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Thermal and Mechanical Durability of Graphite-Fiber-Reinforced PMR-15 Composites

Earlier work, which reported relationships between compression properties and elevated temperature aging times and weight losses, also pointed out the apparent influence of surface layer formation and growth on the retention of compression properties during extended aging times. Since that time, studies have been directed toward evaluating the growth of the surface layer. This layer was found to change in its composition and features as the aging temperature changed. Microcracks and small voids initiated and advanced inward at all temperatures. Visible oxidation at the surface occurred only at temperatures above 260 C. Relationships between layer thickness and aging time and temperature were evaluated and empirically formulated. Then, the compression properties were graphically related to the surface layer thickness with excellent correlation. The surface layer was observed to influence the compression strength of thin samples only.

Bowles, Kenneth J.↗

Thermal and Mechanical Durability of Graphite-Fiber-Reinforced PMR-15 Composites

Earlier work, which reported relationships between compression properties and elevated temperature aging times and weight losses, also pointed out the apparent influence of surface layer formation and growth on the retention of compression properties during extended aging times. Since that time, studies have been directed toward evaluating the growth of the surface layer. This layer was found to change in its composition and features as the aging temperature changed. Microcracks and small voids initiated and advanced inward at all temperatures. Visible oxidation at the surface occurred only at temperatures above 260 deg. C. Relationships between layer thickness and aging time and temperature were evaluated and empirically formulated. Then, the compression properties were graphically related to the surface layer thickness with excellent correlation. The surface layer was observed to influence the compression strength of thin samples only.

Bowles, Kenneth J.↗

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↗

The Role of Cu Species in the Regeneration of a Coked Cu/BEA Zeolite Catalyst

Active site occlusion by carbon species, often referred to as coke, is a common deactivation mechanism for heterogeneous catalysts. While it is known that transition metals can lower the temperature required for oxidative coke removal, the roles of ionic species and metal nanoparticles in coke removal are not well understood. This work aims to differentiate how ionic and nanoparticle Cu sites catalyze oxidative regeneration of a coked beta (BEA) zeolite catalyst. This was accomplished by synthesizing catalysts containing exclusively CuOx nanoparticles (NPs) or Cu2+ ions supported on BEA, physically mixing Cu/BEA with a coked BEA catalyst, and monitoring coke removal using in situ spectroscopy. Our results point to an improved combustion activity for CuOx NPs relative to Cu2+ ions, especially in the combustion of graphitic-type coke species. This improved understanding of coke combustion in transition metal containing catalysts informs strategies to improve catalyst regeneration, thereby increasing operational lifetimes.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

Reinforced Carbon Carbon (RCC) oxidation resistant material samples - Baseline coated, and baseline coated with tetraethyl orthosilicate (TEOS) impregnation

Reinforced carbon-carbon material specimens were machined from 19 and 33 ply flat panels which were fabricated and processed in accordance with the specifications and procedures accepted for the fabrication and processing of the leading edge structural subsystem (LESS) elements for the space shuttle orbiter. The specimens were then baseline coated and tetraethyl orthosilicate impregnated, as applicable, in accordance with the procedures and requirements of the appropriate LESS production specifications. Three heater bars were ATJ graphite silicon carbide coated with the Vought 'pack cementation' coating process, and three were stackpole grade 2020 graphite silicon carbide coated with the chemical vapor deposition process utilized by Vought in coating the LESS shell development program entry heater elements. Nondestructive test results are reported.

Gantz, E. E.↗

Static evaluation of surface coatings for compliant gas bearings in an oxidizing atmosphere to 650 C

Hard wear-resistant coatings and soft low shear strength coatings were developed for an air-lubricated compliant journal bearing for a future automotive gas turbine engine. The coatings were expected to function in either 540 or 650 C ambient. Soft lubricant coatings were generally limited in temperature. Therefore emphasis was on the hard wear-resistant coatings. The coating materials covered were TiC, B4C, Cr3C2, WC, SiC, CrB2, TiB2, Cr2O3, Al2O3, Si3N4, Tribaloy 800, CaF2, CaF2-BaF2 eutectic, Ni-Co, silver, CdO-graphite and proprietary compounds. The coatings on test coupons were subjected to static oven screening tests. The test consisted of exposure of material samples in an oven for 300 h at the maximum temperature (540 or 650 C) and ten temperature cycles from room temperature to the maximum service temperature. On the basis of the specimen examinations the following coatings were recommended for future wear tests: TiC (sputtered), Cr2O3 (sputtered), Si3N4 (sputtered), CdO and graphite (fused), Kaman DES (a proprietary coating), CrB2 (plasma sprayed), Cr3C2 (detonation gun) and NASA PS-106 (plasma sprayed).

Bhushan, B.↗

LSA Large Area Silicon Sheet Task Continuous Czochralski Process Development

A commercial Czochralski crystal growing furnace was converted to a continuous growth facility by installation of a small, in-situ premelter with attendant silicon storage and transport mechanisms. Using a vertical, cylindrical graphite heater containing a small fused quartz test tube linear from which the molten silicon flowed out the bottom, approximately 83 cm of nominal 5 cm diamter crystal was grown with continuous melt addition furnished by the test tube premelter. High perfection crystal was not obtained, however, due primarily to particulate contamination of the melt. A major contributor to the particulate problem was severe silicon oxide buildup on the premelter which would ultimately drop into the primary melt. Elimination of this oxide buildup will require extensive study and experimentation and the ultimate success of continuous Czochralski depends on a successful solution to this problem. Economically, the continuous Czochralski meets near-term cost goals for silicon sheet material.

Rea, S. N.↗

Graphite/PMR polyimide composites with improved toughness

The toughness of composites made with modified PMR (polymerization of monomer reactants) polyimides and Celion 6000 graphite fibers was studied. Various types/levels of monomer reactants containing flexible links were incorporated into PMR resin compositions used to prepare composites. The composites were evaluated for toughness using instrumented drop weight and 10 deg off axis tensile tests at room temperature, and for strength using flexure and short beam shear tests at room temperature and at elevated temperature. The effect of resin composition on composite processability, thermo-oxidative stability, toughness and mechanical properties are discussed.

Vannucci, R. D.↗

Graphite/PMR polyimide composites with improved toughness

The toughness of composites made with modified PMR (Polymerization of monomer reactants) polyimides and Celion 6000 graphite fibers was studied. Various types/levels of monomer reactants containing flexible links were incorporated into PMR resin compositions used to prepare composites. The composites were evaluated for toughness using instrumented drop weight and 10 deg off axis tensile tests at room temperature, and for strength using flexure and short beam shear tests at room temperature and at elevated temperature. The effect of resin composition on composite processability, thermo-oxidative stability, toughness and mechanical properties are discussed.

Vannucci, R. D.↗

Graphite/polyimide composites with improved toughness

Studies were performed to determine the toughness characteristics of composites prepared from modified addition-type polyimides, using Celion 6000 graphite fiber as the reinforcement. The polyimides were prepared from aromatic diamines containing flexibilizing ether connecting groups. The composite flexural and short beam shear strengths were determined at room temperature and elevated temperatures. Composite toughness was evaluated using 10 deg off axis tensile tests and double cantilever beam fracture tests at room temperature. The effects of the flexibilized resin structure on composite mechanical properties, toughness characteristics, and thermo-oxidative stability are discussed.

Delvigs, Peter↗

Carbon Nanotube Nanoelectrode Array as an Electronic Chip for Ultrasensitive Label-free DNA Detection

A reliable nanoelectrode array based on vertically aligned multi-walled carbon nanotubes (MWNTs) embedded in SiO2 is used for ultrasensitive DNA detection. Characteristic nanoelectrode behavior is observed using low-density MWNT arrays for measuring both bulk and surface immobilized redox species such as K4Fe(CN)6 and ferrocene derivatives. The open-end of MWNTs are found to present similar properties as graphite edge-plane electrodes with wide potential window, flexible chemical functionalities, and good biocompatibility. BRCA1 related oligonucleotide probes with 18 bp are selectively functionalized at the open ends of the nanotube array and specifically hybridized with oligonucleotide targets incorporated with a polyG tag. The guanine groups are employed as the signal moieties in the electrochemical measurements. R(bpy)(sup 2+, sub 3) mediator is used to further amplify the guanine oxidation signal. The hybridization of sub-attomoles of DNA targets is detected electrochemically by combining the MWNT nanoelectrode array with the R(bpy)(sup 2+, sub 3) amplification mechanism. This technique was employed for direct electrochemical detection of label-free PCR amplicon from a healthy donor through specific hybridization with the BRCA1 probe. The detection limit is estimated to be less than 1000 DNA molecules since abundant guanine bases in the PCR amplicon provides a large signal. This system provides a general platform for rapid molecular diagnostics in applications requiring ultrahigh sensitivity, high-degree of miniaturization, and simple sample preparation, and low-cost operation.

Li, Jun↗

Study of Graphite Ablation at Arc-Jet Conditions using Finite-Rate and Equilibrium Chemistry Models

Moving at hypersonic speeds through the atmosphere generates immense amount of heat that triggers thermo-chemical non-equilibrium effects in the flow approaching the vehicle and leads to surface chemical reactions that cause ablation and consume the material mass. This complex behavior and interaction of the aerothermal environment with a graphite surface is com- putationally modeled in the present work using a fully-coupled simulation between flow solver CHAMPS NBS-Cart and material response solver KATS-MR. In this study, we account for the thermo-chemical non-equilibrium effects occurring in the flow and use an 11-species air-carbon re- action model to simulate the ablation of the material. The reactions at the surface such oxidation, nitridation and recombination are modeled with a newly developed air-carbon reaction model. The coupled simulation is applied to study two experimental cases performed at IHF arc-jet facility at NASA Ames research center. The obtained results are compared against the measured data of surface recession, as well as surface and in-depth temperatures. Additionally, uncoupled sim- ulations, performed with equilibrium chemistry at the wall, point out the substantial differences between the coupled and uncoupled solutions, leading to higher deviation of the predicted temper- atures. Overall, we show excellent agreement between the coupled simulation predictions and the experimental data in all measured quantities.

EDL↗

Carbon Nanotube Bonding Strength Enhancement Using Metal "Wicking" Process

Carbon nanotubes grown from a surface typically have poor bonding strength at the interface. A process has been developed for adding a metal coat to the surface of carbon nano tubes (CNTs) through a wicking process, which could lead to an enhanced bonding strength at the interface. This process involves merging CNTs with indium as a bump-bonding enhancement. Classical capillary theory would not normally allow materials that do not wet carbon or graphite to be drawn into the spacings by capillary action because the contact angle is greater than 90 degrees. However, capillary action can be induced through JPL's ability to fabricate oriented CNT bundles to desired spacings, and through the use of deposition techniques and temperature to control the size and mobility of the liquid metal streams and associated reservoirs. A reflow and plasma cleaning process has also been developed and demonstrated to remove indium oxide, and to obtain smooth coatings on the CNT bundles.

Lamb, James L.↗

The 371 deg C mechanical properties of graphite/polyimide composites

A series of condensation polyimides based on pyromellitic dianhydride is synthesized and evaluated for potential application at 371 C. Several three-and four-ring benzenoid diamine systems containing oxygen bridging groups are investigated. Thermomechanical analysis of neat resin specimens indicate that the polyimide prepared from the dimethyl ester of pyrometallitic acid (PMDE) and 2,2-bis4-(4'-aminophenoxy) phenyl]-1,1,1,3,3,3- hexafluoropropane (BDAF) is the only resin system which has a glass transition temperature (Tg) above 371 C. The Tg of the PMDE/BDAF polyimide is found to be 390 C after a postcure air at 371 C for 24 hr. Unidirectional composites are fabricated from the PMDE/BDAF system and unsized Celion 6000 graphite fibers. Final cure temperatures in the range of 371 to 427 C with an applied pressure of 10.34 to 13.78 MPa are investigated. The void content of the composites ranges from 4.6 to 8.6 percent. Composites cured at 399 C under a pressure of 10.34 MPa and postcured in air at 371 C for 24 hr exhibit the highest 371 C interlaminar shear strength (ILSS, 40.7 MPa) and flexural strength (758 MPa). The thermo-oxidative stability of the composites is determined by subjecting specimens to isothermal exposure at 371 C in air at atmospheric pressure, as well as a pressure of 0.52 MPa. Specimens exposed at atmospheric pressure exhibit a weight loss of 12 percent after 200 hr of exposure and 88 percent retention of its original 371 C ILSS. In contrast, the specimens exposed at 0.52 MPa pressure exhibit a comparable weight loss after only 72 hr, and a 71 percent retention of its original 371 C ILSS.

Delvigs, P.↗

Ultrasensitive Label-free Electronic Chip for DNA Analysis Using Carbon Nanotube Nanoelectrode Arrays

There is a strong need for faster, cheaper, and simpler methods for nucleic acid analysis in today s clinical tests. Nanotechnologies can potentially provide solutions to these requirements by integrating nanomaterials with biofunctionalities. Dramatic improvement in the sensitivity and multiplexing can be achieved through the high-degree miniaturization. Here, we present our study in the development of an ultrasensitive label-free electronic chip for DNA/RNA analysis based on carbon nanotube nanoelectrode arrays. A reliable nanoelectrode array based on vertically aligned multi-walled carbon nanotubes (MWNTs) embedded in a SiO2 matrix is fabricated using a bottom-up approach. Characteristic nanoelectrode behavior is observed with a low-density MWNT nanoelectrode array in measuring both the bulk and surface immobilized redox species. The open-end of MWNTs are found to present similar properties as graphite edge-plane electrodes, with a wide potential window, flexible chemical functionalities, and good biocompatibility. A BRCA1 related oligonucleotide probe with 18 bases is covalently functionalized at the open ends of the MWNTs and specifically hybridized with an oligonucleotide target as well as a PCR amplicon. The guanine bases in the target molecules are employed as the signal moieties for the electrochemical measurements. Ru(bpy)3(2+) mediator is used to further amplify the guanine oxidation signal. This technique has been employed for direct electrochemical detection of label-free PCR amplicon through specific hybridization with the BRCAl probe. The detection limit is estimated to be less than approximately 1000 DNA molecules, approaching the limit of the sensitivity by laser-based fluorescence techniques in DNA microarray. This system provides a general electronic platform for rapid molecular diagnostics in applications requiring ultrahigh sensitivity, high-degree of miniaturization, simple sample preparation, and low- cost operation.

Li, Jun↗

Methodology of Atomic Force Microscopy Visualization of Electrode–Electrolyte Interfaces

Electrochemical atomic force microscopy (EC-AFM) provides unprecedented insights into the microstructure of electrode–electrolyte interfaces during electrochemical reactions. However, performing EC-AFM measurements has many challenges, for example, drift, contamination, and probe degradation. We present solutions to these experimental issues through electrochemical cell design and carefully chosen experimental parameters. The possibility that the probes can react with the interface during scanning, generating false-positive electrochemical dynamics, is discussed as an example of the challenge of high-fidelity EC-AFM measurement. Here, we demonstrate this effect in highly ordered pyrolytic graphite and show that we could use electrochemical control of the AFM probe to enable high-fidelity in situ AFM visualization of solid–liquid interfaces during electrochemical reactions.

Electrochemical cells↗

Solidification of eutectic system alloys in space (M-19)

It is well known that in the liquid state eutectic alloys are theoretically homogeneous under 1 g conditions. However, the homogeneous solidified structure of this alloy is not obtained because thermal convection and non-equilibrium solidification occur. The present investigators have clarified the solidification mechanisms of the eutectic system alloys under 1 g conditions by using the in situ observation method; in particular, the primary crystals of the eutectic system alloys never nucleated in the liquid, but instead did so on the mold wall, and the crystals separated from the mold wall by fluid motion caused by thermal convection. They also found that the equiaxed eutectic grains (eutectic cells) are formed on the primary crystals. In this case, the leading phase of the eutectic must agree with the phase of the primary crystals. In space, no thermal convection occurs so that primary crystals should not move from the mold wall and should not appear inside the solidified structure. Therefore no equiaxed eutectic grains will be formed under microgravity conditions. Past space experiments concerning eutectic alloys were classified into two types of experiments: one with respect to the solidification mechanisms of the eutectic alloys and the other to the unidirectional solidification of this alloy. The former type of experiment has the problem that the solidified structures between microgravity and 1 g conditions show little difference. This is why the flight samples were prepared by the ordinary cast techniques on Earth. Therefore it is impossible to ascertain whether or not the nucleation and growth of primary crystals in the melt occur and if primary crystals influence the formation of the equiaxed eutectic grains. In this experiment, hypo- and hyper-eutectic aluminum copper alloys which are near eutectic point are used. The chemical compositions of the samples are Al-32.4mass%Cu (Hypo-eutectic) and Al-33.5mass%Cu (hyper-eutectic). Long rods for the samples are cast by the Ohno Continuous Casting Process and they show the unidirectionally solidified structure. Each flight and ground sample was made of these same rods. The dimensions of all samples are 4.5 mm in diameter and 23.5 mm in length. Each sample is put in a graphite capsule and then vacuum sealed in a double silica ampoule. Then the ampoule is put in the tantalum cartridge and sealed by electron beam welding. For onbard experiments, a Continuous Heating Furnance (CHF) will be used for melting and solidifying samples under microgravity conditions. Six flight samples will be used. Four samples are hypo-eutectic and two are hyper-eutectic alloys. The surface of the two hypo-eutectic alloy samples are covered with aluminum oxide film to prevent Marangoni convection expected under microgravity conditions. Each sample will be heated to 700 C and held at that temperature for 5 min. After that the samples will be allowed to cool to 500 C in the furnace and they will be taken out of the furnace for He gas cooling. The heating and cooling diagrams for the flight experiments are shown. After collecting the flight samples, the solidified structures of the samples will be examined and the mechanisms of eutectic solidification under microgravity conditions will be determined. It is likely that successful flight experiment results will lead to production of high quality eutectic alloys and eutectic composite materials in space.

Ohno, Atsumi↗

Magnetic properties of iron-bearing graphite fibers

Carbon fibers containing ferromagnetically-ordered iron or other transition metals could be used in a variety of lightweight magnetic composites. Intercalation of bulk graphite with CoCl2 or FeCl3, followed by reduction with butyl lithium, did indeed produce magnetic samples; however, the observed room temperature permeabilities (mu) were less than 2 G/Oe. Magnetic data are presented on carbon fibers containing large amounts of elemental iron, which were prepared by a new method. In this method Amoco P-75 fibers were intercalated with Br2 and I2 followed by fluorination, forming CF(0.75). This product was then intercalated with FeCl3. Subsequent heat treatments in oxidizing and reducing atmospheres converted most of the iron to the pure alpha phase. Room temperature permeabilities as large as 40 G/Oe are observed.

Ferrante, R.↗