status of the grid. This information exchange must be realized reliably and efficiently due to the mission critical nature of the power grid. Hence, the applications and the network protocols developed for the smart grid need go through rigorous testing and analysis before deployment. Developers usually do not have access to such a large-scale network that can be used as a controlled test-bed; therefore, network simulation becomes an essential tool for testing. Network simulation is a well studied problem in the literature and there are various widely used network simulators. These simulators can be adopted for testing applications and protocols of the smart grid. Due to the scale of these networks, parallel/distributed simulations need to be conducted. Even though most network simulators support distributed simulations, generating a large-scale network model to simulate can still be a cumbersome task. In this survey, we describe a selection of commonly used network simulators and evaluate them with respect to the following features that can aid users in distributed simulations of large-scale networks: transparency of setting up distributed simulation, automated topology generation, information hiding, lightweight routing protocols, network error simulation, evaluation of the network model during simulation and trace analysis tools. As a complementary result, we identify two issues with network simulators that can be addressed with runtime steering methods.

99 GENERAL AND MISCELLANEOUS↗

DE-NE0000724 - Research Performance Final Report - Investigation of Thermal Aging Effects on the Evolution of Microstructure and Mechanical Properties of Cast Duplex Stainless Steels

This report details the research activities carried out under DOE-NEUP award number DE-NE0000724 concerning the evolution of structural and mechanical properties during thermal aging of CF–3 and CF–8 cast duplex stainless steels (CDSS). The overall objective of this project was to use state-of-the-art characterization techniques to elucidate trends and phenomena in the mechanical and structural evolution of cast duplex stainless steels (CDSS) during thermal aging. These steels are commonly used as structural materials in commercial light water nuclear power plants, undergoing aging for decades in operation as cooling water pipes, pump casings, valve bodies, etc. During extended exposure to these conditions, CDSS are known to undergo a change in mechanical properties resulting in a loss of ductility, i.e. embrittlement. While it is generally accepted that structural changes within the ferrite phase, such as decomposition into iron (Fe)-rich and chromium (Cr)-rich domains, lead to the bulk embrittlement of the steels, many questions remain as to the mechanisms of embrittlement at multiple length scales. This work is intended to shed insight into the atomic level composition changes, associated kinetic mechanisms, and effects of changing phase structure on micro- and nano-scale deformation that lead to loss of impact toughness and tensile ductility in these steels. In general, this project provides a route to answer some of these major questions using techniques such as 3-dimensional (3-D) atom probe tomography (APT) and real-microstructure finite element method (FEM) modeling, which were not readily available when these steels were originally selected for service in light water reactors. Mechanical properties evaluated by Charpy V-notch impact testing (CVN), tensile testing, and microhardness and nanohardness measurements were obtained for each condition and compared with the initial baseline properties to view trends in deformation behavior during aging. Concurrent analysis of the microstructure and nanostructure by atom probe tomography (APT) and transmission electron microscopy (TEM) provide mechanistic insight into the kinetic and mechanical behavior occurring on the nano-scale. The presence and morphology of the ferrite, austenite, and carbide phases have been characterized, and formation of new phases during aging, including spinodal decomposition products (α- and α'-ferrite) and G-phase, have been observed. The mechanical and structural characterization have been used to create accurate FEM models based on the real micro- and nano-structures of the systems. These models provide new insight into the local deformation behavior of these steels and the effects of each individual phase (including ferrite, austenite, carbides, and spinodal decomposition products) on the evolving bulk mechanical behavior of the system. The project was divided into three major tasks: 1. Initial Microstructure and Mechanical Property Survey and Initiate Heat Treatment; 2. Microstructural Characterization and Mechanical Property Testing During Aging; and 3. Microstructure-based Finite Element Modeling. Each of these tasks was successfully executed, resulting in reliable data and analysis that add to the overall body of work on the CDSS materials. Baseline properties and aging trends in mechanical data confirm prior observations and add new insights into the mechanical behavior of the steels. Structural characterization on multiple length scales provides new information on phase changes occurring during aging and sheds light on the kinetic processes occurring at the atomic scale. Furthermore, a combination of mechanical testing and microstructural characterization techniques was utilized to design FEM models of local deformation behavior of the ferrite and austenite phases, providing valuable new information regarding the effects of each of the microstructural components on the hardening and embrittlement processes. The data and analysis presented in this report and the publication associated with this project (§V) increase the understanding of aging and deformation in CF–3 and CF–8 steels. These results provide valuable information that can be utilized to aid in making informed decisions regarding the ongoing use of these steels in commercial nuclear infrastructure.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Embedded Sensor Development in Metallic Structures for the Transformational Challenge Reactor

The ability to make minimally intrusive measurements of process conditions has tremendous potential for improving system performance and control in applications such as nuclear power generation. Towards this end, emerging and evolving advanced manufacturing methods, such as additive manufacturing, present new opportunities for more seamlessly integrating sensing with structure. This technical report summarizes the progress of work performed to assess the feasibility of embedding commercial off-the-shelf (COTS) sensors in a metallic reactor core using advanced manufacturing methods. The progress of four research and development tasks are documented: 1) A survey of COTS sensors for nuclear applications that are candidates for embedded fabrication, 2) Development of a conceptual framework for investigating the feasibility of sensor embedment, 3) Definition of structural geometries and other characteristics that will represent compelling proof-of-concept, and 4) Preliminary prototyping of embedded sensors. For the purposes of this initial study, nuclear grade K-type thermocouples were selected for investigation of embedment methodologies. This sensor was selected as an initial candidate because it represents one of the simplest sensor configurations that can provide useful process information. A selective laser melting (SLM) additive manufacturing process was used to fabricate structures with complexity representative of the core design of the transformational challenge reactor (TCR) and methods were developed to embed a thermocouple with a complex two-dimensional routing path. There are many challenges associated with embedding sensors during the additive manufacturing process including securing the sensor in the structure, relocating the part in the additive machine if using a “pick and place” sensor placement method, mitigating the potential for powder contamination, optimizing energy deposition parameters to build as closely as possible around the sensor path and improve structural integrity of the part, and tuning energy deposition to mitigate thermally induced warpage of the sensor and part as well as potential for damaging the sensing device. Preliminary results indicate that it is feasible to integrate the sensor while minimally compromising the structural integrity of the part and preserving sensor performance. This first phase of this work focused on developing a workflow for embedding sensors and controlling energy deposition during the additive manufacturing process to better understand the build characteristics around the sensor. Future work will perform more in-depth characterization of prototype parts using X-ray computed tomography and scanning electron microscopy to better understand fabricated structures, performance testing of embedded sensors in high temperature environments, adding new embedded measurement modalities, embedding devices with dissimilar materials in contact with additive powders, and the development of methods for embedding sensors with three-dimensional routing paths.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Pioneer imaging photopolarimeter optical system.

The imaging photopolarimeter aboard the Pioneer 10 spacecraft en route to the vicinity of Jupiter is described. This instrument is capable of moderate resolution spin-scan imaging and high precision polarimetric and photometric mapping of Jupiter in red and blue light. The field of view can be selectively changed from 0.50 mrad square to 40 mrad square to accommodate resolution and radiance combinations ranging from the zodiacal background to that of Jupiter. Optical materials were chosen to survive, with minimum degradation, the rigors of a nearly 2-year journey to Jupiter including transit through the Jovian trapped radiation belts. The optics are described in detail, and the operational system is outlined. The procedures for preflight and in-flight calibration are described, and some performance characteristics and preliminary flight results are presented.

Pellicori, S. F.↗

Evaluation of routing and scheduling considerations for possible future commercial hypersonic transport aircraft

Travel markets which would be served by high speed commercial transport aircraft and the ability of the airlines to schedule and route the aircraft in a way that would achieve good daily utilization and productivity are examined. The following areas are considered: (1) identification of the major long-haul city pairs that would most likely demand nonstop service; (2) selection of flight tracks observing alternative sonic boom restrictions; (3) estimation of flight times for all city pairs for the various sonic boom constraints; (4) impact of airport curfews on possible departure and arrival schedules; (5) projection of passenger traffic volumes on the selected city pairs; and (6) potential daily utilization and aircraft productivity.

Feir, J. B.↗