Investigation of electrochemistry of high energy compounds in organic electrolytes Third progress report, Nov. 1, 1965 - Apr. 30, 1966
Electrochemical properties, and chemical reactions between cyclic esters and certain metals
ELECTRIC PROPERTY↗
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Development of glass passivation method for semiconductor devices for Saturn system Quarterly progress report, 28 Jun. - 28 Sep. 1966
Techniques and properties of glass passivation for semiconductor devices for Saturn system
SEMICONDUCTOR DEVICE↗
An Intercomparison of Microphysical Retrieval Algorithms for Upper Tropospheric Ice Clouds
The large horizontal extent, location in the cold upper troposphere, and ice composition make cirrus clouds important modulators of the earth's radiation budget and climate. Cirrus cloud microphysical properties are difficult to measure and model because they are inhomogeneous in nature and their ice crystal size distribution and habit are not well characterized. Accurate retrievals of cloud properties are crucial for improving the representation of cloud scale processes in large-scale models and for accurately predicting the earth's future climate. A number of passive and active remote sensing retrieval algorithms exist for estimating the microphysical properties of upper tropospheric clouds. We believe significant progress has been made in the evolution of these retrieval algorithms in the last decade, however, there is room for improvement. Members of the Atmospheric Radiation measurement program (ARM) Cloud properties Working Group are involved in an intercomparison of optical depth(tau), ice water path, and characteristic particle size in clouds retrieved using ground-based instruments. The goals of this intercomparison are to evaluate the accuracy of state-of-the-art algorithms, quantify the uncertainties, and make recommendations for improvement.
Comstock, Jennifer M.↗
Structures and Mechanical Properties of Natural and Synthetic Diamonds
A revolution in diamond technology is in progress as the low-pressure process becomes an industrial reality. It will soon be possible to take advantage of the demanding properties of diamond to develop a myriad of new applications, particularly for self-lubricating, wear, and superhard coatings. The production of large diamond films or sheets at low cost, a distinct possibility in the not-too-distant future, may drastically change tribology technology, particularly solid lubricants and lubricating materials and systems. This chapter reviews the structures and properties of natural and synthetic diamond to gain a better understanding of the tribological properties of diamond and related materials to be described in the following chapters. Atomic and crystal structure, impurities, mechanical properties, and indentation hardness of diamond are described.
Miyoshi, Kazuhisa↗
Geometric and thermodynamic characterization of binary neutron star accretion discs
Accretion disks formed in binary neutron star mergers play a central role in many astrophysical processes of interest, including the launching of relativistic jets or the ejection of neutron-rich matter hosting heavy element nucleosynthesis. In this work we analyze in detail the properties of accretion disks from 44 ab initio binary neutron star merger simulations for a large set of nuclear equations of state, binary mass ratios, and remnant fates, with the aim of furnishing reliable initial conditions for disk simulations and a comprehensive characterization of their properties. We find that the disks have a significant thermal support, with an aspect ratio decreasing with the mass ratio of the binary from ~0.7 to 0.3. Even if the disk sample spans a broad range in mass and angular momentum, their ratio is independent from the equation of state and from the mass ratio. This can be traced back to the rotational profile of the disk, characterized by a constant specific angular momentum (as opposed to a Keplerian one) of 3 – 5×10 16 cm 2 s –1 . The profiles of the entropy per baryon and of the electron fraction depend on the mass ratio of the binary. For more symmetric binaries, they follow a sigmoidal distribution as a function of the rest mass density, for which we provide a detailed description and a fit. Furthermore, the disk properties discussed in this work can be used as a robust set of initial conditions for future long-term simulations of accretion disks from binary neutron star mergers, posing the basis for progress in the quantitative study of the outflow properties.
79 ASTRONOMY AND ASTROPHYSICS↗
Synthesis, structure, and optoelectronic properties of II-IV-V 2 materials
II-IV-V 2 materials offer the promise of enhanced functionality in optoelectronic devices due to their rich ternary chemistry. In this review, we consider the potential for new optoelectronic devices based on nitride, phosphide, and arsenide II-IV-V 2 materials. As ternary analogs to the III-V materials, these compounds share many of the attractive features that have made the III-Vs the basis of modern optoelectronic devices (e.g. high mobility, strong optical absorption). Control of cation order parameter in the II-IV-V 2 materials can produce significant changes in optoelectronic properties at fixed chemical composition, including decoupling band gap from lattice parameter. Recent progress has begun to resolve outstanding questions concerning the structure, dopability, and optical properties of the II-IV-V 2 materials. Furthermore, remaining research challenges include growth optimization and integration into heterostructures and devices.
36 MATERIALS SCIENCE↗
Oxidation Behavior and Property Degradation of Nuclear Graphites
During its multidecade operation in the core of nuclear reactors, graphite components are subjected to aggressive and continuous exposure to a high field of ionizing and neutron irradiation, high temperature, and various types of present and postulated chemical attacks. High density, high crystallinity polygranular synthetic graphite is unique among other materials for its extraordinary capacity of resisting and adapting to the aggression inflicted by high temperature, high energy neutron bombardment and ionizing gamma radiation. But, as a carbonaceous material, even though of very high purity, graphite is reactive towards common oxidizing agents: oxygen, carbon dioxide, water. Safe operation of HTGRs relies, among other aspects, on engineered safeguard systems for efficient and continuous protection of graphite components against oxidation. Graphite oxidation behavior was, and continues to be, an important direction of theoretical and experimental research, engineering analyses, models and simulations, and design and safety regulations. The avalanche of publications, reports, experimental data, computer codes, and regulatory documents related to oxidation behavior of nuclear graphite is now accelerating to new levels, prompted by the increased interest for nuclear energy as a clean, carbon-free energy source. Even though public’s perception of nuclear energy advantages may still be influenced by the memories of past accidents of nuclear reactors from generations II and III, the community of informed scientists and engineers, regulators and statemen knows that generation IV of nuclear reactors is designed at very high safety standards, doubled by great advances of scientific knowledge and technological progress. One of routes of these recent advances is directed at better understanding of graphite oxidation behavior, its relationship with graphite manufacturing and microstructural properties, along with the effects of various environmental factors and process variables. Together, the recent progress in manufacturing, properties characterization, and modeling of intricated physical and chemical processes that concur to the oxidation behavior led to development of powerful simulation codes able to analyze various scenarios of normal operation and hypothetical off-normal events, and thus to clearly specify the allowable parameters envelopes for the designers, constructors, and operators of current and future modular HTGRs. This review begins with an introduction on manufacturing methods, structure, and properties of nuclear graphite, including basic requirements that this specialty graphite type must satisfy for nuclear use. It continues with a chapter on environmental effects on nuclear graphite, where emphasis is placed less on irradiation and much more on oxidation phenomena, their safety implications, and the basic traits of chronic and acute oxidation by air (oxygen) and water (humidity, steam). Particular attention is placed on the three graphite grades of interest for this document (IG-110, NBG-18, PCEA). A chapter on properties degradation induced by oxidation follows, with focus on density, dimensional, and mechanical properties changes. The next chapter is intended as a brief review of various approaches used for modeling of graphite oxidation behavior. It summarizes the progress of oxidation models, from the early attempts to complex computational approaches interfaced with specialized computer codes designed for nuclear reactor simulations. Last, a list is presented of knowledge gaps where more research is needed. A short summary concludes the review.
36 MATERIALS SCIENCE↗
M PX 3 van der Waals magnets under pressure ( M = Mn, Ni, V, Fe, Co, Cd; X = S, Se)
van der Waals antiferromagnets with chemical formula MPX 3 (M = V, Mn, Fe, Co, Ni, Cd; X = S, Se) are superb platforms for exploring the fundamental properties of complex chalcogenides, revealing their structure-property relations and unraveling the physics of confinement. Pressure is extremely effective as an external stimulus, able to tune properties and drive new states of matter. In this review, we summarize experimental and theoretical progress to date with special emphasis on the structural, magnetic, and optical properties of the MPX 3 family of materials. Under compression, these compounds host inter-layer sliding and insulator-to-metal transitions accompanied by dramatic volume reduction and spin state collapse, piezochromism, possible polar metal and orbital Mott phases, as well as superconductivity. Some responses are already providing the basis for spintronic, magneto-optic, and thermoelectric devices. We propose that strain may drive similar functionality in these materials.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Block Copolymers: Synthesis, Self-Assembly, and Applications
Research on block copolymers (BCPs) has played a critical role in the development of polymer chemistry, with numerous pivotal contributions that have advanced our ability to prepare, characterize, theoretically model, and technologically exploit this class of materials in a myriad of ways in the fields of chemistry, physics, material sciences, and biological and medical sciences. The breathtaking progress has been driven by the advancement in experimental techniques enabling the synthesis and characterization of a wide range of block copolymers with tailored composition, architectures, and properties. In this review, we briefly discussed the recent progress in BCP synthesis, followed by a discussion of the fundamentals of self-assembly of BCPs along with their applications.
applications↗
The Origin of Chemical Elements: Connecting Laboratory Nuclear Astrophysics with Astronomical Observations through Nucleosynthesis Modeling
Nuclear astrophysics is a field at the frontier of nuclear science which continues to enjoy significant progress and exciting prospects for the future. It addresses the fundamental question of where and how the chemical elements are made. Except for hydrogen and helium, all other chemical elements are made either in stars or in cosmic explosions such as supernovae or neutron star mergers. To understand the formation of elements we need to understand the relevant nuclear physics processes that govern the interaction between nuclei. We need to understand the conditions in the star or the explosion under which these nuclear processes take place. And we need to understand how individual events of element formation contribute to the overall chemical enrichment of our Galaxy over time. Experimental facilities allow for terrestrial experiments on the nuclear physics governing the element synthesis. Earth-based and space-based telescopes probe the Galaxy around us and provide information about the conditions in stars and supernovae, and about the chemical element enrichment of these different environments. Numerical simulations of stars, supernovae, and other astrophysical phenomena allow us to probe the conditions of extreme densities and temperatures required for element synthesis. Nucleosynthesis research is ideally posed to integrate advances from all three of these areas and advance our understanding of how and where elements are made. Nucleosynthesis research provides theory support for experiments and observations. And it makes predictions that can be tested in nuclear physics experiments and astronomical observations. The goals of this award were in three main areas: 1. Develop and implement an effective core-collapse supernova model that is computationally efficient and that captures the relevant physics for the scientific questions of interest 2. Advance our understanding of the synthesis of the lightest heavy elements 3. Increase the realism of supernova nucleosynthesis and determine its dependence on the properties of the exploding star As the projects progressed, an additional focus was added to this list: 1. Study the explosion properties and the signals from the most massive stars.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Structures and Mechanical Properties of Natural and Synthetic Diamonds
A revolution in the diamond technology is in progress, as the low-pressure process becomes an industrial reality. It will soon be possible to take advantage of the demanding properties of diamond to develop a myriad of new applications, particularly for self-lubricating, wear-resistant, and superhard coatings. The production of large diamond films or sheets at low cost, a distinct possibility in the not-too-distant future, may drastically change tribology technology, particularly regarding solid lubricants and lubricating materials and systems. This paper reviews the structures and properties of natural and synthetic diamonds to gain a better understanding of the tribological properties of diamond and related materials. Atomic and crystal structure, impurities, mechanical properties, and indentation hardness of diamond are described.
Miyoshi, Kazuhisa↗
The Gaseous Disks of Young Stellar Objects
Disks represent a crucial stage in the formation of stars and planets. They are novel astrophysical systems with attributes intermediate between the interstellar medium and stars. Their physical properties are inhomogeneous and are affected by hard stellar radiation and by dynamical evolution. Observing disk structure is difficult because of the small sizes, ranging from as little as 0.05 AU at the inner edge to 100-1000 AU at large radial distances. Nonetheless, substantial progress has been made by observing the radiation emitted by the dust from near infrared to mm wavelengths, i.e., the spectral energy distribution of an unresolved disk. Many fewer results are available for the gas, which is the main mass component of disks over much of their lifetime. The inner disk gas of young stellar objects (henceforth YSOs) have been studied using the near infrared rovibrational transitions of CO and a few other molecules, while the outer regions have been explored with the mm and sub-mm lines of CO and other species. Further progress can be expected in understanding the physical properties of disks from observations with sub-mm arrays like SMA, CARMA and ALMA, with mid infrared measurements using Spitzer, and near infrared spectroscopy with large ground-based telescopes. Intense efforts are also being made to model the observations using complex thermal-chemical models. After a brief review of the existing observations and modeling results, some of the weaknesses of the models will be discussed, including the absence of good laboratory and theoretical calculations for essential microscopic processes.
Glassgold, A. E.↗
RNA nanotechnology to build a dodecahedral genome of single-stranded RNA virus
The quest for artificial RNA viral complexes with authentic structure while being non-replicative is on its way for the development of viral vaccines. RNA viruses contain capsid proteins that interact with the genome during morphogenesis. The sequence and properties of the protein and genome determine the structure of the virus. For example, the Pariacoto virus ssRNA genome assembles into a dodecahedron. Virus-inspired nanotechnology has progressed remarkably due to the unique structural and functional properties of viruses, which can inspire the design of novel nanomaterials. RNA is a programmable biopolymer able to self-assemble sophisticated 3D structures with rich functionalities. RNA dodecahedrons mimicking the Pariacoto virus quasi-icosahedral genome structures were constructed from both native and 2'-F modified RNA oligos. The RNA dodecahedron easily self-assembled using the stable pRNA three-way junction of bacteriophage phi29 as building blocks. The RNA dodecahedron cage was further characterized by cryo-electron microscopy and atomic force microscopy, confirming the spontaneous and homogenous formation of the RNA cage. The reported RNA dodecahedron cage will likely provide further studies on the mechanisms of interaction of the capsid protein with the viral genome while providing a template for further construction of the viral RNA scaffold to add capsid proteins for the assembly of the viral nucleocapsid as a model. Understanding the self-assembly and RNA folding of this RNA cage may offer new insights into the 3D organization of viral RNA genomes. Finally, the reported RNA cage also has the potential to be explored as a novel virus-inspired nanocarrier.
59 BASIC BIOLOGICAL SCIENCES↗
Hydrogen-Bonded Organic Frameworks: A Rising Class of Porous Molecular Materials
Hydrogen-bonded organic frameworks (HOFs) are a class of porous molecular materials that rely on the assembly of organic building blocks by means of hydrogen-bonding interactions to form two-dimensional (2D) and three-dimensional (3D) crystalline networks. The reversible nature of the hydrogen-bond formation endows HOFs with the attributes of solution processability and simple regeneration. High-quality single crystals of HOFs can be grown easily for unambiguous superstructure determination by single-crystal X-ray diffraction, which is crucial for the elucidation of superstructure–property relationships. During the past decade, considerable progress has been achieved in realizing stable HOFs with permanent porosities by focusing on the design of molecular building blocks in order to introduce rigidity, auxiliary [π···π] interactions, and interpenetration of their frameworks to sustain the extended networks. The applications of HOFs are far-reaching, spanning catalysis, energy, and biomedical products as well as the storage and separation of fine chemicals. In this paper, we, first of all, provide an overview of the chronological development of HOFs, starting from the seminal work by Marsh and Duchamp in 1969 on the crystal superstructure of the hydrogen-bonded networks of trimesic acid. We identify the development of novel hydrogen-bonding motifs such as diaminotriazine (DTA), the introduction of the concept of molecular tectonics, and the establishment of permanent porosity in HOFs as being some of the milestones, which incentivized the current burgeoning research endeavors on developing HOFs as multifunctional materials. This Account is focused primarily on surveying the strategies for constructing porous 3D HOFs based on organic building blocks with peripheral carboxyl groups. These strategies are presented in the following categories: (1) the polycatenation of 2D networks by trigonal building blocks to form global 3D frameworks, (2) the utilization of building blocks with 3D geometries—tetrahedral and trigonal prismatic—that are predisposed to form 3D networks, and (3) the docking by shape-fitting of geometrically labile building blocks. We emphasize how the molecular geometry of the building blocks plays an important role in modulating the superstructures of extended frameworks so as to address specific applications. Recognizing that the in silico design of HOFs is the ultimate goal of researchers in this field, we also discuss the recent advances in superstructure prediction that lead to the formation of porous supramolecular crystals and assess the complications in implementing computational methods for HOFs with complex superstructures. We hope this Account will inspire the development of new supramolecular designs and creative approaches to crystal engineering that aid and abet the assembly of multifunctional HOFs with customizable properties.
36 MATERIALS SCIENCE↗
Progress in SiC/SiC Ceramic Composite Development for Gas Turbine Hot-Section Components under NASA EPM and UEET Programs
The successful application of ceramic matrix composites as hot-section components in advanced gas turbine engines will require the development of constituent materials and processes that can provide the material systems with the key thermostructural properties required for long-term component service. Much initial progress in identifying these materials and processes was made under the former NASA Enabling Propulsion Materials Program using stoichiometric Sylramic (trademark) silicon-carbide (SiC) fibers, 2D (two dimensional)-woven fiber architectures, chemically vapor-infiltrated (CVI) BN fiber coatings (interphases), and SiC-based matrices containing CVI SiC interphase over-coatings, slurry-infiltrated SiC particulate, and melt-infiltrated (MI) silicon. The objective of this paper is to discuss the property benefits of this SiC/SiC composite system for high-temperature engine components and to elaborate on further progress in SiC/SiC development made under the new NASA Ultra Efficient Engine Technology Program. This progress stems from the recent development of advanced constituent materials and manufacturing processes, including specific treatments at NASA that improve the creep, rupture, and environmental resistance of the Sylramic fiber as well as the thermal conductivity and creep resistance of the CVI SiC over-coatings. Also discussed are recent observations concerning the detrimental effects of inadvertent carbon in the fiber-BN interfacial region and the beneficial effects of certain 2D-architectures for thin-walled SiC/SiC panels.
DiCarlo, J. A.↗
Autonomous Output‐Oriented Aerosol Jet Printing Enabled by Hybrid Machine Learning
Additive manufacturing (AM) is rapidly revolutionizing modern manufacturing with recent progress in advanced printing methods and improved properties of printed materials. However, traditional AM methods are limited by their input‐oriented nature, which demands tedious trial‐and‐error tuning of printing parameters to achieve desired output properties. Here, in this work, an output‐oriented artificial intelligence‐integrated AM (AIAM) method is reported that enables an user to specify desired output properties while the printer autonomously discovers the optimal input printing parameters by integrating hybrid machine learning models and in situ measurements. Based on a predictive mapping between the input printing parameters and the output properties of interests established with <20 experiments designed by active learning, inverse design tasks are performed to intelligently generate the printing parameter settings that lead to desired outcomes using reinforcement learning. This method is demonstrated by autonomous aerosol jet printing (AJP) of conductive polymer films and achieving user‐defined electrical resistances with an ultralow error of 3.7%. The AIAM method, with its output‐oriented nature, holds the potential to significantly improve the autonomy, predictability, efficiency, and accessibility of the AM processes, which will unlock new possibilities in the autonomous and intelligent printing of a broad range of functional materials and devices.
36 MATERIALS SCIENCE↗
Ionic Liquid Facilitated Solvent‐Phase Polymerization of Ultrasmooth Coatings of Polycatecholamines
Mussel-inspired polycatecholamine coatings and films have proven to be versatile materials for surface modification. However, the progress of chemically modified coatings with tailored properties has been slow due to the lack of definitive evidence of their polymeric structure. Polycatecholamines form aggregates during polymerization, and their formation mechanism has been a subject of debate owing to their insolubility in traditional molecular solvents. Exploiting the capability of ionic liquids (ILs) to exhibit strong electrostatic interactions, herein, the first solution-phase polymerization approach is reported to achieve polymerization of four catecholamines – dopamine (DA), norepinephrine (NE), L-3,4-dihydroxyphenylalanine (L-DOPA), and adrenaline (AD). Kinetic control over the polymerization process in the solution phase enabled it to follow the process with 1 H NMR spectroscopy, revealing the formation of structural features of resulting complex heterogeneous and soluble polymers. The polymers are both covalent and associative in nature. Solution phase polymerization prevented the formation of large aggregates in the solution, thus facilitating the formation of coatings that are ultra-smooth and have root mean square roughness of the order of sub-nm to nm scale.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Photovoltaic Devices Based on Colloidal PbX Quantum Dots: Progress and Prospects
Here, a certified power conversion efficiency (PCE) of 12.0% and an outstanding air stability has been achieved for PbX quantum dots (QDs) solar cells, indicating strong potential for next generation low-cost solution-processed photovoltaics. Similar progress has been made in several other solar cell architectures employing PbX QD absorbers. This article aims to review the recent progress in understanding the photovoltaic-relevant properties of PbX QDs and highlight their application in various types of photovoltaic devices. In doing so, we hope that the unique properties of PbX QDs can be better understood in a broader context, and their potential can be fully realized with the aiding of other photovoltaic materials and novel device structures.
14 SOLAR ENERGY↗