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List of Commercial and Advanced Developmental Niobium-Based Alloys of the Space Age

This report compiles a list of commercial and developmental niobium-based alloys developed during the Space Age (late 1950s through mid-1970s) for extreme-temperature applications, including rocket engine thrust chambers, hypersonic re-entry thermal protection systems, and space fission reactor loops. Niobium (Nb) was widely pursued because it provided the lowest density (~8.6 g/cc) among the primary refractory metals, a high melting temperature (~2470°C), exceptional low-temperature ductility, good formability, and compatibility with liquid alkali metals. An evaluation of physical metallurgy mechanisms, focusing on solid-solution strengthening via heavy refractory solutes (W, Mo, Ta), dual-purpose reactive solutes (Hf, Zr, Ti), and dispersion strengthening using carbides, nitrides, and oxides is presented. Additionally, the report compares Western and Soviet Union metallurgical approaches, explaining how supply chain factors and manufacturing infrastructure influenced element selection, interstitial chemistry, and alloy identification/naming conventions. Cataloging these historical alloy chemical compositions serves as a foundational reference for modern alloy additive manufacturing, thermodynamic CALPHAD modeling, and machine-learning discovery pipelines for next-generation extreme-environment niobium-based alloys.

Physical Metallurgy

Discrete Rotational Energy for Polyatomic Molecules in Direct Simulation Monte Carlo

The environments experienced by vehicles upon entry into planetary atmospheres generally result in severe aerothermodynamic loading. These flows are characterized by the formation of strong shock waves, behind which high temperatures and non-equilibrium environments are generated, and the accurate prediction of internal energy relaxation and chemical kinetics becomes important. This manuscript focuses on the internal relaxation of the rotational energy of polyatomic molecules. Previous work has described the implementation of a discrete rotational energy model for diatomic molecules (linear rotators). Later, Gimelshein et. al extended this model to include polyatomic molecular internal energies. However, they did not include details on how to generate the particles at equilibrium conditions and centrifugal distortion was not included in their model. The purpose of the present study is to extend the afore-mentioned models to the treatment of discrete rotational energy in polyatomic molecules with the addition of centrifugal distortion. An overview of the background theory needed for the implementation of the model will be given followed by the model itself and verification of the model. For example, sampled versus Boltzmann distributions are compared in Figure 1 for CH3 (oblate rotator – two quantum numbers) and examples of thermal relaxation behavior for linear and non-linear rotators are presented in Figure 2. In addition, comparisons of thermophysical properties will be presented, as well as examples of adiabatic relaxation and application to hypersonic flow.

Rarefied Gas Dynamics

Topographic effects on reflected acoustic waves from the OSIRIS-REx reentry observed from stratospheric balloons

During long-distance sound propagation in planetary atmospheres, acoustic waves may reflect off the air/surface interface one or more times. For low sound frequencies and flat interfaces, the incident and reflected wave tend to be nearly identical. However, this may not be the case when the downgoing acoustic wave encounters topography. Here, we describe a set of direct and reflected acoustic signals recorded on free-flying balloons during the hypersonic entry of the OSIRIS-REx sample return capsule (SRC). In two of the three cases presented here, an impulsive reflected arrival similar in form to the direct sonic boom of the SRC is observed, followed by a diffuse coda. In contrast, one of the floating stations lacked an impulsive reflection entirely, with only the coda present. We use full waveform modeling to show how reflection in the presence of complex topography can explain coda seen in all three examples as well as the lack of impulsive arrival on the third. Our results indicate that the complex signals often observed in long range acoustic propagation could be due, in part, to interactions with topography during transmission.

Lees, Jonathan M. [University of North Carolina, C

Thermo-Poro-Mechanical Modeling of RTV Intumescence

Room temperature vulcanizing (RTV) silicone is a high-temperature adhesive used as a gap-filler between heatshield tiles in numerous entry missions. Its propensity to intumesce, or swell upon exposure to heat, is a well-known effect that needs to be carefully quantified during design. At tile interfaces of charring ablators, intumescence, combined with differential recession, could cause the gap filler to protrude past the ablator outer mold line, forming a “fence”. Fencing can in turn cause transition to turbulence of the flow wetting the heat shield, leading to augmented surface heating. Recent experiments conducted at the Plasmatron X facility, the high enthalpy wind tunnel of the Center for Hypersonics and Entry Systems Studies, have shown prominent fencing of RTV gap fillers in PICA, under both nitrogen and air plasmas. Similar observations are well known in the arcjet literature. Further experiments under controlled environment, performed using in situ X-ray micro-computed tomography (micro-CT) at the Advanced Light Source (ALS), have shown heating rate-dependent swelling and shrinkage of RTV during pyrolysis. To simulate RTV intumescence, a novel model was introduced in the Porous Materials Analysis Toolbox based on OpenFOAM, PATO, to account for pore-pressure buildup within both closed- and open-pores. The governing equation for the thermo-poro-mechanical response were developed, assuming linear elasticity for the charring silicone. A new multi-pyrolysis model that tracks non-monotonic advancement of material properties with pyrolysis was proposed. This model addresses the limitations of state-of-the-art ablator models to capture the different stages of thermal degradation and coupled thermomechanics. Swelling of RTV was simulated using the new thermo-poro-mechanical model and compared against in situ micro-CT data. Results showed good agreement in intumescence height and temperature profiles at all heating rates, indicating that the key factor contributing to RTV swelling is the internal pressure build-up within closed- and open-pores. As RTV is cured into a soft (rubbery) compound with low-porosity and permeability, initial temperature increase and pyrolysis gas production cause a significant increase of internal pressure, causing a pronounced volume growth. As thermal degradation progresses, rigidization of the silicone occurs due to char hardening which counteract volume shrinkage after gas pressure relief. Overall, our model shows that accounting for changes in properties such porosity, permeability and key thermomechanical coefficients is crucial for capturing the RTV volume change during ablation and enable a predictive capability for heatshield tile interface response. A plan for future calibration of thermomechanical properties evolution during degradation is discussed, as a key next step to close the new model.

RTV

Thermo-Poro-Mechanical Modeling of RTV Intumescence

Room temperature vulcanizing (RTV) silicone is a high-temperature adhesive used as a gap-filler between heatshield tiles in numerous entry missions. Its propensity to intumesce, or swell upon exposure to heat, is a well-known effect that needs to be carefully quantified during design. At tile interfaces of charring ablators, intumescence, combined with differential recession, could cause the gap filler to protrude past the ablator outer mold line, forming a “fence”. Fencing can in turn cause transition to turbulence of the flow wetting the heat shield, leading to augmented surface heating. Recent experiments conducted at the Plasmatron X facility, the high enthalpy wind tunnel of the Center for Hypersonics and Entry Systems Studies, have shown prominent fencing of RTV gap fillers in PICA, under both nitrogen and air plasmas. Similar observations are well known in the arcjet literature. Further experiments under controlled environment, performed using in situ X-ray micro-computed tomography (micro-CT) at the Advanced Light Source (ALS), have shown heating rate-dependent swelling and shrinkage of RTV during pyrolysis. To simulate RTV intumescence, a novel model was introduced in the Porous Materials Analysis Toolbox based on OpenFOAM, PATO, to account for pore-pressure buildup within both closed- and open-pores. The governing equation for the thermo-poro-mechanical response were developed, assuming linear elasticity for the charring silicone. A new multi-pyrolysis model that tracks non-monotonic advancement of material properties with pyrolysis was proposed. This model addresses the limitations of state-of-the-art ablator models to capture the different stages of thermal degradation and coupled thermomechanics. Swelling of RTV was simulated using the new thermo-poro-mechanical model and compared against in situ micro-CT data. Results showed good agreement in intumescence height and temperature profiles at all heating rates, indicating that the key factor contributing to RTV swelling is the internal pressure build-up within closed- and open-pores. As RTV is cured into a soft (rubbery) compound with low-porosity and permeability, initial temperature increase and pyrolysis gas production cause a significant increase of internal pressure, causing a pronounced volume growth. As thermal degradation progresses, rigidization of the silicone occurs due to char hardening which counteract volume shrinkage after gas pressure relief. Overall, our model shows that accounting for changes in properties such porosity, permeability and key thermomechanical coefficients is crucial for capturing the RTV volume change during ablation and enable a predictive capability for heatshield tile interface response. A plan for future calibration of thermomechanical properties evolution during degradation is discussed, as a key next step to close the new model.

silicone intumescence

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