Results for “surface complexation” — Page 45

NASA NTRS1996

Spray Combustion Modeling with VOF and Finite-Rate Chemistry

A spray atomization and combustion model is developed based on the volume-of-fluid (VOF) transport equation with finite-rate chemistry model. The gas-liquid interface mass, momentum and energy conservation laws are modeled by continuum surface force mechanisms. A new solution method is developed such that the present VOF model can be applied for all-speed range flows. The objectives of the present study are: (1) to develop and verify the fractional volume-of-fluid (VOF) cell partitioning approach into a predictor-corrector algorithm to deal with multiphase (gas-liquid) free surface flow problems; (2) to implement the developed unified algorithm in a general purpose computational fluid dynamics (CFD) code, Finite Difference Navier-Stokes (FDNS), with droplet dynamics and finite-rate chemistry models; and (3) to demonstrate the effectiveness of the present approach by simulating benchmark problems of jet breakup/spray atomization and combustion. Modeling multiphase fluid flows poses a significant challenge because a required boundary must be applied to a transient, irregular surface that is discontinuous, and the flow regimes considered can range from incompressible to highspeed compressible flows. The flow-process modeling is further complicated by surface tension, interfacial heat and mass transfer, spray formation and turbulence, and their interactions. The major contribution of the present method is to combine the novel feature of the Volume of Fluid (VOF) method and the Eulerian/Lagrangian method into a unified algorithm for efficient noniterative, time-accurate calculations of multiphase free surface flows valid at all speeds. The proposed method reformulated the VOF equation to strongly couple two distinct phases (liquid and gas), and tracks droplets on a Lagrangian frame when spray model is required, using a unified predictor-corrector technique to account for the non-linear linkages through the convective contributions of VOF. The discontinuities within the sharp interface will be modeled as a volume force to avoid stiffness. Formations of droplets, tracking of droplet dynamics and modeling of the droplet breakup/evaporation, are handled through the same unified predictor-corrector procedure. Thus the new algorithm is non-iterative and is flexible for general geometries with arbitrarily complex topology in free surfaces. The FDNS finite-difference Navier-Stokes code is employed as the baseline of the current development. Benchmark test cases of shear coaxial LOX/H2 liquid jet with atomization/combustion and impinging jet test cases are investigated in the present work. Preliminary data comparisons show good qualitative agreement between data and the present analysis. It is indicative from these results that the present method has great potential to become a general engineering design analysis and diagnostics tool for problems involving spray combustion.

Chen, Yen-Sen↗

NASA NTRSDate not supplied

Uncrewed Lunar Surface Operations and Support Activities

This presentation summarizes the contents of the uncrewed lunar surface operations and support activities paper. It outlines the functions, features, and capabilities that support sustained human and robotic surface operations. It summarizes the complexities associated with the development and operation of autonomous systems and discusses a simulation tool for integrated surface operations planning.

Lunar↗

DOE OSTI2019

Interparticle Interactions in Dilute Solutions of Polyelectrolyte Complex Micelles.

The application of dilute solutions of poly electrolyte complex (PEC) micelles for delivering therapeutic nucleic acids into disease sites has gained momentum. This Letter reports a detailed characterization of PEC micelles in dilute solutions including their internal structures and the determination of the interparticle interactions. The polymer concentration ranges from 0.1 to 0.5 wt %, a regime where micelle-micelle interactions are infrequent. We employ synchrotron small-angle X-ray scattering (SAXS) to simultaneously probe the morphology, internal structure, and radius of gyration (R-g) of the self-assemblies formed by charged diblock polyelectrolytes and homopolyelectrolytes. The emerging appearance of the structure factor in SAXS profiles with the increasing polymer concentration demonstrates the presence of the repulsive intermicellar correlations, which is further confirmed by the differences between the "reciprocal R-g" estimated by Guinier approximation and the "real space R-g" determined by pair distribution functions. We find that the soft corona chains tethered on the surface of phase-separated complex domains are compressed when micelles come close to the point where a hard-sphere interaction takes over. These findings contribute to the fundamental understanding of the structure and space-filling constraints in the complexation-driven self-assemblies and advance the rational design of cationic polymer-based nonviral gene delivery vectors.

Wu, Hao↗

DOE OSTI2019

Probing the Dissociation of Protein Complexes by Means of Gas-Phase H/D Exchange Mass Spectrometry

Gas-phase hydrogen/deuterium exchange measured by mass spectrometry (gas-phase HDX-MS) is a fast method to probe the conformation of protein ions. The use of gas-phase HDX-MS to investigate the structure and interactions of protein complexes is however mostly unharnessed. Ionizing proteins under conditions that maximize preservation of their native structure (native MS) enables the study of solution-like conformation for milliseconds after electrospray ionization (ESI), which enables the use of ND{sub 3}-gas inside the mass spectrometer to rapidly deuterate heteroatom-bound non-amide hydrogens. Here, we explored the utility of gas-phase HDX-MS to examine protein-protein complexes and inform on their binding surface and the structural consequences of gas-phase dissociation. Protein complexes ranging from 24 kDa dimers to 395 kDa 24mers were analyzed by gas-phase HDX-MS with subsequent collision-induced dissociation (CID). The number of exchangeable sites involved in complex formation could, therefore, be estimated. For instance, dimers of cytochrome c or α-lactalbumin incorporated less deuterium/subunit than their unbound monomer counterparts, providing a measure of the number of heteroatom-bound side-chain hydrogens involved in complex formation. We furthermore studied if asymmetric charge-partitioning upon dissociation of protein complexes caused intermolecular H/D migration. In larger multimeric protein complexes, the dissociated monomer showed a significant increase in deuterium. This indicates that intermolecular H/D migration occurs as part of the asymmetric partitioning of charge during CID. We discuss several models that may explain this increase deuterium content and find that a model where only deuterium involved in migrating charge can account for most of the deuterium enrichment observed on the ejected monomer. In summary, the deuterium content of the ejected subunit can be used to estimate that of the intact complex with deviations observed for large complexes accounted for by charge migration. .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

NASA NTRS2007

Probabilistic Thermal Analysis During Mars Reconnaissance Orbiter Aerobraking

A method for performing a probabilistic thermal analysis during aerobraking has been developed. The analysis is performed on the Mars Reconnaissance Orbiter solar array during aerobraking. The methodology makes use of a response surface model derived from a more complex finite element thermal model of the solar array. The response surface is a quadratic equation which calculates the peak temperature for a given orbit drag pass at a specific location on the solar panel. Five different response surface equations are used, one of which predicts the overall maximum solar panel temperature, and the remaining four predict the temperatures of the solar panel thermal sensors. The variables used to define the response surface can be characterized as either environmental, material property, or modeling variables. Response surface variables are statistically varied in a Monte Carlo simulation. The Monte Carlo simulation produces mean temperatures and 3 sigma bounds as well as the probability of exceeding the designated flight allowable temperature for a given orbit. Response surface temperature predictions are compared with the Mars Reconnaissance Orbiter flight temperature data.

Dec, John A.↗

DOE OSTI2024

Role of Dynamic Polarization Interactions in the Electrical Double Layer at Calcite (104) Interfaces with Aqueous Solutions

Reactions at mineral interfaces with aqueous solutions control many geochemical and biogeochemical processes in the Earth’s critical zone. At the molecular level, insights into important properties such as the structure of the electrical double layer (EDL) at specific mineral interfaces continue to improve due to the increasing fidelity of laboratory instrumentation and computational approaches. However, molecular simulation approaches suffer from limited reach into relevant scales of time, length, and system complexity. To span this gap, a novel hybrid approach that couples first principle plane-wave density functional theory (DFT) with classical DFT (cDFT) is demonstrated and applied to calcite (104) interfaces with various electrolytes. In this approach, a region of interest described using DFT interacts with the surrounding medium described using cDFT to arrive at a self-consistent ground state. Benchmarking against experimental observations and entirely first principle DFT simulations demonstrates that this hybrid model efficiently encompasses the key short-range and collective interactions in the EDL. Simulations of calcite (104)/solution interfaces reveal the key static and dynamic polarization interactions that give rise to structuring of ions and water. Ion hydration interactions have the strongest effect on the depth of the first minimum in the density distribution of counterions at the surface, and the position and width of the first density peak is largely determined by the strength of ion-correlation forces. Finer details of ion distributions are controlled by mutual polarization of the calcite surface and interfacial electrolyte. Finally, this new ability to efficiently and rigorously predict EDL structure at mineral surfaces in contact with complex solutions paves the way to accurately modeling sorption, nucleation, dissolution, and growth in realistic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Recovery of Rare Earth Elements from Geothermal Fluids through Bacterial Cell Surface Adsorption

The increasing demand for rare earth elements (REEs) in the modern economy motivates the development of novel strategies for cost-effective REE recovery from nontraditional feedstocks. We previously engineered E. coli to express lanthanide binding tags on the cell surface, which increased the REE biosorption capacity and selectivity. Here we examined how REE adsorption by the engineered E. coli is affected by various geochemical factors relevant to geothermal fluids, including total dissolved solids (TDS), temperature, pH, and the presence of specific competing metals. REE biosorption is robust to TDS, with high REE recovery efficiency and selectivity observed with TDS as high as 165,000 ppm. Among several metals tested, U, Al, and Pb were found to be the most competitive, causing >25% reduction in REE biosorption when present at concentrations ~3- to 11-fold higher than the REEs. Optimal REE biosorption occurred between pH 5-6, and sorption capacity was reduced by ~65% at pH 2. REE recovery efficiency and selectivity increased as a function of temperature up to ~70 °C due to the thermodynamic properties of metal complexation on the bacterial surface. Ultimately, these data define the optimal and boundary conditions for biosorption and demonstrate its potential utility for selective REE recovery from geofluids.

58 GEOSCIENCES↗

NASA NTRS2004

A Versatile Platform for Nanotechnology Based on Circular Permutation of a Chaperonin Protein

A number of protein complexes have been developed as nanoscale templates. These templates can be functionalized using the peptide sequences that bind inorganic materials. However, it is difficult to integrate peptides into a specific position within a protein template. Integrating intact proteins with desirable binding or catalytic activities is an even greater challenge. We present a general method for modifying protein templates using circular permutation so that additional peptide sequence can be added in a wide variety of specific locations. Circular permutation is a reordering of the polypeptide chain such that the original termini are joined and new termini are created elsewhere in the protein. New sequence can be joined to the protein termini without perturbing the protein structure and with minimal limitation on the size and conformation of the added sequence. We have used this approach to modify a chaperonin protein template, placing termini at five different locations distributed across the surface of the protein complex. These permutants are competent to form the double-ring structures typical of chaperonin proteins. The permuted double-rings also form the same assemblies as the unmodified protein. We fused a fluorescent protein to two representative permutants and demonstrated that it assumes its active structure and does not interfere with assembly of chaperonin double-rings.

Paavola, Chad↗

NASA NTRS2004

A Subsurface Soil Composition and Physical Properties Experiment to Address Mars Regolith Stratigraphy

Previous in-situ measurements of soil-like materials on the surface of Mars, in particular during the on-going Mars Exploration Rover missions, have shown complex relationships between composition, exposure to the surface environment, texture, and local rocks. In particular, a diversity in both compositional and physical properties could be established that is interpreted to be diagnostic of the complex geologic history of the martian surface layer. Physical and chemical properties vary laterally and vertically, providing insight into the composition of rocks from which soils derive, and environmental conditions that led to soil formation. They are central to understanding whether habitable environments existed on Mars in the distant past. An instrument the Mole for Soil Compositional Studies and Sampling (MOCSS) - is proposed to allow repeated access to subsurface regolith on Mars to depths of up to 1.5 meters for in-situ measurements of elemental composition and of physical and thermophysical properties, as well as for subsurface sample acquisition. MOCSS is based on the compact PLUTO (PLanetary Underground TOol) Mole system developed for the Beagle 2 lander and incorporates a small X-ray fluorescence spectrometer within the Mole which is a new development. Overall MOCSS mass is approximately 1.4 kilograms. Taken together, the MOCSS science data support to decipher the geologic history at the landing site as compositional and textural stratigraphy if they exist - can be detected at a number of places if the MOCSS were accommodated on a rover such as MSL. Based on uncovered stratigraphy, the regional sequence of depositional and erosional styles can be constrained which has an impact on understanding the ancient history of the Martian near-surface layer, considering estimates of Mars soil production rates of 0.5... 1.0 meters per billion years on the one hand and Mole subsurface access capability of approximately 1.5 meters. An overview of the MOCSS, XRS instrument accomodation and the impact that these instruments have on Mars science is discussed.

Richter, L.↗

DOE OSTI2019

Comparison of Mesoscale Model Setups for Offshore Wind Resource Assessment: A New Jersey Case Study

As the offshore wind energy industry begins to emerge on the U.S. northeast coast, there is an urgent need for an accurate characterization of the offshore wind resource. The offshore regime features various resource characteristics not seen onshore, including frequent coastal low-level jets, non-steady surface conditions (e.g. waves), complex air-sea and land-sea interactions, and coastal mesoscale circulations (e.g. sea breeze). An accurate characterization of these phenomena in mesoscale models is critical to support accurate energy production estimates and forecasting for future offshore wind farms. However, a robust validation of mesoscale model performance in the offshore U.S. has been limited due to sparse data and difficulty obtaining offshore measurements. Consequently, it is unclear how mesoscale models perform offshore and which suite of parameterizations and input data are best suited for accurate resource characterization. To begin addressing this knowledge gap, the National Renewable Energy Laboratory, in collaboration with the Rutgers Center for Ocean Observing Leadership, conducted a mesoscale model validation campaign in the offshore environment. The Weather Research and Forecasting (WRF) model was assessed and the New Jersey offshore coastal area served as the validation domain. An ensemble of WRF simulations conducted over a one-year period sampled from a range of model setups, including different reanalysis and forecast data inputs, sea surface temperature data inputs, planetary boundary layer parameterizations, and WRF versions. The performance of each ensemble member was validated against a network of observations including offshore floating lidars, coastal met towers, offshore platform measurements, and offshore buoys. Model performance was assessed on annual, seasonal, and diurnal scales with particular emphasis on the vertical wind speed profile and temperature stratification. Preliminary results from this validation work will be presented here. The key WRF inputs and parameters driving changes in the modeled wind resource will be discussed and preliminary recommendations on WRF setups for offshore wind resource modeling will be proposed. The application of this validation exercise to other proposed offshore wind energy areas in the U.S. will also be discussed. mesoscale circulations (e.g. sea breeze). An accurate characterization of these phenomena in mesoscale models is critical to support accurate energy production estimates and forecasting for future offshore wind farms. However, a robust validation of mesoscale model performance in the offshore U.S. has been limited due to sparse data and difficulty obtaining offshore measurements. Consequently, it is unclear how mesoscale models perform offshore and which suite of parameterizations and input data are best suited for accurate resource characterization. To begin addressing this knowledge gap, the National Renewable Energy Laboratory, in collaboration with the Rutgers Center for Ocean Observing Leadership, conducted a mesoscale model validation campaign in the offshore environment. The Weather Research and Forecasting (WRF) model was assessed and the New Jersey offshore coastal area served as the validation domain. An ensemble of WRF simulations conducted over a one-year period sampled from a range of model setups, including different reanalysis and forecast data inputs, sea surface temperature data inputs, planetary boundary layer parameterizations, and WRF versions. The performance of each ensemble member was validated against a network of observations including offshore floating lidars, coastal met towers, offshore platform measurements, and offshore buoys. Model performance was assessed on annual, seasonal, and diurnal scales with particular emphasis on the vertical wind speed profile and temperature stratification. Preliminary results from this validation work will be presented here. The key WRF inputs and parameters driving changes in the modeled wind resource will be discussed and preliminary recommendations on WRF setups for offshore wind resource modeling will be proposed. The application of this validation exercise to other proposed offshore wind energy areas in the U.S. will also be discussed.

17 WIND ENERGY↗

DOE OSTI2019

Effect of Anions on the Changes in the Structure and Adsorption Mechanism of Zirconium Species at the Muscovite (001)–Water Interface

Multivalent cations primarily exist as polynuclear hydroxo and oxyhydroxo clusters and/or nanoparticles (NPs) in aqueous environments, where their interactions with mineral surfaces can be influenced by complexing anions. In this work, we explored the distribution of tetravalent Zr adsorbed on the negatively charged basal surface of muscovite mica in four background electrolytes (0.1 M NaClO 4 , 0.1 M NaCl, 0.04 M Na 2 SO 4 , and 0.045 M Na 2 HPO 4 ) at constant pH (= 3), total Zr(IV) concentration (= 0.1 mM), and ionic strength (= 0.1 M). The results show that aqueous Zr speciation determined by reactions with anions controls the formation and structure of Zr-containing adsorbates on the mica surface. The Zr coverages measured by X-ray fluorescence (XRF) in ClO 4 - and Cl - systems were 1.3 and 2.1 Zr/A UC (where A UC = 46.72 Å 2 is the area of the unit cell of the mica (001) surface), respectively, and mostly remained unchanged during the reaction time from 6 to 50 h. In these conditions, Zr adsorption occurred both as small NPs (with an average height of ~4 nm observed by ex situ atomic force microscopy, AFM) and in a ~2 nm-thick molecular layer (observed by in situ resonant anomalous X-ray reflectivity, RAXR). In comparison, higher Zr coverages that increased with reaction time (i.e., from ~4 to ~7 Zr/A UC from 6 to 50 h reactions) were observed in the SO 4 2- system. Ex situ AFM showed that the Zr uptake in this system occurred predominantly as NPs that were ~5 to 15 nm tall and 20 to 40 nm wide, but no evidence of the interfacial molecular-layer formation was observed by RAXR. In the HPO 4 2– solution, all measurements unequivocally showed no significant Zr sorption, in stark contrast to the observations in the other solutions. Details of the Zr surface coverage and sorption modes are consistent with the known clustering of tetravalent Zr in solutions in the presence of these anions. These results reveal the critical impact of anions on the adsorption affinity and mechanism of Zr on the negatively charged mica surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Magnetic Field-Driven Convection for Directed Surface Patterning of Colloids

Drying sessile droplets is a promising route to transform colloidal dispersions into surface coatings, which are widely used in material design and biochemical detection. However, directing the assembly of the particles within drying droplets and achieving surface patterns beyond the well-known coffee-ring formation remain a challenge. Here, we present a new principle of directing the assembly of nonmagnetic colloidal particles dispersed in a magnetic fluid and generating unusual surface patterns. We use the ability of ferrofluids to change phases with the application of magnetic fields to program the assembly of nonmagnetic microparticles present in drying sessile droplets. We show that in the absence of external magnetic field, the superparamagnetic nanoparticles in the magnetic fluid are spontaneously transported to the droplet edge because of solvent evaporation. This nanoparticle transport leads to the formation of nanoparticle-rich edge and nanoparticle-depleted center of the drying droplet. Upon the application of a uniform external magnetic field, the asymmetry in the magnetic nanoparticle distribution drives a magnetostatic convection and finger-like instability from the droplet edge to the center. This magnetic microconvection from droplet edge-to-center reverses the particle transport from center-to-edge, well-known for drying droplets in the absence of external field. We use this magnetostatic microconvection to assemble secondary nonmagnetic microspheres in droplets, overwriting ring formation and direct their assembly into four distinct kinetically stable states. As a result, the method presented here offers an active control over the colloidal assembly achieved by drying sessile droplets and thus enables a new route for fabricating complex patterns and functional surface coating.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

Adsorption of Rare Earth Elements onto DNA-Functionalized Mesoporous Carbon

The recovery and separation of rare earth elements (REEs) are of national importance owing to the specific usages, high demand, and low supply of these elements. In this research, we have investigated the adsorption of rare earth elements onto DNA-functionalized mesoporous carbons with a BET surface area of 605 m2/g and a median mesopore width of 48 Å. Additionally, three types of single-stranded DNA, one with 100 base units of thymine, another with 20 units of thymine, and the third, a 2000 unit long DNA from salmon milt were grafted on the carboxylated mesoporous carbon surface. All of the DNA-functionalized mesoporous carbons demonstrated higher adsorption of REEs compared to pristine mesoporous carbon and DNA grafted with 100 units of thymine demonstrated slightly higher adsorbed amounts compared to others. Pure neodymium (Nd(III)) adsorption in the aqueous phase demonstrated an adsorbed amount of 110.4 mg/g with respect to the initial concentration of 500 mg/g. A pH variation study with pure Nd(III) demonstrated that the adsorbed amount is higher at elevated pH compared to that at lower pH, thereby suggesting possible recovery at lower pH. Adsorption of a mixture of 16 REEs, including Sc, Lu, Tm, Yb, Er, Ho, Tb, Dy, Y, Eu, Gd, Sm, Ce, Nd, Pr, and La revealed that the adsorbed amount increased with an increase in the atomic weight and metallic radii of elements within the lanthanides. The calculation of the distribution coefficients for all of the equilibrium adsorption amounts suggested that adsorption is more effective in the lower concentration region. The Nd L3-edge X-ray absorption near edge structure (XANES) confirmed a 3+ oxidation state of Nd in the adsorbed phase. The extended X-ray absorption fine structure (EXAFS) confirmed the local atomic structure relaxation of Nd complexes in the adsorbed phase and shortening of the Nd–O bond distance by about 0.03–0.04 Å, which may be associated with their local complexation at the carbon surface.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Nickel(ii) complexes based on dithiolate–polyamine binary ligand systems: crystal structures, hirshfeld surface analysis, theoretical study, and catalytic activity study on photocatalytic hydrogen generation

To ascertain the influence of binary ligand systems [1,1-dicyanoethylene-2,2-dithiolate (i-mnt -2 ) and polyamine {tetraen = tris(2-aminoethyl)amine, tren = diethylene triamine and opda = o-phenylenediamine}] on the coordination modes of the Ni(II) metal center and resulting supramolecular architectures, a series of nickel(II) thiolate complexes [Ni(tetraen)(i-mnt)](DMSO) (1), [Ni 2 (tren) 2 (i-mnt) 2 ] (2), and [Ni 2 (i-mnt) 2 (opda) 2 ] n (3) have been synthesized in high yield in one step in water and structurally characterized by single crystal X-ray crystallography and spectroscopic techniques. X-ray diffraction studies disclose the diverse i-mnt -2 coordination to the Ni +2 center in the presence of active polyamine ligands, forming a slightly distorted octahedral geometry (NiN 4 S 2 ) in 1, square planar (NiS 4 ) and distorted octahedral geometries (NiN 6 ) in the bimetallic co-crystallized aggregate of cationic [Ni(tren) 2 ] +2 and anionic [Ni(i-mnt) 2 ] -2 in 2, and a one dimensional (1D) polymeric chain along the [100] axis in 3, having consecutive square planar (NiS 4 ) and octahedral (NiN 6 ) coordination kernels. The N–H···O, N–H···S, N–H···N, N–H···S, N–H···N, and N–H···O type hydrogen bonds stabilize the supramolecular assemblies in 1, 2, and 3 respectively imparting interesting graph-set-motifs. The molecular Hirshfeld surface analyses (HS) and 2D fingerprint plots were utilized for decoding all types of non-covalent contacts in the crystal networks. Atomic HS analysis of the Ni +2 centers reveals significant Ni–N metal–ligand interactions compared to Ni–S interactions. We have also studied the unorthodox interactions observed in the solid state structures of 1–3 by QTAIM and NBO analyses. Moreover, all the complexes proved to be highly active water reduction co-catalysts (WRC) in a photo-catalytic hydrogen evolution process involving iridium photosensitizers, wherein 2 and 3 having a square planar arrangement around the nickel center(s) – were found to be the most active ones, achieving 1000 and 1119 turnover numbers (TON), respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRSDate not supplied

Simulation of Oxidative Etch Pit Formation and Growth on FiberForm

Erosion of carbon surfaces due to oxidation does not occur uniformly but through the formation of localized etch pits because of active surface sites. These active sites are formed due to the presence of atomic defects on the carbon surface and have much higher reactivity compared to average non-defective sites. Thus, these active sites are the first to react during ablation, resulting in their removal. This causes all the neighboring atoms to be defective, and increasing their reactivity, thus leading to localized carbon removal around these “active” sites. In this manner, these highly reactive defects serve as nucleation sites for the formation and growth of etch pits, with detrimental effects on the structural integrity. In order to understand the influence of these etch pits on the material properties of carbon fiber microstructures, we have developed a new capability within direct simulation Monte Carlo (DSMC) to capture the etch pit formation process. This capability is developed within the DSMC code SPARTA (Stochastic PArallel Rarefied-gas Time-accurate Analyzer) and can model the material removal in the presence of active sites leading to the formation of etch pits. The focus of the current work will be to study the effect of etch pits on the material properties of FiberForm, the precursor substrate of the PICA Thermal Protection System (TPS) material. The microstructure of virgin FiberForm obtained directly from X-ray microtomography scans is used within SPARTA to obtain the ablated geometries with etch pits. These pitted microstructures are then imported into the Porous Microstructure Analysis (PuMA) software and various material properties such as thermal conductivity, elasticity, and permeability are computed. The variation of these properties because of the complex evolution of the surface topology due to the formation of etch pits is studied and analyzed. Furthermore, the effect of pitting is compared to the case of uniform radial shrinking of fibers, which has been the standard for modelling ablation of carbon structures, and significant differences are observed. Thus, a physically realistic model of material removal through the formation of etch pits will be helpful in predicting the degradation of carbon-based TPS more accurately during oxidation; as well as other mechanisms such as spallation, which involves the removal of chunks of material into the flow due to the growth of etch pits. This will ultimately improve our understanding of the failure modes in these materials due to ablation.

DSMC↗

NASA NTRSDate not supplied

Simulation of Oxidative Etch Pit Formation and Growth on FiberForm

Erosion of carbon surfaces due to oxidation does not occur uniformly but through the formation of localized etch pits because of active surface sites. These active sites are formed due to the presence of atomic defects on the carbon surface and have much higher reactivity compared to average non-defective sites. Thus, these active sites are the first to react during ablation, resulting in their removal. This causes all the neighboring atoms to be defective, and increasing their reactivity, thus leading to localized carbon removal around these “active” sites. In this manner, these highly reactive defects serve as nucleation sites for the formation and growth of etch pits, with detrimental effects on the structural integrity. In order to understand the influence of these etch pits on the material properties of carbon fiber microstructures, we have developed a new capability within direct simulation Monte Carlo (DSMC) to capture the etch pit formation process. This capability is developed within the DSMC code SPARTA (Stochastic PArallel Rarefied-gas Time-accurate Analyzer) and can model the material removal in the presence of active sites leading to the formation of etch pits. The focus of the current work will be to study the effect of etch pits on the material properties of FiberForm, the precursor substrate of the PICA Thermal Protection System (TPS) material. The microstructure of virgin FiberForm obtained directly from X-ray microtomography scans is used within SPARTA to obtain the ablated geometries with etch pits. These pitted microstructures are then imported into the Porous Microstructure Analysis (PuMA) software and various material properties such as thermal conductivity, elasticity, and permeability are computed. The variation of these properties because of the complex evolution of the surface topology due to the formation of etch pits is studied and analyzed. Furthermore, the effect of pitting is compared to the case of uniform radial shrinking of fibers, which has been the standard for modelling ablation of carbon structures, and significant differences are observed. Thus, a physically realistic model of material removal through the formation of etch pits will be helpful in predicting the degradation of carbon-based TPS more accurately during oxidation; as well as other mechanisms such as spallation, which involves the removal of chunks of material into the flow due to the growth of etch pits. This will ultimately improve our understanding of the failure modes in these materials due to ablation.

DSMC↗

NASA NTRSDate not supplied

Computational Study of Oxidative Etch Pitting in FiberForm and the Effect on Its Material Properties

Erosion of carbon due to oxidation does not occur uniformly but through the formation of localized etch pits because of active surface sites. These active sites are formed due to the presence of atomic defects on the carbon surface, and have much higher reactivity compared to average non-defective sites. Thus, these active sites are first to react during ablation, resulting in their removal. This causes all the neighboring atoms to be defective and increase their reactivity, thus leading to the localized carbon removal around these “active” sites. In this manner, these highly reactive defective sites serve as nucleation sites for the formation and growth of etch pits with potentially detrimental effects on the structural integrity. In order to understand the influence of these etch pits on the material properties of carbon fiber microstructures, we have developed a new capability within direct simulation Monte Carlo (DSMC) to capture the etch pit formation process. This capability is developed within the DSMC code SPARTA (Stochastic PArallel Rarefied-gas Time-accurate Analyzer) and can model the material removal in presence of active sites leading to the formation of etch pits. The focus of the current work will be to study the effect of etch pits on the material properties of FiberForm, a commonly used base material within many thermal protection system materials (TPS). The microstructure of virgin FiberForm obtained directly from X-ray microtomography experiments is used within SPARTA to obtain the ablated geometries with etch pits. These pitted microstructures are then imported within the Porous Microstructure Analysis (PuMA) software and various material properties such as elasticity, thermal conductivity, and permeability are computed. The variation of these properties as a result of the complex evolution of the surface topology due to etch pit formation is studied and analyzed. Furthermore, the effect of pitting is compared to the case of shrinking fibers, which has been the standard for modelling ablation of carbon structures; and significant differences are observed. Thus, such a physically realistic modeling of material removal through the formation of etch pits will be helpful in predicting the degradation of carbon-based TPS more accurately during oxidation; as well as other mechanisms such as spallation, which involves the removal of chunks of material into the flow due to etch pit growth. This will ultimately improve our understanding of the failure modes in these materials due to ablation.

Carbon Ablators↗

NASA NTRSDate not supplied

Computational Study of Oxidative Etch Pitting in FiberForm and the Effect on Its Material Properties

Erosion of carbon due to oxidation does not occur uniformly but through the formation of localized etch pits because of active surface sites. These active sites are formed due to the presence of atomic defects on the carbon surface, and have much higher reactivity compared to average non-defective sites. Thus, these active sites are first to react during ablation, resulting in their removal. This causes all the neighboring atoms to be defective and increase their reactivity, thus leading to the localized carbon removal around these “active” sites. In this manner, these highly reactive defective sites serve as nucleation sites for the formation and growth of etch pits with potentially detrimental effects on the structural integrity. In order to understand the influence of these etch pits on the material properties of carbon fiber microstructures, we have developed a new capability within direct simulation Monte Carlo (DSMC) to capture the etch pit formation process. This capability is developed within the DSMC code SPARTA (Stochastic PArallel Rarefied-gas Time-accurate Analyzer) and can model the material removal in presence of active sites leading to the formation of etch pits. The focus of the current work will be to study the effect of etch pits on the material properties of FiberForm, a commonly used base material within many thermal protection system materials (TPS). The microstructure of virgin FiberForm obtained directly from X-ray microtomography experiments is used within SPARTA to obtain the ablated geometries with etch pits. These pitted microstructures are then imported within the Porous Microstructure Analysis (PuMA) software and various material properties such as elasticity, thermal conductivity, and permeability are computed. The variation of these properties as a result of the complex evolution of the surface topology due to etch pit formation is studied and analyzed. Furthermore, the effect of pitting is compared to the case of shrinking fibers, which has been the standard for modelling ablation of carbon structures; and significant differences are observed. Thus, such a physically realistic modeling of material removal through the formation of etch pits will be helpful in predicting the degradation of carbon-based TPS more accurately during oxidation; as well as other mechanisms such as spallation, which involves the removal of chunks of material into the flow due to etch pit growth. This will ultimately improve our understanding of the failure modes in these materials due to ablation.

Carbon Ablators↗