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Final Report on the Detection of Green Monopropellants

In 2014, National Aeronautics and Space Administration (NASA) Kennedy Space Center (KSC) funded a project titled "Familiarization and Detection of Green Monopropellants" utilizing Independent Research and Technology Development (IR&TD) and Center Innovation Fund (CIF) funding. The purpose of the project was to evaluate methods of detection for ammonium dinitramide (ADN) and hydroxylammonium nitrate (HAN). An Engineering Services Contract (ESC) task order was created with the scope of evaluation of several methods of detecting ADN- and HAN-based propellants, as well as development of methods for detection. Detection methods include developed methods such as colorimetric indicating absorbent socks, and commercial-off-the- shelf (COTS) units for ammonia detection. An additional goal of the task order was for ESC to become familiar with ADN's and HAN's material properties and material compatibility. Two approaches were initially investigated as possible methods for the detection of HAN (or AFM315E) and ADN (or LMP-103S). These approaches were colorimetric analysis and instrumentation-based COTS vapor sensors utilization. Initial testing showed that the relatively non-existent vapor pressure of the AF-M315E (of which HAN is a major component) propellant would make the use of COTS sensors difficult for real-time area monitoring of HAN; a small response was detected through the use of active COTS sensors, including the RAE Systems MultiRAE Lite and Drager X-act (registered) 5000, but the levels detected were below the threshold limit value for the toxic gas ammonia. Therefore, a detection system ased upon a colorimetric indicator impregnated into an absorbent material was developed. Preliminary analysis (ESC-245-FDG-001) identified a particularly outstanding candidate as a colorimetric indicator for the detection of the presence of AF-M315E in the form of a Methyl Red (Basic) indicator. Materials impregnated with this indicator exhibit significant color change and the materials are not susceptible to interference from exposure to water or carbon dioxide. The completed detection system for HAN/AF-M315E consists of absorbent socks packed with Fisher Universal Spill Absorbent capable of absorbing and containing any propellant spills that they come into contact with along with indicating wipes. The absorbent socks are also chemically treated with a Methyl Red (Basic) indicator solution to provide the end user with a visual indication that a leak has occurred and proper protective precautions must be undertaken. An added benefit of this detection system is that the absorbent socks should neutralize/absorb any commodity that it comes into contact with (until saturation is reached). Additional adsorbent socks can be deployed until a color change is not seen, indicating that the HAN/AF-M315E contamination has been contained. The indicating wipes provide the user the opportunity to wipe surfaces to determine if there is any HAN/AF-M315E or HAN/AFM315E residue present. The wipes should allow the detection of fuel levels that may be too small to detect with the absorbent socks. The development of a detection system for the ADN/LMP-103S focused on the use of various COTS sensors used as real-time area monitoring devices and personal dosimeters. These COTS based sensor systems were of several different types, including both actively pumped and diffusion-based passive systems, as well as a "rope"-type chemical sensing cable. The results highlighted some of the major differences between the two monopropellants undergoing evaluation. Unlike HAN, ADN (which is the major constituent of LMP-103S) exhibits a much more volatile nature in comparison to AF-M315E. In fact, testing showed that a large percentage of the fuel was lost during the sampling measurement (greater than 10 percent by mass); although this testing cannot tell if the volatile component is the ADN itself or another component of the monopropellant solution. Not surprisingly, all four of the procured vapor-based COTS sensors showed positive results when exposed to solutions of the LMP-103S (ESC-245-FDG-002). The completed detection system for ADN/LMP-103S consists of a combination of two of the tested COTS sensor systems, the RAE Systems MultiRAE Lite and the BW Technologies GasAlert Extreme. These systems are meant to be used in conjunction with one another, which allows for the end-user to have both real-time area monitoring (MultiRAE Lite) as well as a personal dosimeter device (GasAlert Extreme) which can be worn as additional personal protective equipment. An stainless steel extension wand was fabricated and included in the detection system for the MultiRAE Lite to allow for more remote sensing, and connects via the active pumping inlet of the sensor. As stated, the final results of this testing resulted in the production of two "kits" which can be used for the detection of HAN/AF-M315E and ADN/LMP-103s (ESC-245-FDG-003).

Detection↗

Silicon Carbide Nanotube Synthesized

Carbon nanotubes (CNTs) have generated a great deal of scientific and commercial interest because of the countless envisioned applications that stem from their extraordinary materials properties. Included among these properties are high mechanical strength (tensile and modulus), high thermal conductivity, and electrical properties that make different forms of single-walled CNTs either conducting or semiconducting, and therefore, suitable for making ultraminiature, high-performance CNT-based electronics, sensors, and actuators. Among the limitations for CNTs is their inability to survive in high-temperature, harsh-environment applications. Silicon carbon nanotubes (SiCNTs) are being developed for their superior material properties under such conditions. For example, SiC is stable in regards to oxidation in air to temperatures exceeding 1000 C, whereas carbon-based materials are limited to 600 C. The high-temperature stability of SiCNTs is envisioned to enable high-temperature, harsh-environment nanofiber- and nanotube-reinforced ceramics. In addition, single-crystal SiC-based semiconductors are being developed for hightemperature, high-power electronics, and by analogy to CNTs with silicon semiconductors, SiCNTs with single-crystal SiC-based semiconductors may allow high-temperature harsh-environment nanoelectronics, nanosensors, and nanoactuators to be realized. Another challenge in CNT development is the difficulty of chemically modifying the tube walls, which are composed of chemically stable graphene sheets. The chemical substitution of the CNTs walls will be necessary for nanotube self-assembly and biological- and chemical-sensing applications. SiCNTs are expected to have a different multiple-bilayer wall structure, allowing the surface Si atoms to be functionalized readily with molecules that will allow SiCNTs to undergo self-assembly and be compatible with a variety of materials (for biotechnology applications and high-performance fiber-reinforced ceramics).

Lienhard, Michael A.↗

Structural Health System for Crew Habitats

This viewgraph presentation reviews the history of JPL, and its affilation with CalTech and NASA. It continues by examining some of the sensors, and systems to ensure structural health that JPL has developed. It also reviews some of the habitat designs that are being developed for the lunar base. With these crew habitats, there is a requirement to have embedded systems health monitoring, to alert the crew in time about adverse structural conditions. The use of sensing technologies and smart materials are being developed to assure mechanical flexibility, minimumally invasive, autonomous, and enhanced reliability.

self healing↗

Field-Sensitive Materials for Optical Applications

The purpose of investigation is to develop the fundamental materials and fabrication technology for field-controlled spectrally active optics that are essential for industry, NASA, and DOD (Department of Defense) applications such as: membrane optics, filters for LIDARs (Light Detection and Ranging), windows for sensors and probes, telescopes, spectroscopes, cameras, light valves, light switches, flat-panel displays, etc. The proposed idea is based on the quantum-dots (QD) array or thin-film of field-sensitive Stark and Zeeman materials and the bound excitonic state of organic crystals that will offer optical adaptability and reconfigurability. Major tasks are the development of concept demonstration article and test data of field-controlled spectrally smart active optics (FCSAO) for optical multi-functional capabilities on a selected spectral range.

Choi, Sang H.↗

Effect of Rare Earth Elements (Er, Ho) on Semi-Metallic Materials (ScN) in an Applied Electric Field

The development of materials and fabrication technology for field-controlled spectrally active optics is essential for applications such as membrane optics, filters for LIDARs, windows for sensors, telescopes, spectroscopes, cameras and flat-panel displays. The dopants of rare earth elements, in a host of optical systems, create a number of absorption and emission band structures and can easily be incorporated into many high quality crystalline and amorphous hosts. In wide band-gap semiconductors like ScN, the existing deep levels can capture or emit the mobile charges, and can be ionized with the loss or capture of the carriers which are the fundamental basis of concept for smart optic materials. The band gap shrinkage or splitting with dopants supports the possibility of this concept. In the present work, a semi-metallic material (ScN) was doped with rare earth elements (Er, Ho) and tested under an applied electric field to characterize spectral and refractive index shifts by either Stark or Zeeman Effect. These effects can be verified using the UV-Vis spectroscopy, the Hall Effect measurement and the ellipsometric spectroscopy. The optical band gaps of ScN doped with Er and doped with Ho were experimentally estimated as 2.33eV and 2.24eV ( 0.2eV) respectively. This is less than that of undoped ScN (2.5 0.2eV). The red-shifted absorption onset is a direct evidence for the decrease of band gap energy (Eg), and the broadening of valence band states is attributable to the doping cases. A decrease in refractive index with an applied field was observed as a small shift in absorption coefficient using a variable angle spectroscopic ellipsometer. In the presence of an electric field, mobile carriers are redistributed within the space charge region (SCR) to produce this electro-refractive effect. The shift in refractive index is also affected by the density and location of deep potential wells within the SCR. In addition, the microstructure change was observed by a TEM analysis. These results give an insight for future applications for the field-controlled spectrally active material systems.

Kim, Hyunjung↗

Feasibility of using Low-Cost COTS Sensors for Particulate Monitoring in Space Missions

Real-time measurement of particles suspended in the spacecraft cabin is of great importance to verify that maximum allowable dust concentrations are not exceeded. This is primarily to protect astronaut health, but also has implications for dust-sensitive equipment. Recently, there is growing interest in low-cost commercial off-the-shelf (COTS) particle sensors by air quality researchers for their ability to map concentrations of airborne particulate matter in various terrestrial settings. In addition to low cost (< $2,000), the compact size and minimal weight of these sensors make them a potential choice for space missions. The detection mechanism for these aerosol sensors is typically measurement of light scattered by particles as they flow through a sensing volume. The amount of scattered light for detection depends on the particle size, shape, density, and refractive index of the particle material. Ideally, particle instruments should be calibrated with reference instruments for each different type of aerosol measurement. In this study we review multiple parameters that may impact the performance of state-of-the-art low-cost aerosol sensors. Environmental factors such as temperature, relative humidity, low ambient pressure, radiation and charge environment, partial-gravity and microgravity can affect the accuracy of particle measurements. Characteristics of the dust aerosols including particle size distribution, aerosol composition, refractive index, morphology and concentration levels also affect the measurement accuracy. Finally, we look at these parameters and issues with respect to an example COTS low-cost aerosol sensor. Instrument performance specifications are evaluated, and experiments are performed to measure real-time concentrations of Arizona Road Dust (a terrestrial reference test dust) and lunar dust simulant in a laboratory chamber. Overall, this study provides insight for evaluating spacecraft particulate monitoring technologies and raises questions to be answered before incorporating low-cost COTS sensors in future space missions to dusty destinations.

lunar dust↗

Space Environment Stability and Physical Properties of New Materials for Space Power and Commercial Applications

Useful and informative results were obtained on virtually all materials investigated. For example, the stability of ITO-based arc-proof transparent coatings was greatly improved by substitution of silicon oxide for magnesium fluoride as a dopant. Research on 'air-doped' ITO films has yielded new insight into their conduction mechanism which will help in further development of these coatings. Some air-doped films were found to be extremely pressure sensitive. This work may lead to improved, low-cost gas sensors and vacuum gauges. Work on another promising transparent arc-proof coating (titanium oxide) was initiated in collaboration with industry. Graphite oxide-like materials were synthesized and tested for possible use in high energy-density batteries and other applications. We also started a high-priority project to find the cause of unexpected environmental damage to the exterior of the Hubble Space Telescope (HST) discovered on a recent Shuttle mission. Materials were characterized before and after exposure to soft x-rays and other threats in ground-based simulators.

Hambourger, Paul D.↗

An Overview of Experiments and Modeling of Polysiloxane-Coated Thermal Protection Systems for Missions to Mars, Titan, and Beyond.

Phenolic Impregnated Carbon Ablator (PICA) gained heritage during the historic Stardust mission, where it successfully returned samples from a comet’s tail and has since been instrumental in delivering payloads to the surface of Mars [1-3]. Most recently, PICA enabled the safe return of samples collected from asteroid Bennu as part of the OSIRIS-REx mission. This rich legacy underscores PICA’s critical role in allowing NASA’s most ambitious exploration missions. However, the friable nature of its phenolic phase presents challenges during handling and pre-launch activities. To mitigate this issue, PICA is coated with a polysiloxane resin system, which serves to suppress particulate dispersion and thereby safeguard spacecraft components. A comprehensive understanding of the polysiloxane resin’s behavior is imperative, as it profoundly shapes the material response of PICA during atmospheric entry by influencing its thermal and oxidative stability. This influence extends to thermocouple plugs embedded within thermal protection systems. These plugs have demonstrated their significance in missions such as Mars Science Laboratory (MSL) and Mars 2020, where the MEDLI and MEDLI2 instrumentation suites delivered in-valuable insights into the performance of thermal protection systems during entry into the Martian atmosphere [4]. Looking ahead, missions such as Dragonfly, set to descend into Titan’s dense atmosphere, aim to leverage advanced sensor technologies to further refine our understanding of thermal protection response [5]. Moreover, thermocouple plugs play an essential role in validating cutting-edge material response models, such as those pioneered under NASA’s Entry Systems Modeling Project (ESM), designed, in-part, to predict the operational integrity of thermal protection systems under the extreme stresses of atmospheric entry. To achieve these modeling goals, ground-based experiments are crucial to provide the foundational data necessary for developing and refining these predictive tools. To this end, an extensive test campaign was conducted at the Hypersonic Materials Environmental Test System (HyMETS) to investigate the high-temperature behavior of the polysiloxane resin in an air environment [6]. These experiments revealed critical phenomena, including the formation of a silicon oxycarbide layer that enhances oxidation resistance, moderates surface temperatures, and alters in-depth thermal response. Building on these findings, subsequent tests were designed to simulate atmospheric entry conditions in reactive gases, such as CO2 and N2, to mimic the environments of Mars and Titan, respectively, as well as non-reactive gases representing the atmospheres of the Ice Giants (Neptune and Uranus). A heating rate dependent decomposition mechanism has been identified for the polysiloxane resin under oxidizing conditions (Fig. 1). In the initial stage, the resin and the underlying thermal protection system undergo pyrolysis, rapidly generating a thin amorphous silicon oxycarbide interwoven with carbonaceous char and residual fibers from PICA. During the second stage, the nascent oxide layer establishes a robust, oxidation-resistant thermal barrier coating, which significantly impedes heat transfer to the underlying carbonaceous char, resulting in a stagnation of the surface temperature. A key factor contributing to this thermal resistance is the low recombination efficiency of atomic oxygen (γ), which further diminishes the heat load on the material’s interior layers [7]. Moreover, as the surface temperature stagnates, the silicon oxycarbide phase separates into distinct regions of silica and free graphite. Ultimately, when the heat flux reaches a critical threshold, a third stage is triggered, leading to the breakdown of the coating through carbothermal reduction, exposing the underlying char layer. This exposure leads to a dramatic surface temperature spike, driven by highly exothermic reactions between atomic oxygen and the char layer, further accelerating material degradation. A detailed mass and heat transfer model of PICA coated with polysiloxane resin was implemented in the Porous material Analysis Toolbox based on OpenFOAM, PATO [8]. The initial stage was considered negligible in this model because the resin decomposition occurs rapidly within a thin surface layer. Instead, the coating was directly considered as an oxygen-resistant thermal barrier coating. For the second stage, the thin amorphous silicon oxycarbide was treated as a pure silica surface to simplify the thermochemical behavior. The model ac-counts for surface equilibrium processes using representative elements of the coating-environment system. For the third stage, specific boundary conditions were developed to estimate the onset and progression of the coating removal. Two-dimensional material response simulations were conducted to compare uncoated and coated PICA using boundary conditions calibrated with HyMETS data. Fig. 2 illustrates that the simulations closely align with experimental data, successfully reproducing measured temperature profiles. This work will include the latest advancements in the coating model, including the calibration of recombination of atomic oxygen at the surface during the second phase. These simulated results will be further validated against additional CO2 data points from HyMETS, reinforcing the models’ predictive capabilities. These mechanisms and their effects on thermal protection systems, including thermochemical behavior and thermocouple probe performance in extreme environments, provide crucial insights for optimizing spacecraft designs that safeguard scientific payload and ensure mission success in future planetary exploration endeavors.

Active Oxidation↗

Demonstration of a Fiber Optic Regression Probe

The capability to provide localized, real-time monitoring of material regression rates in various applications has the potential to provide a new stream of data for development testing of various components and systems, as well as serving as a monitoring tool in flight applications. These applications include, but are not limited to, the regression of a combusting solid fuel surface, the ablation of the throat in a chemical rocket or the heat shield of an aeroshell, and the monitoring of erosion in long-life plasma thrusters. The rate of regression in the first application is very fast, while the second and third are increasingly slower. A recent fundamental sensor development effort has led to a novel regression, erosion, and ablation sensor technology (REAST). The REAST sensor allows for measurement of real-time surface erosion rates at a discrete surface location. The sensor is optical, using two different, co-located fiber-optics to perform the regression measurement. The disparate optical transmission properties of the two fiber-optics makes it possible to measure the regression rate by monitoring the relative light attenuation through the fibers. As the fibers regress along with the parent material in which they are embedded, the relative light intensities through the two fibers changes, providing a measure of the regression rate. The optical nature of the system makes it relatively easy to use in a variety of harsh, high temperature environments, and it is also unaffected by the presence of electric and magnetic fields. In addition, the sensor could be used to perform optical spectroscopy on the light emitted by a process and collected by fibers, giving localized measurements of various properties. The capability to perform an in-situ measurement of material regression rates is useful in addressing a variety of physical issues in various applications. An in-situ measurement allows for real-time data regarding the erosion rates, providing a quick method for empirically anchoring any analysis geared towards lifetime qualification. Erosion rate data over an operating envelope could also be useful in the modeling detailed physical processes. The sensor has been embedded in many regressing media for the purposes of proof-of-concept testing. A gross demonstration of its capabilities was performed using a sanding wheel to remove layers of metal. A longer-term demonstration measurement involved the placement of the sensor in a brake pad, monitoring the removal of pad material associated with the normal wear-and-tear of driving. It was used to measure the regression rates of the combustable media in small model rocket motors and road flares. Finally, a test was performed using a sand blaster to remove small amounts of material at a time. This test was aimed at demonstrating the unit's present resolution, and is compared with laser profilometry data obtained simultaneously. At the lowest resolution levels, this unit should be useful in locally quantifying the erosion rates of the channel walls in plasma thrusters. .

Korman, Valentin↗

Imaging spectrometry for earth remote sensing

Initial results of the novel remote earth sensing technique of imaging spectrometry, which is technically feasible from both spacecraft and aircraft platforms, indicate that the direct identification of surface materials on a picture-element basis is possible through proper sampling of absorption features in the reflectance spectrum. Sensors of this type are able to acquire images simultaneously in 100-200 contiguous spectral bands. Computerized data reduction and storage techniques are available for the large data sets thus generated, and novel analytic techniques are under development to maximize information content extraction.

Goetz, A. F. H.↗

Measurement of the light flux density patterns from luminaires proposed as photon sources for photosynthesis during space travel

Two luminaires were evaluated to determine the light flux density pattern on a horizontal plane surface. NASA supplied both luminaires; one was made by NASA and the other is commercially available. Tests were made for three combinations of luminaire height and luminaire lens material using the NASA luminaire; only one configuration of the commercial luminaire was tested. Measurements were made using four sensors with different wavelength range capabilities. The data are presented in graphical and tabular formats.

Walker, Paul N.↗

Postflight aerothermodynamic analysis of Pegasus(tm) using computational fluid dynamic techniques

The objective was to validate the computational capability of the NASA Ames Navier-Stokes code, F3D, for flows at high Mach numbers using comparison flight test data from the Pegasus (tm) air launched, winged space booster. Comparisons were made with temperature and heat fluxes estimated from measurements on the wing surfaces and wing-fuselage fairings. Tests were conducted for solution convergence, sensitivity to grid density, and effects of distributing grid points to provide high density near temperature and heat flux sensors. The measured temperatures were from sensors embedded in the ablating thermal protection system. Surface heat fluxes were from plugs fabricated of highly insulative, nonablating material, and mounted level with the surface of the surrounding ablative material. As a preflight design tool, the F3D code produces accurate predictions of heat transfer and other aerodynamic properties, and it can provide detailed data for assessment of boundary layer separation, shock waves, and vortex formation. As a postflight analysis tool, the code provides a way to clarify and interpret the measured results.

Kuhn, Gary D.↗

Infrared technology XVII; Proceedings of the Meeting, San Diego, CA, July 22-26, 1991

Recent advances in IR technologies and their application to all types of IR systems are reported focusing on the JPL Space Infrared Telescope Facility (SIRTF), JPL instruments and systems for observation of earth and the atmosphere, staring arrays and thermal imaging, ten-year updates of IR techniques, infrared in the USSR, simulation and testing, focal-plane and optical technologies, and military and scientific applications. Particular attention is given to SIRTF stray light analysis, SIRTF focal-plane technologies, long-wave IR detectors based on III-V materials, IR lidars for atmospheric remote sensing, a firefly system concept, a high-fill-factor monolithic IR image sensor, atmospheric laser-transmission tables simply generated, ORION semiconductor optical detectors, postprocessing of thermograms in IR nondestructive testing, evaluation of the IR signature of dynamic air targets, the current status of InGaAs detector arrays for 1-3 microns, a dual-band optical system for IR multicolor signal processing, and blackbody radiators for field calibration.

Andresen, Bjorn F.↗

Microbial biofilm formation and its consequences for the CELSS program

A major goal of the Controlled Ecology Life Support System (CELSS) program is to provide reliable and efficient life support systems for long-duration space flights. A principal focus of the program is on the growth of higher plants in growth chambers. These crops should be grown without the risk of damage from microbial contamination. While it is unlikely that plant pathogens will pose a risk, there are serious hazards associated with microorganisms carried in the nutrient delivery systems and in the atmosphere of the growth chamber. Our experience in surface microbiology showed that colonization of surfaces with microorganisms is extremely rapid even when the inoculum is small. After initial colonization extensive biofilms accumulate on moist surfaces. These microbial films metabolize actively and slough off continuously to the air and water. During plant growth in the CELSS program, microbial biofilms have the potential to foul sensors and to plug nutrient delivery systems. In addition both metabolic products of microbial growth and degradation products of materials being considered for use as nutrient reservoirs and for delivery are likely sources of chemicals known to adversly affect plant growth.

Mitchell, R.↗

Research and Development Annual Report, 1992

Issued as a companion to Johnson Space Center's Research and Technology Annual Report, which reports JSC accomplishments under NASA Research and Technology Operating Plan (RTOP) funding, this report describes 42 additional JSC projects that are funded through sources other than the RTOP. Emerging technologies in four major disciplines are summarized: space systems technology, medical and life sciences, mission operations, and computer systems. Although these projects focus on support of human spacecraft design, development, and safety, most have wide civil and commercial applications in areas such as advanced materials, superconductors, advanced semiconductors, digital imaging, high density data storage, high performance computers, optoelectronics, artificial intelligence, robotics and automation, sensors, biotechnology, medical devices and diagnosis, and human factors engineering.

Source record↗

The JSC Research and Development Annual Report 1993

Issued as a companion to Johnson Space Center's Research and Technology Annual Report, which reports JSC accomplishments under NASA Research and Technology Operating Plan (RTOP) funding, this report describes 47 additional projects that are funded through sources other than the RTOP. Emerging technologies in four major disciplines are summarized: space systems technology, medical and life sciences, mission operations, and computer systems. Although these projects focus on support of human spacecraft design, development, and safety, most have wide civil and commercial applications in areas such as advanced materials, superconductors, advanced semiconductors, digital imaging, high density data storage, high performance computers, optoelectronics, artificial intelligence, robotics and automation, sensors, biotechnology, medical devices and diagnosis, and human factors engineering.

Source record↗

Apparatus Tests Peeling Of Bonded Rubbery Material

Instrumented hydraulic constrained blister-peel apparatus obtains data on degree of bonding between specimen of rubbery material and rigid plate. Growth of blister tracked by video camera, digital clock, pressure transducer, and piston-displacement sensor. Cylinder pressure controlled by hydraulic actuator system. Linear variable-differential transformer (LVDT) and float provide second, independent measure of change in blister volume used as more precise volume feedback in low-growth-rate test.

Crook, Russell A.↗

In-situ Frequency Dependent Dielectric Sensing of Cure

With the expanding use of polymeric materials as composite matrices, adhesives, coatings and films, the need to develop low cost, automated fabrication processes to produce consistently high quality parts is critical. Essential to the development of reliable, automated, intelligent processing is the ability to continuously monitor the changing state of the polymeric resin in-situ in the fabrication tool. This final report discusses work done on developing dielectric sensing to monitor polymeric material cure and which provides a fundamental understanding of the underlying science for the use of frequency dependent dielectri sensors to monitor the cure process.

Kranbuehl, David E.↗