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All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Effects of Convection During the Photodeposition of Polydiacetylene Thin Films

In this work, we describe a preliminary investigation of buoyancy-driven heat transfer during the growth of thin films from solution following exposure to ultraviolet (UV) light. Irradiation of the growth cell occurs at various directions relative to gravitational acceleration. Through numerical computations, the steady-state flow and temperature profiles are simulated during the course of light exposure. Light-induced polymerization accompanies a heat transfer process through a fairly complicated recirculating flow pattern. A scaling analysis shows that buoyancy-driven velocities only reduce by a factor of 10 for gravity levels as low as 10(exp -2)g(sub 0). Paley et al. observe what appears to be gravitationally sensitive particle development and inclusion in thin films using a photodeposition process. From this study it is clear that production of homogeneous thin films would have to occur in the environment of a complicated flow pattern of recirculation with a nonuniform temperature distribution. Indeed, even when irradiation occurs from the top of the cell, the most stable stratified cell orientation, defects remain in our films due to the persistence of buoyancy-driven convection. To achieve homogeneity, minimal scattering centers, and possible molecular order, photodeposition of polymer films by UV light exposure must proceed in a reduced-convection environment. Fluid mechanics simulations are useful for establishing gravitational sensitivity to this recently discovered process (patent # 5,451,433) for preparing thin films having quite promising nonlinear optical characteristics.

Frazier, D. O.↗
NASA NTRS1997

Effects of Convection during the Photodeposition of Polydiacetylene Thin Films

In this work, we describe a preliminary investigation of buoyancy-driven heat transfer during the growth of thin films from solution following exposure to ultraviolet (UV) light. Irradiation of the growth cell occurs at various directions relative to gravitational acceleration. Through numerical computations, the steady-state flow and temperature profiles are simulated during the course of light exposure. Light-induced polymerization accompanies a heat transfer process through a fairly complicated recirculating flow pattern. A scaling analysis shows that buoyancy-driven velocities only reduce by a factor of 10 for gravity levels as low as 10(exp -2) g(sub 0). Paley et al. observe what appears to be gravitationally sensitive particle development and inclusion in thin films using a photodeposition process. From this study, it is clear that production of homogeneous thin films would have to occur in the environment of a complicated flow pattern of recirculation with a nonuniform temperature distribution. Indeed, even when irradiation occurs from the top of the cell, the most stable stratified cell orientation, defects remain in our films due to the persistence of buoyancy-driven convection. To achieve homogeneity, minimal scattering centers, and possible molecular order, photodeposition of polymer films by UV light exposure must proceed in a reduced-convection environment. Fluid mechanics simulations are useful for establishing gravitational sensitivity to this recently discovered process (patent # 5,451,433) for preparing thin films having quite promising nonlinear optical characteristics.

Frazier, D. O.↗
NASA NTRS1996

Excess chemical potential of small solutes across water--membrane and water--hexane interfaces

The excess chemical potentials of five small, structurally related solutes, CH4, CH3F, CH2F2, CHF3, and CF4, across the water-glycerol 1-monooleate bilayer and water-hexane interfaces were calculated at 300, 310, and 340 K using the particle insertion method. The excess chemical potentials of nonpolar molecules (CH4 and CF4) decrease monotonically or nearly monotonically from water to a nonpolar phase. In contrast, for molecules that possess permanent dipole moments (CH3F, CH2F, and CHF3), the excess chemical potentials exhibit an interfacial minimum that arises from superposition of two monotonically and oppositely changing contributions: electrostatic and nonelectrostatic. The nonelectrostatic term, dominated by the reversible work of creating a cavity that accommodates the solute, decreases, whereas the electrostatic term increases across the interface from water to the membrane interior. In water, the dependence of this term on the dipole moment is accurately described by second order perturbation theory. To achieve the same accuracy at the interface, third order terms must also be included. In the interfacial region, the molecular structure of the solvent influences both the excess chemical potential and solute orientations. The excess chemical potential across the interface increases with temperature, but this effect is rather small. Our analysis indicates that a broad range of small, moderately polar molecules should be surface active at the water-membrane and water-oil interfaces. The biological and medical significance of this result, especially in relation to the mechanism of anesthetic action, is discussed.

NASA Center ARC↗
NASA NTRS2008

NASA's Ares I and Ares V Launch Vehicles -- Effective Space Operations Through Efficient Ground Operations

The United States (U.S.) plans to return to the Moon by 2020, with the development of a new human-rated space transportation system to replace the Space Shuttle, which is due for retirement in 2010 after it completes its missions of building the International Space Station and servicing the Hubble Space Telescope. Powering the future of space-based scientific exploration will be the Ares I Crew Launch Vehicle, which will transport the Orion Crew Exploration Vehicle to orbit where it will rendezvous with the Lunar Lander. which will be delivered by the Ares V Cargo Launch Vehicle. This new transportation infrastructure, developed by the National Aeronautics and Space Administration (NASA), will allow astronauts to leave low-Earth orbit for extended lunar exploration and preparation for the first footprint on Mars. All space-based operations begin and are controlled from Earth. NASA's philosophy is to deliver safe, reliable, and cost-effective solutions to sustain a multi-billion-dollar program across several decades. Leveraging 50 years of lessons learned, NASA is partnering with private industry, while building on proven hardware experience. This paper will discuss how the Engineering Directorate at NASA's Marshall Space Flight Center is working with the Ares Projects Office to streamline ground operations concepts and reduce costs. Currently, NASA's budget is around $17 billion, which is less than 1 percent of the U.S. Federal budget. Of this amount, NASA invests approximately $4.5 billion each year in Space Shuttle operations, regardless of whether the spacecraft is flying or not. The affordability requirement is for the Ares I to reduce this expense by 50 percent, in order to allow NASA to invest more in space-based scientific operations. Focusing on this metric, the Engineering Directorate provides several solutions-oriented approaches, including Lean/Six Sigma practices and streamlined hardware testing and integration, such as assembling major hardware elements before shipping to the Kennedy Space Center for launch operations. This paper provides top-level details for several cost saving initiatives, including both process and product improvements that will result in space transportation systems that are designed with operations efficiencies in mind. The Engineering Directorate provides both the intellectual capital embodied in an experienced workforce and unique facilities in which to validate the information technology tools that allow a nationwide team to collaboratively connect across miles that separate them and the engineering disciplines that integrate various piece parts into a whole system. As NASA transforms ground-based operations, it also is transitioning its workforce from an era of intense hands-on labor to a new one of mechanized conveniences and robust hardware with simpler interfaces. Ensuring that space exploration is on sound footing requires that operations efficiencies be designed into the transportation system and implemented in the development stage. Applying experience gained through decades of ground and space op'erations, while using value-added processes and modern business and engineering tools, is the philosophy upon which a new era of exploration will be built to solve some of the most pressing exploration challenges today -- namely, safety, reliability, and affordability.

Dumbacher, Daniel L.↗
NASA NTRS2009

Protocol for Communication Networking for Formation Flying

An application-layer protocol and a network architecture have been proposed for data communications among multiple autonomous spacecraft that are required to fly in a precise formation in order to perform scientific observations. The protocol could also be applied to other autonomous vehicles operating in formation, including robotic aircraft, robotic land vehicles, and robotic underwater vehicles. A group of spacecraft or other vehicles to which the protocol applies could be characterized as a precision-formation- flying (PFF) network, and each vehicle could be characterized as a node in the PFF network. In order to support precise formation flying, it would be necessary to establish a corresponding communication network, through which the vehicles could exchange position and orientation data and formation-control commands. The communication network must enable communication during early phases of a mission, when little positional knowledge is available. Particularly during early mission phases, the distances among vehicles may be so large that communication could be achieved only by relaying across multiple links. The large distances and need for omnidirectional coverage would limit communication links to operation at low bandwidth during these mission phases. Once the vehicles were in formation and distances were shorter, the communication network would be required to provide high-bandwidth, low-jitter service to support tight formation-control loops. The proposed protocol and architecture, intended to satisfy the aforementioned and other requirements, are based on a standard layered-reference-model concept. The proposed application protocol would be used in conjunction with conventional network, data-link, and physical-layer protocols. The proposed protocol includes the ubiquitous Institute of Electrical and Electronics Engineers (IEEE) 802.11 medium access control (MAC) protocol to be used in the datalink layer. In addition to its widespread and proven use in diverse local-area networks, this protocol offers both (1) a random- access mode needed for the early PFF deployment phase and (2) a time-bounded-services mode needed during PFF-maintenance operations. Switching between these two modes could be controlled by upper-layer entities using standard link-management mechanisms. Because the early deployment phase of a PFF mission can be expected to involve multihop relaying to achieve network connectivity (see figure), the proposed protocol includes the open shortest path first (OSPF) network protocol that is commonly used in the Internet. Each spacecraft in a PFF network would be in one of seven distinct states as the mission evolved from initial deployment, through coarse formation, and into precise formation. Reconfiguration of the formation to perform different scientific observations would also cause state changes among the network nodes. The application protocol provides for recognition and tracking of the seven states for each node and for protocol changes under specified conditions to adapt the network and satisfy communication requirements associated with the current PFF mission phase. Except during early deployment, when peer-to-peer random access discovery methods would be used, the application protocol provides for operation in a centralized manner.

Jennings, Esther↗
NASA NTRS2009

Testbed for LISA Photodetectors

The Laser Interferometer Space Antenna (LISA) is a gravitational wave observatory consisting of three spacecraft separated by 5 million km in an equilateral triangle whose center follows the Earth in orbit around the Sun but offset in orbital phase by 20 degrees. LISA is designed to observe sources in the frequency range of 0.1 mHz-100 mHz by measuring fluctuations of the inter-spacecraft separation with laser interferometry. Quadrant photodetectors are used to measure both separation and angular orientation. Noise level, phase and amplitude inhomogeneities of the semiconductor response, and channel cross-talk between quadrant cells need to be assessed in order to ensure the 10 pm/Square root(Hz) sensitivity required for the interferometric length measurement in LISA. To this end, we are currently developing a testbed that allows us to evaluate photodetectors to the sensitivity levels required for LISA. A detailed description of the testbed and preliminary results will be presented.

Guzman, Felipe↗
NASA NTRS2010

Fluvial Channel Networks as Analogs for the Ridge-Forming Unit, Sinus Meridiani, Mars

Fluvial models have been generally discounted as analogs for the younger layered rock units of Sinus Meridiani. A fluvial model based on the large fluvial fan provides a possibly close analog for various features of the sinuous ridges of the etched, ridge-forming unit (RFU) in particular. The close spacing of the RFU ridges, their apparently chaotic orientations, and their organization in dense networks all appear unlike classical stream channel patterns. However, drainage patterns on large fluvial fans low-angle, fluvial aggradational features, 100s of km long, documented worldwide by us provide parallels. Some large fan characteristics resemble those of classical floodplains, but many differences have been demonstrated. One major distinction relevant to the RFU is that channel landscapes of large fans can dominate large areas (1.2 million km2 in one S. American study area). We compare channel morphologies on large fans in the southern Sahara Desert with ridge patterns in Sinus Meridiani (fig 1). Stream channels are the dominant landform on large terrestrial fans: they may equate to the ubiquitous, sinuous, elongated ridges of the RFU that cover areas region wide. Networks of convergent/divergent and crossing channels may equate to similar features in the ridge networks. Downslope divergence is absent in channels of terrestrial upland erosional landscapes (fig. 1, left), whereas it is common to both large fans (fig. 1, center) and RFU ridge patterns (fig 1, right downslope defined as the regional NW slope of Sinus Meridiani). RFU ridge orientation, judged from those areas apparently devoid of impact crater control, is broadly parallel with the regional slope (arrow, fig. 1, right), as is mean orientation of major channels on large fans (arrow, fig. 1, center). High densities per unit area characterize fan channels and martian ridges reaching an order of magnitude higher than those in uplands just upstream of the terrestrial study areas fig. 1. In concert with several other regional features, these morphological similarities argue for the RFU as a possibly fluvial unit.

Wilkinson, M. J.↗
NASA NTRS2016

Bladed Terrain on Pluto: Possible Origins and Evolutions

Pluto's Bladed Terrain (centered roughly 20 deg N, 225 deg E) covers the flanks and crests of the informally named Tartarus Dorsa with numerous roughly aligned blade-like ridges oriented approx. North-South; it may also stretch considerably farther east onto the non-close approach hemisphere but that inference is tentative. Individual ridges are typically several hundred meters high, and are spaced 5 to 10 km crest to crest, separated by V-shaped valleys. Many ridges merge at acute angles to form Y-shape junctions in plan view. The principle composition of the blades themselves we suspect is methane or a methane-rich mixture. (Methane is spectroscopically strongly observed on the optical surfaces of blades.) Nitrogen ice is very probably too soft to support their topography. Cemented mixtures of volatile and non-volatile ices may also provide a degradable but relief supporting "bedrock" for the blades, perhaps analogous to Callisto. Currently we are considering several hypotheses for the origins of the deposit from which Bladed Terrain has evolved, including aeolian disposition, atmospheric condensation, updoming and exhumation, volcanic intrusions or extrusions, crystal growth, among others. We are reviewing several processes as candidate creators or sculptors of the blades. Perhaps they are primary depositional patterns such as dunes, or differential condensation patterns (like on Callisto), or fissure extrusions. Or alternatively perhaps they are the consequence of differential erosion (such as sublimation erosion widening and deepening along cracks), variations in substrate properties, mass wasting into the subsurface, or sculpted by a combination of directional winds and solar isolation orientation. We will consider the roles of the long-term increasing solar flux and short periods of warm thick atmospheres. Hypotheses will be ordered based on observational constrains and modeling to be presented at the conference.

methane↗
NASA NTRS2016

Bladed Terrain on Pluto: Possible Origins and Evolutions

Pluto’s Bladed Terrain (centered roughly 20°N, 225°E) covers the flanks and crests of the informally named Tartarus Dorsa with numerous roughly aligned blade-like ridges oriented ~North-South; it may also stretch considerably farther east onto the non-close approach hemisphere but that inference is tentative. Individual ridges are typically several hundred meters high, and are spaced 5 to 10 km crest to crest, separated by Vshaped valleys. Many ridges merge at acute angles to form Y-shape junctions in plan view. The principle composition of the blades themselves we suspect is methane or a methane-rich mixture. (Methane is spectroscopically strongly observed on the optical surfaces of blades.) Nitrogen ice is very probably too soft to support their topography. Cemented mixtures of volatile and non-volatile ices may also provide a degradable but relief supporting “bedrock” for the blades, perhaps analogous to Callisto. Currently we are considering several hypotheses for the origins of the deposit from which Bladed Terrain has evolved, including aeolian disposition, atmospheric condensation, updoming and exhumation, volcanic intrusions or extrusions, crystal growth, among others. We are reviewing several processes as candidate creators or sculptors of the blades. Perhaps they are primary depositional patterns such as dunes, or differential condensation patterns (like on Callisto), or fissure extrusions. Or alternatively perhaps they are the consequence of differential erosion (such as sublimation erosion widening and deepening along cracks), variations in substrate properties, mass wasting into the subsurface, or sculpted by a combination of directional winds and solar isolation orientation. We will consider the roles of the long-term increasing solar flux and short periods of warm thick atmospheres. Hypotheses will be ordered based on observational constrains and modeling to be presented at the conference.

Nitrogen ice↗
DOE OSTI2020

Accelerated Aging Humidity Chamber for Nuclear Grade HEPA Filter Media

A unique accelerated aging humidity chamber for simulating the natural aging process of nuclear grade high efficiency particulate air (HEPA) filter media is being designed, implemented, and tested. The nuclear industry currently lacks information regarding the shelf life and service life of HEPA filter media. The Department of Energy recommends disposing of HEPA filters 10 years after the manufacture date for filters operated under dry conditions. Studies have shown the tensile strength and water repellency of HEPA filter media diminish with age. The chamber's principal function is to sustain an elevated relative humidity condition for an extended duration specified by the Arrhenius aging model. To accomplish this, various design parameters were established: (1) consistently achieve uniform humidity conditions within the chamber to equally expose media sheets, (2) ensure the chamber is sufficiently sealed to mitigate the uncontrolled infiltration of air, (3) confidently secure the media sheets to avert the introduction of unnecessary stressing/creasing, (4) fabricate the chamber from clear polycarbonate material to allow inspection of the media sheets, (5) provide a safe and ergonomic design for personnel, (6) ensure the chamber design is replicable and relatively easy to fabricate/assemble. A humidity source, fan, PID controller, humidity and temperature transmitters, and data loggers are required for proper operation and control of the chamber. The humidity source must accommodate target values up to 95% relative humidity throughout the chamber. The three humidity and temperature transmitters are strategically spaced throughout the chamber to ensure uniform conditions. The 10 cubic feet per minute (CFM) fan selected intends to accomplish the desired air change rate inside the chamber of approximately 20 air changes per hour (ACH). The 2 plenums on the upper and lower portions of the chamber utilize a perforated design to uniformly distribute air, promote air mixing, and control the air velocity entering the chamber. Industrial blueprint hanging clamps are being retrofitted to be seated within the chamber drawers and firmly secure the nuclear grade filter media. The aged media will be evaluated using autopsy methodology, and the results obtained intend to help clarify the useful life of nuclear grade HEPA filters. Nuclear grade high efficiency particulate air (HEPA) filters are defined as disposable, extended-media, dry-type filters with a rigid casing enclosing the full depth of the pleats and have a minimum particle removal efficiency of 99.97%. [1] - HEPA filters are constantly exposed to stressors and subsequently have been shown to degrade as the filter ages. Properties such as tensile strength and water repellency, along with others, are negatively impacted. [2] - Due to the scarcity of naturally aged HEPA filters available, it is crucial to develop accelerated aging methods which effectively mimic the natural degradation effects. - After accelerated aging, the filters are subject to testing in the Axial Flow Large Scale Test Stand (ALSTS) and other analysis techniques such as the same qualification tests performed directly after being manufactured. - Quality data is necessary for future decisions regarding the lifetime of nuclear grade HEPA filters. - The objective is to develop a prototype accelerated aging humidity chamber for nuclear grade HEPA filter media. The chamber should expose the media to commonly occurring stressors to expedite the degradation process caused by aging. PID yields reliable and reproducible results: - CFD model correlates well with actual performance; - Further analysis is needed to complete characterization; - Future work for the chamber is still to be completed. The data shown in Figure 5 and Table 1 indicate the system is functioning as designed. As can be determined from the system response evaluation in Table 1, the PID controller is yielding reliable and reproducible results at each set point. As the set point increases, the time constant and 20% settling time increase accordingly. From the results in Table 1, it stands to reason that the CFD model correlates well with the actual performance of the system. Each system response parameter for the 90%RH* CFD model is slightly lower than the parameters collected from the physical model tested at an equivalent set point. This is to be expected considering the inlet in the CFD model is a constant supply of water vapor, whereas the physical model uses a PID controller to monitor the amount of water vapor needed and reacts accordingly. More analysis is still to be done on the prototype chamber. A pressure test will be conducted in order to determine the hourly leak rate of the chamber. This test will involve constant air flow into the chamber until the desired pressure is reached. A uniformity test will also be conducted in order to ensure each filter medium is being exposed to equivalent relative humidity levels. This test will involve an array of humidity meters strategically oriented inside the chamber to record any possible gradients. Future work for the chamber includes dehumidification abilities, tests while fully loaded with filters, and temperature control. Once completed, the autopsy team at Institute of Clean Energy Technology will conduct necessary accelerated aging studies as needed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS2012

Virtual Machine Language 2.1

VML (Virtual Machine Language) is an advanced computing environment that allows spacecraft to operate using mechanisms ranging from simple, time-oriented sequencing to advanced, multicomponent reactive systems. VML has developed in four evolutionary stages. VML 0 is a core execution capability providing multi-threaded command execution, integer data types, and rudimentary branching. VML 1 added named parameterized procedures, extensive polymorphism, data typing, branching, looping issuance of commands using run-time parameters, and named global variables. VML 2 added for loops, data verification, telemetry reaction, and an open flight adaptation architecture. VML 2.1 contains major advances in control flow capabilities for executable state machines. On the resource requirements front, VML 2.1 features a reduced memory footprint in order to fit more capability into modestly sized flight processors, and endian-neutral data access for compatibility with Intel little-endian processors. Sequence packaging has been improved with object-oriented programming constructs and the use of implicit (rather than explicit) time tags on statements. Sequence event detection has been significantly enhanced with multi-variable waiting, which allows a sequence to detect and react to conditions defined by complex expressions with multiple global variables. This multi-variable waiting serves as the basis for implementing parallel rule checking, which in turn, makes possible executable state machines. The new state machine feature in VML 2.1 allows the creation of sophisticated autonomous reactive systems without the need to develop expensive flight software. Users specify named states and transitions, along with the truth conditions required, before taking transitions. Transitions with the same signal name allow separate state machines to coordinate actions: the conditions distributed across all state machines necessary to arm a particular signal are evaluated, and once found true, that signal is raised. The selected signal then causes all identically named transitions in all present state machines to be taken simultaneously. VML 2.1 has relevance to all potential space missions, both manned and unmanned. It was under consideration for use on Orion.

Riedel, Joseph E.↗
NASA NTRS1985

Mission-oriented requirements for updating MIL-H-8501. Volume 2: STI background and rationale

A supplement to the structure of a new flying and ground handling qualities specification for military rotorcraft structure is presented in order to explain the background and rationale for the specification structure, the proposed forms of criteria, and the status of the existing data base. Critical gaps in the data base for the new structure are defined, and recommendations are provided for the research required to address the most important of these gaps.

Clement, W. F.↗
DOE OSTI2023

Directional effects of antiferromagnetic ordering on the electronic structure in NdSb

The recent discovery of unconventional surface-state pairs, which give rise to Fermi arcs and spin textures, in antiferromagnetically ordered NdBi raised the interest in rare-earth monopnictides. Several scenarios of antiferromagnetic (AFM) order have been suggested to explain the origin of these states with some of them being consistent with the presence of nontrivial topologies. Here, in this paper, we use angle-resolved photoemission spectroscopy (ARPES) and density-functional-theory (DFT) calculations to investigate the electronic structure of NdSb. We found the presence of distinct domains that have different electronic structures at the surface. These domains correspond to different orientations of magnetic moments in the AFM state with respect to the surface. We demonstrated remarkable agreement between DFT calculations and ARPES that capture all essential changes in the band structure caused by the transition to a magnetically ordered state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS2000

Asymptotic Solutions for Optical Properties of Large Particles with Strong Absorption

For scattering calculations involving nonspherical particles such as ice crystals, we show that the transverse wave condition is not applicable to the refracted electromagnetic wave in the context of geometric optics when absorption is involved. Either the TM wave condition (i.e., where the magnetic field of the refracted wave is transverse with respect to the wave direction) or the TE wave condition (i.e., where the electric field is transverse with respect to the propagating direction of the wave) may be assumed for the refracted wave in an absorbing medium to locally satisfy the electromagnetic boundary condition in the ray tracing calculation. The wave mode assumed for the refracted wave affects both the reflection and refraction coefficients. As a result, a nonunique solution for these coefficients is derived from the electromagnetic boundary condition. In this study we have identified the appropriate solution for the Fresnel reflection/refraction coefficients in light scattering calculation based on the ray tracing technique. We present the 3 x 2 refraction or transmission matrix that completely accounts for the inhomogeneity of the refracted wave in an absorbing medium. Using the Fresnel coefficients for an absorbing medium, we derive an asymptotic solution in an analytical format for the scattering properties of a general polyhedral particle. Numerical results are presented for hexagonal plates and columns with both preferred and random orientations. The asymptotic theory can produce reasonable accuracy in the phase function calculations in the infrared window region (wavelengths near 10 micron) if the particle size (in diameter) is on the order of 40 micron or larger. However, since strong absorption is assumed in the computation of the single-scattering albedo in the asymptotic theory, the single scattering albedo does not change with variation of the particle size. As a result, the asymptotic theory can lead to substantial errors in the computation of single-scattering albedo for small and moderate particle sizes. However, from comparison of the asymptotic results with the FDTD solution, it is expected that a convergence between the FDTD results and the asymptotic theory results can be reached when the particle size approaches 200 micron. We show that the phase function at side-scattering and backscattering angles is insensitive to particle shape if the random orientation condition is assumed. However, if preferred orientations are assumed for particles, the phase function has a strong dependence on scattering azimuthal angle. The single-scattering albedo also shows very strong dependence on the inclination angle of incident radiation with respect to the rotating axis for the preferred particle orientations.

Yang, Ping↗
DOE OSTI2020

Molecular Orientation for Vapor-Deposited Organic Glasses Follows Rate-Temperature Superposition: The Case of Posaconazole

The anisotropic properties of organic glasses produced by physical vapor deposition (PVD) depend upon substrate temperature and deposition rate. In recent work, it was shown for a liquid crystalline system that the anisotropic structure of the glass was controlled by a single combined variable as indicated by the observation of deposition rate-substrate temperature superposition (RTS). Here we test the utility of RTS for posaconazole, a molecule that does not form liquid crystals. We prepare glasses of posaconazole utilizing a range of deposition rates covering 2 orders of magnitude and an 18 K range in substrate temperature. We characterize the glasses using ellipsometry and X-ray scattering. Consistent with RTS, we find that decreasing the deposition rate has the same effect upon molecular orientation as increasing the substrate temperature during deposition. Thus, RTS can be used to predict and control the structure of glasses prepared at a wide range of deposition conditions. We use RTS to infer a characteristic time for molecular reorientation at the surface of posaconazole.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Hydrolysis-Induced Morphology Evolution of Linear and Bottlebrush Block Copolymers in Thin Films with Acid Vapor or Photoacid Generators

The self-assembly of high-χ low-N block copolymers (BCPs) can give patterns with sub-10 nm full pitch, serving as a promising alternative to photolithographic methods. Here, in this work, we synthesized poly(solketal methacrylate)-block-polystyrene copolymers, PSM-b-PS, with various volume ratios of the two blocks. After hydrolysis of the PSM block into poly(glycerol monomethacrylate), PGM, the BCPs had both lamellar and cylindrical microdomain morphologies in the bulk phase and in thin films. In addition to our previously developed solid-state hydrolysis strategy involving trifluoroacetic acid vapor, we developed a new photoinduced solid-state hydrolysis using photoacid generators, PAGs, embedded within the polymer films. After exposure to UV followed by a postexposure baking or solvent vapor annealing, the BCPs transitioned from the disordered, phase-mixed state into laterally ordered cylindrical patterns. In comparison to linear BCPs that rely on a random copolymer layer to modify interfacial interactions with the substrate to promote an orientation of the microdomains normal to the interface, we found that the microdomains in bottlebrush multiblock copolymers oriented normal to the interface absent substrate modification due to the chain architecture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Quantifying Stern layer water alignment before and during the oxygen evolution reaction

While water’s oxygen is the electron source in the industrially important oxygen evolution reaction, the strong absorber problem clouds our view of how the Stern layer water molecules orient themselves in response to applied potentials. Here, we report nonlinear optical measurements on nickel electrodes held at pH 13 indicating a disorder-to-order transition in the Stern layer water molecules before the onset of Faradaic current. A full water monolayer (1.1 × 10 15 centimeter −2 ) aligns with oxygen atoms pointing toward the electrode at +0.8 volt and the associated work is 80 kilojoule per mole. Our experiments identify water flipping energetics as a target for understanding overpotentials, advance molecular electrochemistry, provide benchmarks for electrical double layer models, and serve as a diagnostic tool for understanding electrocatalysis.

Science & Technology - Other Topics↗
NASA NTRS1972

Effects of electrons and protons on science instruments

The radiation effects on typical science instruments according to the Jupiter trapped radiation design restraint model are described, and specific aspects of the model where an improved understanding would be beneficial are suggested. The spacecraft design used is the TOPS 12L configuration. Ionization and displacement damage are considered, and damage criteria are placed on the most sensitive components. Possible protective measures are mentioned: selecting components as radiation resistant as possible, using a difference in desired and undesired signal shapes for electronic shielding, orienting and locating the component on the spacecraft for better shielding, and adding passive shields to protect specific components. Available options are listed in decreasing order of attractiveness: attempt to lower the design restraints without compromising the success of the missions, trade off experiment objectives for increased reliability, alter the trajectory, and remove sensitive instruments from the payload.

Parker, R. H.↗