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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Microgravity Processing and Photonic Applications of Organic and Polymeric Materials

In recent years, a great deal of interest has been directed toward the use of organic materials in the development of high-efficiency optoelectronic and photonic devices. There is a myriad of possibilities among organics which allow flexibility in the design of unique structures with a variety of functional groups. The use of nonlinear optical (NLO) organic materials such as thin-film waveguides allows full exploitation of their desirable qualities by permitting long interaction lengths and large susceptibilities allowing modest power input. There are several methods in use to prepare thin films, such as Langmuir-Blodgett (LB) and self-assembly techniques, vapor deposition, growth from sheared solution or melt, and melt growth between glass plates. Organics have many features that make them desirable for use in optical devices such as high second- and third-order nonlinearities, flexibility of molecular design, and damage resistance to optical radiation. However, their use in devices has been hindered by processing difficulties for crystals and thin films. In this chapter, we discuss photonic and optoelectronic applications of a few organic materials and the potential role of microgravity on processing these materials. It is of interest to note how materials with second- and third-order nonlinear optical behavior may be improved in a diffusion-limited environment and ways in which convection may be detrimental to these materials.

Frazier, Donald O.↗
NASA NTRS1998

Microgravity Processing and Photonic Applications of Organic and Polymeric Materials

In recent years, a great deal of interest has been directed toward the use of organic materials in the development of high-efficiency optoelectronic and photonic devices. There is a myriad of possibilities among organic which allow flexibility in the design of unique structures with a variety of functional groups. The use of nonlinear optical (NLO) organic materials such as thin-film waveguides allows full exploitation of their desirable qualities by permitting long interaction lengths and large susceptibilities allowing modest power input. There are several methods in use to prepare thin films, such as Langmuir-Blodgett (LB) and self-assembly techniques, vapor deposition, growth from sheared solution or melt, and melt growth between glass plates. Organics have many features that make Abstract: them desirable for use in optical devices such as high second- and third-order nonlinearities, flexibility of molecular design, and damage resistance to optical radiation. However, their use in devices has been hindered by processing difficulties for crystals and thin films. In this chapter, we discuss photonic and optoelectronic applications of a few organic materials and the potential role of microgravity on processing these materials. It is of interest to note how materials with second- and third-order nonlinear optical behavior may be improved in a diffusion-limited environment and ways in which convection may be detrimental to these materials. We focus our discussion on third-order materials for all-optical switching, and second-order materials for all-optical switching, and second-order materials for frequency conversion and electrooptics.

Frazier, Donald 0↗
NASA NTRS1998

The Effects of Ground and Space Processing on the Properties of Organic, Polymeric, and Colloidal Materials

In recent years, a great deal of interest has been directed toward the use of organic materials in the development of high-efficiency optoelectronic and phototonic devices. There is a myriad of possibilities among organic materials which allow flexibility in the design of unique structures with a variety of functional groups. The use of nonlinear optical (NLO) organic materials as thin film wave-guides allows full exploitation of their desirable qualifies by permitting long interaction lengths and large susceptibilities allowing modest power input. There are several methods in use to prepare thin films such as Langmuir-Blodgett (LB) and self-assembly techniques, vapor deposition, growth from sheared solution or melt, and melt growth between glass plates. Organic-based materials have many features that make them desirable for use in optical devices, such as high second-and third-order nonlinearity, flexibility of molecular design, and damage resistance to optical radiation. However, their use in devices has been hindered by processing difficulties for crystals and thin films. We discuss the potential role of microgravity processing of a few organic and polymeric materials. It is of interest to note how materials with second-and third-order NLO behavior may be improved in a diffusion-limited environment and ways in which convection may be detrimental to these materials. We focus our discussion on third-order materials for all-optical switching, and second-order materials for frequency conversion and electrooptics. The goal of minimizing optical loss obviously depends on processing methods. For solution-based processes, such as solution crystal growth and solution photopolymerization, it is well known that thermal and solutal density gradients can initiate buoyancy-driven convection. Resultant fluid flows can affect transport of material to and from growth interfaces and become manifest in the morphology and homogeneity of the growing film or crystal. Likewise, buoyancy-driven convection can hinder production of defect-free, high-quality crystals or films during crystal and film growth by vapor deposition.

Frazier, Donald O.↗
DOE OSTI2021

Harnessing autocatalytic reactions in polymerization and depolymerization

Abstract Autocatalysis and its relevance to various polymeric systems are discussed by taking inspiration from biology. A number of research directions related to synthesis, characterization, and multi-scale modeling are discussed in order to harness autocatalytic reactions in a useful manner for different applications ranging from chemical upcycling of polymers (depolymerization and reconstruction after depolymerization), self-generating micelles and vesicles, and polymer membranes. Overall, a concerted effort involving in situ experiments, multi-scale modeling, and machine learning algorithms is proposed to understand the mechanisms of physical and chemical autocatalysis. It is argued that a control of the autocatalytic behavior in polymeric systems can revolutionize areas such as kinetic control of the self-assembly of polymeric materials, synthesis of self-healing and self-immolative polymers, as next generation of materials for a sustainable circular economy. Graphic Abstract

36 MATERIALS SCIENCE↗
DOE OSTI2023

Atomic-Scale Corrugations in Crystalline Polypeptoid Nanosheets Revealed by Three-Dimensional Cryogenic Electron Microscopy

Amphiphilic molecules that can crystallize often form molecularly thin nanosheets in aqueous solutions. The possibility of atomic-scale corrugations in these structures has not yet been recognized. We have studied the self-assembly of amphiphilic polypeptoids, a family of bio-inspired polymers that can self-assemble into various crystalline nanostructures. Atomic-scale structure of the crystals in these systems has been inferred using both X-ray diffraction and electron microscopy. We use cryogenic electron microscopy to determine the in-plane and out-of-plane structures of a crystalline nanosheet. Data were collected as a function of tilt angle and analyzed using a hybrid single-particle crystallographic approach. The analysis reveals that adjacent rows of peptoid chains, which are separated by 4.5 Å in the plane of the nanosheet, are offset by 6 Å in the direction perpendicular to the plane of the nanosheet. These atomic-scale corrugations lead to a doubling of the unit cell dimension from 4.5 to 9 Å. Our work provides an alternative interpretation for the observed Å X-ray diffraction peak often reported in polypeptoid crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy

Metal-organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation. We use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. Our observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Triclinic nematic colloidal crystals from competing elastic and electrostatic interactions

The self-assembly of nanoparticles can enable the generation of composites with predesigned properties, but reproducing the structural diversity of atomic and molecular crystals remains a challenge. We combined anisotropic elastic and weakly screened electrostatic interactions to guide both orientational and triclinic positional self-ordering of inorganic nanocrystals in a nematic fluid host. The lattice periodicity of these low-symmetry colloidal crystals is more than an order of magnitude larger than the nanoparticle size. The orientations of the nanocrystals, as well as the crystallographic axes of the ensuing triclinic colloidal crystals, are coupled to the uniform alignment direction of the nematic host, which can be readily controlled on large scales. We examine colloidal pair and many-body interactions and show how triclinic crystals with orientational ordering of the semiconductor nanorods emerge from competing long-range elastic and electrostatic forces.

42 ENGINEERING↗
DOE OSTI2012

Nanostructured Materials for Improved Photovoltaics

This research addresses the fundamental issues of cell morphology and phase dimensions that determine conversion efficiency in polymeric organic photovoltaic devices. The approach will help explain the relationships between morphological control, domain size, and power conversion efficiency in OPV devices, with the goal of providing direction for development of OPV systems with greater efficiency. The program addresses the DOE Office of Energy Efficiency and Renewable Energy goals of providing economically sustainable clean energy technologies to reduce dependence on foreign oil. This research focused on synthesis, fabrication and analysis of both active and protective layers for improved organic and inorganic hybrid PV (PhotoVoltaic) materials. A systematic study of phase size, shape, and distance was conducted to determine the effects of morphology in each process. Four classes of nanostructured materials were studied: 1) functional block copolymers (AB, acceptor-donor blocks) that self-assemble into matched domain sizes 2) synthetic core-shell particles with separate acceptor and donor layers 3) bacterial micro-compartment (BMC) proteins as self-assembling shells for core-shell nanoparticle constructs and 4) polyhedral oligomeric silsesquioxane (POSS) nanostructured chemicals for enhanced efficiency and durability.

14 SOLAR ENERGY↗
DOE OSTI2017

Catalytic and Transport Behaviors of Model and Porous and Composite Nanostructures

As stressed in the Basic Energy Sciences Advisory Committee (BESAC) Report “New Science for a Secure and Sustainable Energy Future” (December 2008), solving our Nation’s energy challenges will entail more than incremental changes in present materials-related technologies; new, advanced routes to nanostructured materials with transformational properties will be required. Herein we describe the design and fabrication of a hybrid biotic/abiotic membrane reactor that, mimicking natural systems, employs the metalloenzyme, carbonic anhydrase, to separate CO 2 from N 2 with unprecedented purity and rate. The membrane design, synthesis, and operation are based on multiple biomimetic and nanoscale fabrication strategies, nanoscale dimensional features, and nanoscale physical phenomena, for example: 1) Bottom-up self-assembly of a membrane comprising a periodic, aligned, cylindrical nanopore array with 8 nm diameter pores designed to accommodate carbonic anhydrase (CA) enzymes 2) Top-down Atomic Layer Deposition (ALD) and plasma processing of the nanopore array to create 18nm deep (by 8nm in diameter) superhydrophilic pores bounded by hydrophobic/superhydrophobic interfaces 3) Formation of a continuous, defect free, ultra-thin (~18-nm thick) but strong water membrane by capillary condensation within the uniformly-sized, superhydrophilic nanopore array 4) Accommodation of CA within the water filled nanopore array (~2 CAs per hydrophilic pore channel) to achieve an effective CA concentration within the 18-nm thick water membrane over 10X greater than achievable in solution Exposed to a mixture of CO 2 and N 2 this biomimetic membrane rapidly and selectively dissolves CO 2 within the CA filled water nano-channels on the ‘upstream side’ and regenerates CO 2 at the superhydrophobic interface on the ‘downstream’ side. In combination, the high CA concentration and exceptionally short diffusion distances enable rapid and highly selective CO 2 separation from N 2 and H 2 . Our membrane has a combined CO 2 flux and selectivity that exceed by orders of magnitude all existing CO 2 membranes and for the first time meet the US Department of Energy guidelines for CO 2 sequestration technologies. (The performance of our membrane was recognized by an R&D100 Award and the first R&D100 Green Technology Award in 2015 and an issued US Patent in 2017). We believe this membrane could be employed in combination with sequestration to help reduce greenhouse gas emissions and provide a viable, economically feasible pathway to achieve the goals of the 2016 Paris Accord, which aims to maintain a global temperature rise this century less than 2°C above pre-industrial levels. Further this membrane concept could be adapted to other enzymes to accomplish other separations of interest, e.g. H 2 . We also have established processing-structure-property relationships of ultrathin membrane-like monolayer materials that are intrinsically catalytic. Establishing processing-structure-property relationships for monolayer materials is crucial for a vast range of applications spanning optics, catalysis, electronics, and energy. Presently, for MoS 2 , a promising catalyst for artificial photosynthesis, considerable debate surrounds the structure/property relationships of its various allotropes. Using high-resolution transmission electron microscopy supported by density functional theory, we unambiguously solved the structure of MoS 2 monolayers and showed lithium intercalation to direct a preferential transformation of the basal plane from 2H (trigonal prismatic) to 1T’ (clustered Mo). These changes alter the energetics of MoS 2 interactions with hydrogen ((GH), and, with respect to catalysis, the 1T’ transformation renders the normally inert basal plane amenable towards hydrogen adsorption and H 2 evolution achieving Hydrogen Evolution Reaction (HER) catalytic activity comparable to 2H MoS 2 edges on Au(111), one of the most active HER catalysts known.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

“Uncontrolled” Preparation of Disperse Poly(lactide)- block -poly(styrene)- block -poly(lactide) for Nanopatterning Applications

We report the facile synthesis of well-defined ABA poly(lactide)-block-poly(styrene)-block-poly(lactide) (LSL) triblock copolymers having a disperse poly(styrene) midblock (Ð = 1.27–2.24). The direct synthesis of telechelic α,ω-hydroxypoly(styrene) (HO-PS-OH) midblocks was achieved using a commercially available difunctional free radical diazo initiator 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]. Poly(lactide) (PLA) end blocks were subsequently grown from HO-PS-OH macroinitiators via ring-opening transesterification polymerization of (±)-lactide using the most common and prevalent catalyst system available, tin(II) 2-ethylhexanoate. Fourteen LSL triblock copolymers with total molar masses Mn,total = 24–181 kg/mol and PLA volume fractions fPLA = 0.15–0.68 were synthesized and thoroughly characterized. The self-assembly of symmetric triblocks was analyzed in the bulk using small-angle X-ray scattering and in thin films using grazing incidence small-angle X-ray scattering and atomic force microscopy. We demonstrate both the bulk and thin film self-assembly of LSL disperse triblocks gave well-organized nanostructures with uniform domain sizes suitable for nanopatterning applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Advancing Understanding and Design of Functional Materials Through Theoretical and Computational Chemical Physics. In: Practical Aspects of Computational Chemistry II

Theoretical and computational chemical physics and materials science offers great opportunity toward helping solve some of the grand challenges in science and engineering, because structure and properties of molecules, solids, and liquids are direct reflections of the underlying quantum motion of their electrons. With the advent of semilocal and especially nonlocal descriptions of exchange and correlation effects, density functional theory (DFT) can now describe bonding in molecules and solids with an accuracy which, for many classes of systems, is sufficient to compare quantitatively to experiments. It is therefore becoming possible to develop a semiquantitative description of a large number of systems and processes. In this chapter, we briefly review DFT and its various extensions to include nonlocal terms that are important for long-range dispersion interactions that dominate many self-assembly processes, molecular surface adsorption processes, solution processes, and biological and polymeric materials. Applications of DFT toward problems relevant to energy systems, including energy storage materials, functional nanoelectronics/optoelectronics, and energy conversion, are highlighted.

Chemical reactions↗
DOE OSTI2012

Advancing Understanding and Design of Functional Materials Through Theoretical and Computational Chemical Physics

Theoretical and computational chemical physics and materials science offers great opportunity toward helping solve some of the grand challenges in science and engineering, because structure and properties of molecules, solids, and liquids are direct reflections of the underlying quantum motion of their electrons. With the advent of semilocal and especially nonlocal descriptions of exchange and correlation effects, density functional theory (DFT) can now describe bonding in molecules and solids with an accuracy which, for many classes of systems, is sufficient to compare quantitatively to experiments. It is therefore becoming possible to develop a semiquantitative description of a large number of systems and processes. In this chapter, we briefly review DFT and its various extensions to include nonlocal terms that are important for long-range dispersion interactions that dominate many self-assembly processes, molecular surface adsorption processes, solution processes, and biological and polymeric materials. Applications of DFT toward problems relevant to energy systems, including energy storage materials, functional nanoelectronics/optoelectronics, and energy conversion, are highlighted.

36 MATERIALS SCIENCE↗