Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “protective layer”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,153 records · Page 64

Degradation of electro-optic components aboard LDEF

Re-measurement of the properties of a set of electro-optic components exposed to the low earth orbital environment aboard the Long Duration Exposure Facility (LDEF) indicates that most components survived quite well. Typical components showed some effects related to the space environment unless well protected. The effects were often small but significant. Results for semiconductor infrared detectors, lasers, LED's, filter, mirrors, and black paints will be presented. Semiconductor detectors and emitters were scarred but reproduced their original characteristics. Spectral characteristics of multi-layer dielectric filters and mirrors were found to be altered and degraded. Increased absorption in black paints indicates an increase in absorption sites, giving rise to enhanced performance as coatings for baffles and sunscreens. We find plastics and multi-layer dielectric coatings to be potentially unstable. Semiconductor devices, metal, and glass are more likely to be stable.

Blue, M. D.↗

Thermal/environmental barrier coating system for silicon-based materials

A coating system for a substrate containing a silicon-based material, such as silicon carbide-containing ceramic matrix materials containing silicon carbide and used to form articles exposed to high temperatures, including the hostile thermal environment of a gas turbine engine. The coating system includes a layer of barium strontium aluminosilicate (BSAS) as a bond coat for a thermal-insulating top coat. As a bond coat, the BSAS layer serves to adhere the top coat to a SiC-containing substrate. The BSAS bond coat exhibits sufficient environmental resistance such that, if the top coat should spall, the BSAS bond coat continues to provide a level of environmental protection to the underlying SiC-containing substrate.

Spitsberg, Irene T.↗

Thermal Management and Thermal Protection Systems

During my internship in the Thermal Design Branch (ES3), I contributed to two main projects: i) novel passive thermal management system for future human exploration, ii) AVCOAT undercut thermal analysis. i) As NASA prepares to further expand human and robotic presence in space, it is well known that spacecraft architectures will be challenged with unprecedented thermal environments. Future exploration activities will have the need of thermal management systems that can provide higher reliability, mass and power reduction and increased performance. In an effort to start addressing the current technical gaps the NASA Johnson Space Center Passive Thermal Discipline has engaged in technology development activities. One of these activities was done through an in-house Passive Thermal Management System (PTMS) design for a lunar lander. The proposed PTMS, functional in both microgravity and gravity environments, consists of three main components: a heat spreader, a novel hybrid wick Variable Conductance Heat Pipe (VCHP), and a radiator. The aim of this PTMS is to keep electronics on a vehicle within their temperature limits (0 and 50 C for the current design) during all mission phases including multiple lunar day/night cycles. The VCHP was tested to verify its thermal performance. I created a thermal math model using Thermal Desktop (TD) and analyzed it to predict the PTMS performance. After testing, the test data provided a means to correlate the thermal math model. This correlation took into account conduction and convection heat transfer, representing the actual benchtop test. Since this PTMS is proposed for space missions, a vacuum test will be taking place to provide confidence that the system is functional in space environments. Therefore, the model was modified to include a vacuum chamber with a liquid nitrogen shroud while taking into account conduction and radiation heat transfer. Infrared Lamps were modelled and introduced into the model to simulate the sun's rays directly impinging on the system. Heating rate of the lamps were calculated by knowing fraction of emitted energy in a wavelength interval and the filament temperature. This version of the model can be used to predict performance of the system under vacuum with extreme cold or hot conditions. Initial testing of the PTMS showed promise, and the thermal math model predicts even better performance in thermal vacuum testing. ii) Thermal Protection Systems (TPS) are required for vehicles which enter earth's atmosphere to protect from aerodynamic heating caused by the friction between the vehicle and atmospheric gases. Orion's heat shield design has two aspects which needed to be analyzed thermally: i) a small excess of adhesive used to bond the outer AVCOAT layer to the inner composite structure tends to seep from under the AVCOAT and form a small bead in between two bricks of AVCOAT, ii) a silicone rubber with different thermophysical properties than AVCOAT fills the gap between two bricks of AVCOAT. I created a thermal model using TD to determine temperature differences that are caused by these two features. To prevent false results, all TD models must be verified against something known. In this case, the TD model was correlated to CHAR, an ablation modelling software used to analyze TPS. Analyzing a node far from the concerning features, we saw that the TD model data match CHAR data, verifying the TD model. Next, the temperature of the silicone rubber as well as the bead of adhesive were analyzed to determine if they exceeded allowable temperatures. It was determined that these two features do not have a significant effect on the max temperature of the heat shield. This model can be modified to check temperatures at various locations of the heat shield where the composite thickness varies.

Hasnain, Aqib↗

Temperature Mapping at the Thermal Barrier Coating/Bond Coat Interface by Luminescence Lifetime Imaging Using Integrated Erbium-Doped Sublayers

Full-field temperature mapping of thermal barrier coated components by either infrared thermography or phosphor thermometry has been limited to surface temperature mapping even though temperature mapping at the thermal barrier coating (TBC)/bond coat interface is more relevant for evaluating the TBC thermal protection performance. For the first time, 2D temperature mapping at the TBC/bond coat interface has now been achieved by full-field luminescence lifetime imaging measurements of emission from a thin erbium-doped yttria-stabilized zirconia (YSZ) sensing layer integrated into the TBC below the overlying undoped YSZ. This new capability was applied to map temperatures at the TBC/bond coat interface for TBC-coated specimens subjected to a heat flux produced by the NASA Glenn high heat flux laser facility. In particular, thermal gradients at the TBC/bond coat interface were mapped in regions where the TBC was subjected to erosion or to mechanically induced delamination crack propagation. Finally, temperature mapping of the TBC/bond coat interface was used to evaluate the effectiveness of surface air film cooling at the TBC/bond coat interface.

Eldridge, Jeffrey I.↗

Development of an Effective Finite-rate Oxidation Model for NuSil-coated Charred Carbon Preform Ablators

Recently, a detailed effective finite-rate surface chemistry model was developed for the oxidation of FiberForm [1] using the molecular beam experimental data of Poovathingal et al., [2]. FiberForm is the major building block of the thermal protection system (TPS) material Phenolic Impregnated Carbon Ablator (PICA), commonly used by NASA. The surface chemistry model consists of detailed surface reaction mechanisms such as adsorption, desorption, and several types of Langmuir-Hinshelwood (LH) reactions to characterize the oxygen-carbon interactions at the surface. This model provides excellent agreement with the experimental data for oxidation product compositions and corresponding translational energy distributions. Further, an effective oxidation model was constructed that captures the equivalent interaction of oxygen inside the microstructure (including multiple surface collisions) via a modified reactivity for a smooth wall boundary condition. This enables the use of this model directly into Computational Fluid Dynamics (CFD) codes and Material Response (MR) codes to accurately simulate the gas–surface interactions within FiberForm without using the detailed micro-structure. However, this effective model is valid only for the virgin FiberForm. As the TPS material undergoes ablation, the preform carbon burns and turns into char. In addition, PICA is also coated with a protective silicon coating called NuSil for the purpose of mitigating the spread of phenolic dust, and limit contamination during clean room operations. Fig. 1 shows a X-ray microtomography image of a charred NuSil-coated PICA. The NuSil layer introduces species containing silicon into the product mixture. Further, the reactivity of the carbon within the char layer is different from the virgin FiberForm as shown in Fig. 2. Recently a new set of molecular beam experiments were performed on this NuSil-coated TPS material [3] with the same type of oxygen beam used in the previous experiments. Using the latest experimental data, the previously developed effective model will be extended to account for the charred carbon as well as the NuSil coating. Finally, this new effective model with three phases – preform carbon, char, and NuSil; will be compared and validated against the experimental product compositions.

K Swaminathan Gopalan↗

Aerothermal Analysis of the Dragonfly Titan Entry

The Dragonfly mission will send a rotorcraft lander to the surface of Saturn’s moon Titan as part of the New-Frontiers program. This will be the first spacecraft to land on Titan since the Huygens probe’s descent in January of 2005 and only the second spacecraft to enter Titan’s atmosphere. The Dragonfly entry capsule is significantly larger than the Huygens probe and will experience higher aerothermal environments. This poster will provide an overview of the aerothermodynamic models used in the Dragonfly aeroshell design process. Titan provides a unique entry environment that has several fundamental differences from the environments at the more common entry destinations of Earth and Mars. The lack of atmospheric oxygen significantly reduces heatshield recession (expected to be negligible), which simplifies material response analysis but also reduces the efficiency of the thermal protection system. The atmos-phere is composed of mostly nitrogen and trace amounts of methane. During hypersonic entry this methane dissociates and leads to the formation of the molecule CN, which is known to radiate strongly in the shock layer. Current Dragonfly heating predictions estimate that radiation contributes about 50% of the total heat flux along the forebody and up to 90% on the aftbody, making radiation a key element of aerothermal analysis. To properly address the importance of radiation, a unique radiative-heating correlation was developed that incorporates normal-shock equilibrium chemistry predictions based on work from the Mars 2020 program. These new heating correlations agree well with Computational Fluid Dynamics (CFD) predictions and enable large-scale trajectory analyses by providing rapid heating predictions along candidate trajectories. Dragonfly aerothermal environments are generated with the Data Parallel Line Relaxation (DPLR) finite-volume Navier-Stokes solver alongside the Nonequilibrium Radiative Transport and Spectra (NEQAIR) radiation transport code. DPLR produces shock-aligned flowfields that incorporate the effects of both chemical and thermal nonequilibrium while NEQAIR solves the radiation transport equations along lines-of-sight through the flowfield solutions to predict the radiative heating on the aeroshell. Titan’s atmosphere produces complex thermal and chemical nonequilibria and so classical radiation approximations that extrapolate from a single line-of-sight, such as the Tangent-Slab method, were found to overpredict peak radiative heat fluxes by 10-20%. Therefore, all radiative heating is directly calculated using 3-D transport for both the forebody and aftbody to reduce unnecessary conservatism. A 21-species finite-rate chemistry model, including electrons and ionized species, is used in the CFD to ensure accurate vehicle heating predictions (the level of ionization is particularly for accurate radiative flux predictions). This poster will cover: 1) The models and assumptions used to simulate entry into Titan’s atmosphere, 2) Dragonfly aerothermal engineering correlations alongside statistical heating values, and 3) Driving aerothermal considerations for a Titan entry such as CN formation and radiation-flowfield coupling.

EDL↗

Post-Flight Assessment of Avcoat Thermal Protection System for the Exploration Flight Test-1

On December 5, 2014 NASA conducted the first flight test of its next generation human-class Orion spacecraft. The flight was called the Exploration Flight Test -1 (EFT-1) which lasted for 4 hours and culminated into a re-entry trajectory at 9 km/s. This flight test of the 5-meter Orion Crew Module demonstrated various sub-systems including the Avcoat ablative thermal protection system (TPS) on the heat shield. The Avcoat TPS had been developed from the Apollo-era recipe with a few key modifications. The engineering for thermal sizing was supported by modeling, analysis, and ground tests in arc jet facilities. This paper will describe a postlfight analysis plan and present results from post-recovery inspections, data analysis from embedded sensors, TPS sample extraction and characterization in the laboratory. After the recovery of the vehicle, a full photographic survey and surface scans of the TPS were performed. The recovered vehicle showed physical evidence of flow disturbances, varying degrees of surface roughness, and excessive recession downstream of compression pads. The TPS recession was measured at more than 200 locations of interest on the Avcoat surface. The heat shield was then processed for sample extraction prior to TPS removal using the 7-Axis Milling machine at Marshall Space Flight Center. Around 182 rectangular TPS samples were extracted for subsequent analysis and investigation. The final paper will also present results of sample analysis. The planned investigation includes sidewall imaging, followed by image analysis to characterize TPS response by quantifying different layers in the char and pyrolysis zones. A full postmortem of the instrumentation and sensor ports will also be performed to confirm no adverse effects due to the sensors themselves. A subset of the samples will undergo structural testing and perform detailed characterization of any cracks and integrity of gore seams. Finally, the material will be characterized with layer-by-layer density measurements and SEM investigations to evaluate material morphology at microstructural level including identification of elements and compounds.

Aerothermodynamics↗

Analysis of furnace contamination on superconducting radio frequency niobium using secondary-ion mass spectrometry

Detection of surface contamination on niobium materials used in superconducting radio frequency (SRF) applications is difficult due to quantitative sensitivity and near-atomic depth resolution needed. Inspection of samples known to have experienced surface contamination was found to have inconsistent nitride coverage after high-temperature nitrogen gas exposure (“doping”). Here we compare contaminating species found on samples treated in several different vacuum furnaces, both “exposed” directly in the chamber and “protected” by containment shielding from evaporative sources with “furnace caps.” Typically, furnace caps are used to impede contamination from reaching the interior surface of cavities during the high-temperature vacuum bake that immediately precedes exposure to nitrogen gas. Although, to date, little is known about the effectiveness of these caps, SIMS results showed that they were effective in limiting contamination arising from the furnace environment. Inspection of sample surfaces by SEM showed a lack of nitrides present on contaminated specimens. TEM with energy dispersive spectroscopy performed on these samples revealed that a carbon-rich layer now existed, indicating that a relatively high contaminant load prevents the nucleation and growth of surface nitrides, while thus inhibiting interstitial nitrogen uptake. Except in extreme cases, subsequent removal of the top several micrometers of the surface via electropolishing appears to effectively eliminate any strong influence on the subsequent SRF cavity performance. With the absence of furnace cleaning, carbon contamination was found to be nearly 10× higher for protected nitrogen-doped and electropolished samples, with minimal metallic contamination detected for both processes. SIMS analysis was also performed to compare the cleanliness of samples fully prepared by such nitrogen “doping” with those prepared by a related process, involving the dissolution of niobium surface oxide and diffusion of oxygen into the surface. This oxygen doping or alloying process offers attractive advantages.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Metal-Insulation REBCO Pancake Coil With Solder Surface Shunt: Testing and Modeling

Rare-earth barium copper oxide (REBCO) high-temperature superconducting (HTS) magnets can generate very high magnetic fields with superior engineering current density and robust mechanical integrity. The no-insulation (NI) winding technique, including its metal-insulation (MI) variant, enables “self-protection” against localized overheating through inter-turn current sharing, improving defect tolerance and allowing temporary current overloads. In REBCO pancake coils, the current-sharing path is predominantly confined to the edges of the REBCO tapes due to insulating buffer layers. Applying a surface shunt using solder can effectively enhance current sharing in NI/MI coils via the REBCO tape edges. Here, in this paper, we present both experimental and numerical research on the current distribution in surface-shunt metal-insulation (SSMI) REBCO pancake coils. We tested a stainless steel co-wound MI REBCO double-pancake coil, before and after applying a soldered surface shunt, in a saturated liquid nitrogen bath. The SSMI coil was modeled using the H-formulation and rotated anisotropic resistivity to study its dynamic behavior, including inter-turn current sharing and intra-turn screening currents. Benchmarked by experimental data, the numerical model is able to study the defect tolerance of the SSMI coil during energization.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Development and Test of a Large Aperture $Nb_3Sn$ Cos-Theta Dipole Coil with Stress Management

An innovative stress-management (SM) concept for cos-theta (CT) coils (SMCT coil concept) has been proposed at Fermilab. A large-aperture two-layer Nb3Sn SMCT dipole coil was designed and manufactured to validate and test the SM concept including coil design, fabrication technology, and performance. The first large-aperture SMCT coil (SMCT1) was fabricated and assembled with a small-aperture Nb3Sn coil inside a dipole mirror magnet. SMCT1 coil tests in a dipole mirror structure was performed in two configurations - SMCTM1a with only powered two-layer SMCT1 coil and SMCTM1b with the SMCT coil connected in series with an inner two-layer dipole coil. The test goals are to prove the SMCT coil concept in two-layer and four-layer mirror configurations; demonstrate that the magnet can reach the targeted quench current at the established preload; study magnet training, training memory after thermal cycle, ramp rate and temperature dependences of the magnet quench current; and test the SMCT1 coil quench protection parameters. This paper summarizes the SMCT1 coil design and parameters, the coil main fabrication steps, its assembly in the dipole mirror structure. The results of the SMCTM1a/b mirror test are presented and discussed.

43 PARTICLE ACCELERATORS↗

Gate protective device for SOS array

Protective gate device consisting of alternating heavily doped n(+) and p(+) diffusions eliminates breakdown voltages in silicon oxide on sapphire arrays caused by electrostatic discharge from person or equipment. Diffusions are easily produced during normal double epitaxial processing. Devices with nine layers had 27-volt breakdown.

Meyer, J. E., Jr.↗

Data correlation and analysis of arc tunnel and wind tunnel tests of RSI joints and gaps, phase 2. Volume 1: Technical report

Heat transfer data measured in gaps representative of those being employed for joints in the space shuttle reusable surface insulation (RSI) thermal protection systems (TPS) were assimilated, analyzed, and correlated. Several types of gap were investigated with emphasis on simple butt joints. Gap widths ranged from 0.0 to 0.76 cm and depths ranged from 1 to 6 cm. Laminar, transitional, and turbulent boundary layer flows over the gap opening were investigated. The angle between gap axis and external flow was varied between 0 and pi/2 radians. The contoured cross section gap performed significantly better than all other wide gaps and slightly better than all other narrow gap geometries. Three dimensional heating variations were observed within gaps in the absence of external flow pressure gradients. Interactions between heating within gaps and heating of adjacent top tile surfaces were observed. Gaps aligned with the flow were observed to promote boundary layer transition. Heat transfer correlation equations were obtained for many of the tests. The TPS thickness requirements with and without gaps were computed for a current shuttle entry trajectory. Experimental data employed in the study are summarized. A description of each test facility, run schedule and test conditions, model descriptive information, and heat flux data are included.

Cristensen, H. E.↗

Environmental Barrier Coatings for Ceramic Matrix Composites - An Overview

Ceramic Matrix Composites (CMCs) are increasingly being considered as structural materials for advanced power generation equipment. Broadly speaking the two classes of materials are oxide-based CMCs and non-oxide based CMCs. The non-oxide CMCs are primarily silicon-based. Under conditions prevalent in the gas turbine hot section the water vapor formed in the combustion of gaseous or liquid hydrocarbons reacts with the surface-SiO2 to form volatile products. Progressive surface recession of the SiC-SiC CMC component, strength loss as a result of wall thinning and chemical changes in the component occur, which leads to the loss of structural integrity and mechanical strength and becomes life limiting to the equipment in service. The solutions pursued to improve the life of SiC-SiC CMCs include the incorporation of an external barrier coating to provide surface protection to the CMC substrate. The coating system has become known as an Environmental Barrier Coating (EBC). The relevant early coatings work was focused on coatings for corrosion protection of silicon-based monolithic ceramics operating under severely corrosive conditions. The development of EBCs for gas turbine hot section components was built on the early work for silicon-based monolithics. The first generation EBC is a three-layer coating, which in its simplest configuration consists of a silicon (Si) base coat applied on top of the CMC, a barium-strontium-aluminosilicate (BSAS) surface coat resistant to water vapor attack, and a mullite-based intermediate coating layer between the Si base coat and BSAS top coat. This system can be represented as Si-Mullite-BSAS. While this baseline EBC presented a significant improvement over the uncoated SiC-SiC CMC, for the very long durations of 3-4 years or more expected for industrial operation further improvements in coating durability are desirable. Also, for very demanding applications with higher component temperatures but shorter service lives more rugged EBCs will be necessary. A second generation of EBCs incorporates rare earth silicates which have extremely favorable resistance against environmental attack and a higher temperature capability. Performance data for this class of EBCs is more limited and especially field data are not as extensive as for the first generation EBCs. Extensive laboratory, rig and engine testing, including testing of EBC coated SiC-SiC CMCs in actual field applications is in progress. The development of next generation EBCs with even higher temperature capability than the second generation EBC is also underway. This paper will discuss the current status of EBC technology and future direction based on literature survey.

Laboratory↗

Advanced TUFROC Thermal Protection System Evolution Under Re-entry like Conditions

Toughened Unipiece Fibrous Reinforced Oxidation-resistant Composite (TUFROC) and its successor, Advanced TUFROC, are state-of-the-art thermal protection systems (TPS) for high temperature reusable applications. Originally designed for use on the wing-leading edge of X-37B, TUFROC is an insulative tiled system consisting of a low-conductivity ceramic base, a carbonaceous cap, and multiple coatings for thermal performance. The improved Advanced TUFROC has demonstrated reusability up to 2900 °F and single use capabilities exceeding 3200 °F. This effort explores the evolution of Advanced TUFROC when exposed to re-entry like conditions via arc jet testing. Chemical reactions and constituent migration resulting from the aerothermal heating are known to occur and are studied in detail. Further, the interaction between the multiple constituents and layers will be discussed as this is believed to have a significant impact on the overall performance. Characterization includes structural analysis via optical microscopy, scanning electron microscopy and energy-dispersive x-ray spectroscopy.

Thermal protection system↗

Advances in Design Capabilities for Planetary Missions from the NASA Entry Systems Modeling and Instrumentation Portfolio

The Entry Systems Modeling project (ESM) is supported by both the NASA Space Technology and the Science Mission Directorates and focuses on developing simulation tools and validated models for characterizing the performance of entry systems tailored to planetary destinations across the Solar System. ESM is organized into six technical capability areas that together address all relevant factors related to spacecraft entry, as well as some aspects of descent: Thermal Protection System (TPS) Materials; Aerothermodynamics; Entry & Descent Vehicle Dynamics; Guidance, Navigation, and Control; Vehicle Systems Analysis; and Advanced Tools and Numerical Methods. Development within the capability areas is undertaken explicitly with a focus on transition and infusion to science missions, human exploration missions, and commercial space activities. The present talk details developments that specifically impact science missions, including simulation tool capabilities that aid in mission design and model development to understand entry system performance at a given destination. Examples of the successful infusion and transition of such project outcomes to science missions also are provided. Several simulation tool development efforts within ESM have resulted in new design capabilities for missions. One such outcome is improved toolsets for mission trajectory and concept of operations design. Specifically, an initiative to couple a leading tool for entry, ascent/descent, and orbital trajectory optimization (Program to Optimize Simulated Trajectories II or POST2) to those used within the Agency for interplanetary trajectory optimization (Copernicus and Monte) has made substantial progress, with the outcomes to date promising to allow efficient trajectory optimization across mission phases. Additionally, toolchains for the evaluation of vehicle performance during entry and descent have been developed that allow assessment of multi-dimensional aeroheating on detailed vehicle geometries, characterization of deployment and inflation of parachutes, and assessment of vehicle dynamic stability during descent. These capabilities are achieved by coupling diverse sets of physics together – material response, computational fluid dynamics, radiation, and vehicle dynamics – to suitably describe complex entry and descent phenomena. Several model development and validation efforts for specific destinations and entry regimes also are underway within the ESM project. For instance, new experimental capabilities to validate radiation models at low densities/high altitudes recently have been established with project support, specifically the Low-Density Shock Tube (LDST) at the NASA Ames Research Center Electric Arc Shock Tube (EAST) facility. The LDST is being leveraged to develop improved models of shock layer kinetics and radiation in Titan atmospheres, while future studies will be conducted in the LDST and the existing high velocity shock tube to provide validation data for radiation models of Venus, Ice Giants, and Mars atmospheres. Models describing the aerothermal and thermo-structural performance of Thermal Protection System (TPS) materials has been another focus, with multiscale modeling activities on-going for the two leading TPS materials applicable to a range of entry conditions and science missions: the Phenolic-Impregnated Carbon Ablator (PICA) and woven materials like 3D Mid-Density Carbon Phenolic (3MDCP). A continual effort is made to infuse and transition outcomes from ESM simulation tool and model development activities into relevant science missions. Significant progress has been made on this front, with missions such as Dragonfly, DAVINCI, and Mars Missions benefitting from project outcomes. The groundwork also is being laid to provide insights into forward looking missions to Gas/Ice Giants as well as for potential sample returns.

Justin Haskins↗

ITO-MgF2 Film Development for PowerSphere Polymer Surface Protection

Multi-kilogram class microsatellites with a PowerSphere electric power system are attractive for fulfilling a variety of potential NASA missions. However, PowerSphere polymer surfaces must be coated with a film that has suitable electrical sheet resistivity for electrostatic discharge control, be resistant to atomic oxygen attack, be transparent to ultraviolet light for composite structure curing and resist ultraviolet light induced darkening for efficient photovoltaic cell operation. In addition, the film must be tolerant of polymer layer folding associated with launch stowage of PowerSphere inflatable structures. An excellent film material candidate to meet these requirements is co-sputtered, indium oxide (In2O3) - tin oxide (SnO2), known as 'ITO', and magnesium fluoride (MgF2). While basic ITO-MgF2 film properties have been the subject of research over the last decade, further research is required in the areas of film durability for space-inflatable applications and precise film property control for large scale commercial production. In this paper, the authors present film durability results for a folded polymer substrate and film resistance to vacuum UV darkening. The authors discuss methods and results in the area of film sheet resistivity measurement and active control, particularly dual-channel, plasma emission line measurement of ITO and MgF2 plasma sources. ITO-MgF2 film polymer coupon preparation is described as well as film deposition equipment, procedures and film characterization. Durability testing methods are also described. The pre- and post-test condition of the films is assessed microscopically and electrically. Results show that an approx. 500A ITO-18vol% MgF2 film is a promising candidate to protect PowerSphere polymer surfaces for Earth orbit missions. Preliminary data also indicate that in situ film measurement methods are promising for active film resistivity control in future large scale production. Future film research plans are also discussed.

Hambourger, Paul D.↗

Operation of Layered LiCoO 2 to Higher Voltages with a Localized Saturated Electrolyte

The commercialization of lithium-ion batteries started with the layered LiCoO 2 (LCO) cathode for portable electronics, but only 50% of its theoretical capacity can be used in practical cells due to detrimental surface and bulk degradations when charged to high voltages. Here we demonstrate here that the stability of electrolyte plays a critical role in the performance of LCO at high voltages by employing a localized saturated electrolyte (LSE). With a cutoff voltage of 4.5 V, LCO achieves an initial 1C discharge capacity of 176 mA h g -1 and a capacity retention of 80% over 230 cycles. Even with a cutoff voltage of 4.6 V, LCO with 2% aluminum doping displays an initial discharge capacity of 189 mA h g -1 at 1C rate with 80% capacity retention over 137 cycles. With extensive analytical characterization, we show that the improved cycling stability stems from a suppression of the O3 to H1-3 phase transition as well as a robust inorganic-rich cathode-electrolyte interphase (CEI) facilitated by the LSE. This work highlights the importance of protecting the surface as well as the bulk with appropriate electrolytes for the high-voltage, higher-energy-density operation of LCO.

25 ENERGY STORAGE↗

In Situ Characterization of Surface Recombination in p-Si/SiO x Based Photoelectrochemical Cells

Time-resolved infrared (TRIR) and electrochemical impedance spectroscopy (EIS) were utilized to quantify surface states present at silicon oxide (SiO x ) protected crystalline p-Si electrolyte interfaces. The primary goal was to identify p-Si/SiO x photoelectrodes with both low surface recombination rates and efficient multi-electron transfer to an acceptor present in the external electrolyte. Three SiO x layers were investigated: native oxide (nOx), chemical oxide (cOx), and rapid thermal annealed (RTA) thermal oxide (tOx). Comparative study with [Ru(bpy) 3 ](PF 6 ) 2 as the electron acceptor indicated that tOx was most optimal with a small effective recombination rate, multi-electron transfer capability, and photovoltage of 500 ± 50 mV. A secondary goal was to analyze the surface recombination rates with the Shockley–Read–Hall (SRH) kinetic model. Two surface states were identified from this analysis, one closer to the CB edge (V t,1 ) and the other near the midgap (V t,2 ). EIS and SRH analyses revealed that a forming gas (5% H 2 /N 2 ) anneal (FGA) decreased surface recombination for tOx and nOx through a lower density of surface states. In the case of tOx, the infrared data indicated that V t,2 was completely removed. Here, the energetic positions of the band edges were correlated with the surface state density; low densities corresponded to more favorable potentials for inversion layer formation, which is expected to be most optimal for photocatalysis. Collectively this study indicates that the free carrier dynamics provided by TRIR represent a powerful in situ probe of the band edge and the surface state energetics in silicon based photoelectrochemical cells.

Electrochemical Impedance Spectroscopy↗