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All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

The role of clinical pharmacology in molecular genetics

PROBLEM: Discovering the causes of unusual phenotypes in human subjects is an important aspect of patient-oriented research. MATERIAL: The tools of clinical pharmacology are uniquely useful in addressing these problems. PATIENTS, SUBJECTS, OR CASE HISTORIES: We evaluated a 42-year-old patient with lifelong orthostatic hypotension and ptosis of the eyelids. He underwent a series of biochemical, physiological, and pharmacological tests outlined in this article. RESULTS: These studies indicated that sympathetic innervation was intact but that the sympathetic neurotransmitter was dopamine rather than norepinephrine. These results demonstrated that dopamine-beta-hydroxylase deficiency underlies the clinical abnormalities of this patient. CONCLUSION: In selected individuals with unusual phenotypes, the techniques of clinical chemistry and clinical pharmacology can define the nature of the defect at almost the resolution of the human genome.

NASA Discipline Regulatory Physiology↗
NASA NTRS1984

Plasma variables and tribological properties of coatings in low pressure (0.1 - 10.0 torr) plasma systems

A detailed treatment is presented of the dialog known as plasma surface interactions (PSI) with respect to the coating process and its tribological behavior. Adsorption, morphological changes, defect formation, sputtering, chemical etching, and secondary electron emission are all discussed as promoting and enhancing the surface chemistry, thus influencing the tribological properties of the deposited flux. Phenomenological correlations of rate of deposition, flux composition, microhardness, and wear with the plasma layer variables give an insight to the formation of chemical bonding between the deposited flux and the substrate surface.

Avni, R.↗
NASA NTRSDate not supplied

Implementation of Active Sites in DSMC to Capture Pitting of Oxidizing Carbon Materials

In this work we demonstrate a newly developed capability to capture pitting of carbon fibers in DSMC simulations, specifically using the Stochastic PArallel Rarefied-gas Time-accurate Analyzer (SPARTA) code. State-of-the-art reactive surface models in DSMC compute collision dependent carbon consumption rates (usually through desorption of CO) based on a set of surface reactions that has been derived from molecular beam experiments. The reactivity on each carbon surface element is constant in those models, such that the carbon surface recedes uniformly as a result of ablation. However, it is well known that in reality the carbon surface has locally different reaction rates due to the presence of defects at the atomic scale. These defective sites have a much higher reactivity than the average sites (2-3 orders of magnitude) and are first to react during ablation leading to its 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. Recently a detailed surface chemistry framework was developed in SPARTA, capable of incorporating various reaction mechanisms such as adsorption, desorption, Eley-Rideal (ER) and Langmuir-Hinshelwood (LH) mechanisms. Within this framework, we have implemented the capability of a single surface having multiple site sets with different reactivities. Using this feature, we can simulate the presence of active sites on carbon surfaces, whose reactivity is much greater than an average site as a result of defects. We have implemented the active site fraction as a property of surface elements within SPARTA, which is directly proportional to the local reactivity of each surface element. By introducing an initial distribution of the active site fraction across the carbon surface, and propagating it in a manner that mimics the evolution of real reacting carbon surfaces, we are able to capture the formation and growth of etch pits as a result of surface consumption reactions such as oxidation.

DSMC↗
NASA NTRSDate not supplied

Implementation of active sites to capture pitting of oxidizing carbon materials in DSMC.

In this work we demonstrate a newly developed capability to capture pitting of carbon fibers in DSMC simulations, specifically using the Stochastic PArallel Rarefied-gas Time-accurate Analyzer (SPARTA) code [1]. State-of-the-art reactive surface models in DSMC compute collision dependent carbon consumption rates (usually through desorption of CO) based on a set of surface reactions that has been derived from molecular beam experiments [2]. The reactivity on each carbon surface element is constant in those models, such that the carbon surface recedes uniformly as a result of ablation. However, it is well known that in reality the carbon surface has locally different reaction rates due to the presence of defects at the atomic scale [3]. These defective sites have a much higher reactivity than the average sites (2-3 orders of magnitude) and are first to react during ablation leading to its 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 (as shown in Fig. 1). 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. Recently a detailed surface chemistry framework was developed in SPARTA, capable of incorporating various reaction mechanisms such as adsorption, desorption, Eley-Rideal (ER) and Langmuir-Hinshelwood (LH) mechanisms [4]. Within this framework, we have implemented the capability of a single surface having multiple site sets with different reactivities. Using this feature, we can simulate the presence of active sites on carbon surfaces, whose reactivity is much greater than an average site as a result of defects. We have implemented the active site fraction as a property of surface elements within SPARTA, which is directly proportional to the local reactivity of each surface element. By introducing an initial distribution of the active site fraction across the carbon surface, and propagating it in a manner that mimics the evolution of real reacting carbon surfaces, we are able to capture the formation and growth of etch pits as a result of surface consumption reactions such as oxidation.

DSMC↗
NASA NTRS1985

Experimental and Theoretical Analysis of Chemical Vapor Deposition with Prediction of Gravity Effects

A combined experimental and theoretical study to characterize the effects of gravitationally-induced transport on atmospheric pressure silicon epitaxy by SiH4 pyrolysis is planned. Experimentally, flow regimes in which free convective transport contributes to the Chemical Vapor Deposition (CVD) process will be identified, and, for these conditions, the flow and deposition process will be characterized. Specifically, this will include measurements of three dimensional temperature variations using in situ Rayleigh scattering, gas phase composition profiles using laser absorption and fluorescence techniques, and deposition rates and defect densities. Subsequently, the free convective transport contribution to the CVD process will be minimized and/or altered while leaving deposition chemistry unaltered, and the characterization will be repeated. Based on these analyses, the effects of gravitationally-induced transport on atmospheric pressure CVD will be assessed.

Charter D. Stinespring↗
NASA NTRS1989

Interfacial analysis of tribological systems containing molybdenum disulfide and iron using XPS and CEMS

In the present evaluation of results from studies of the interfacial chemistry and morphology of a buried lubricant-substrate interface, specimens of increasing complexity that culminated with the effects of excess sulfur and defects were characterized by XPS and SEM, as well as conversion-electron Moessbauer spectroscopy (CEMS). In order to simulate sputtered systems, single crystals of MoS2 were damaged with Ar(+) bombardment and coated with Fe. Fe is found to react differently with MoS2 depending on surface treatments, surface defects, annealing treatments, and the presence of excess sulfur. The annealing temperature determines which compounds are formed, as well as the crystal habit and plane at the Fe-MoS2 interface.

Zabinski, J. S.↗
NASA NTRS1988

Supercomputer chemistry at the University of Minnesota

The focus of cluster chemistry studies at the University of Minnesota is on the adsorption of small hydrocarbon molecules on metal and graphite surfaces, and on the substitution defects in diamond and silicon. Of particular interest is the study of very large systems such as the C60 molecule and the C150H30 molecule. Many of the properties of such clusters converge extremely slowly toward bulk values. Ultrathin films and microporous media are discussed as well as the Brownian dynamics of polymers.

Almlof, Jan↗
NASA NTRSDate not supplied

Simulation of Etch Pit Formation in DSMC Through Active Sites in Carbon Fiber Micro-Structures

Erosion of carbon due to oxidation does not occur uniformly but through localized etch pit formation because of active surface sites. In this work we demonstrate a newly developed capability to capture pitting of carbon fiber microstructures such as FiberForm, which is commonly used as the base material for NASA’s spacecraft ablative thermal protection systems (TPS). The simulations are performed at the meso-scale in order to capture the pit formation and growth using direct simulation Monte Carlo (DSMC), specifically using the Stochastic PArallel Rarefied-gas Time-accurate Analyzer (SPARTA) code. Legacy and latest models both assume uniform reactivity of carbon surface sites with oxygen even at the meso-scale level. However, in reality the carbon surface has locally different reaction rates due to the presence of defects at the atomic scale. The defective nature of these sites enhances their reactivity with atmospheric gases compared to the non-defective sites (2-3 orders of magnitude) and are termed as “active sites”. Thus, these sites tend to be the first to react and eventually get removed through the formation of gases such as CO, CO2, and CN. Their removal results in all the neighboring atoms becoming defective, thus leading to chain reaction of localized carbon removal and formation of etch pits. Capturing the formation of pits during the ablation simulation of carbon micro-structures is critical to predicting their structural failure. Recently a detailed surface chemistry framework was developed in SPARTA, capable of incorporating various detailed surface reaction mechanisms. We have implemented the capability of a single surface having multiple site sets with different reactivities within this framework. We have used this feature to model the presence of active sites on carbon surfaces, whose reactivity is orders of magnitude higher than that of the passive sites due to the presence of defects. The active site fraction is a property of surface elements within SPARTA and is directly proportional to the local reactivity of each surface element. By introducing an initial distribution of the active site fraction across the carbon surface and propagating it in a manner that mimics the evolution of real reacting carbon surfaces, we can capture the formation and growth of etch pits as a result of surface consumption reactions such as oxidation.

DSMC↗
NASA NTRSDate not supplied

DSMC Simulation of Etch Pit Formation Through Active Sites in Carbon Fiber Micro-Structures

Erosion of carbon due to oxidation does not occur uniformly but through localized etch pit formation because of active surface sites. In this work we demonstrate a newly developed capability to capture pitting of carbon fiber microstructures such as FiberForm, which is commonly used as the base material for NASA’s spacecraft ablative thermal protection systems (TPS). The simulations are performed at the meso-scale in order to capture the pit formation and growth using direct simulation Monte Carlo (DSMC), specifically using the Stochastic PArallel Rarefied-gas Time-accurate Analyzer (SPARTA) code. Legacy and latest models both assume uniform reactivity of carbon surface sites with oxygen even at the meso-scale level. However, in reality the carbon surface has locally different reaction rates due to the presence of defects at the atomic scale. The defective nature of these sites enhances their reactivity with atmospheric gases compared to the non-defective sites (2-3 orders of magnitude) and are termed as “active sites”. Thus, these sites tend to be the first to react and eventually get removed through the formation of gases such as CO, CO2, and CN. Their removal results in all the neighboring atoms becoming defective, thus leading to chain reaction of localized carbon removal and formation of etch pits. Capturing the formation of pits during the ablation simulation of carbon micro-structures is critical to predicting their structural failure. Recently a detailed surface chemistry framework was developed in SPARTA, capable of incorporating various detailed surface reaction mechanisms. We have implemented the capability of a single surface having multiple site sets with different reactivities within this framework. We have used this feature to model the presence of active sites on carbon surfaces, whose reactivity is orders of magnitude higher than that of the passive sites due to the presence of defects. The active site fraction is a property of surface elements within SPARTA and is directly proportional to the local reactivity of each surface element. By introducing an initial distribution of the active site fraction across the carbon surface and propagating it in a manner that mimics the evolution of real reacting carbon surfaces, we can capture the formation and growth of etch pits as a result of surface consumption reactions such as oxidation.

DSMC↗
NASA NTRS2003

Thermomechanical Properties of Interface Modified M40J Carbon/PMR-II-50 Composites

To increase performance and durability of high-temperature composites for potential rocket engine components, it is necessary to optimize wetting and interfacial bonding between high modulus carbon fibers and high-temperature polyimide resins. It has been previously demonstrated that the electro-oxidative shear treatments used by fiber manufacturers are not effective on higher modulus fibers that have fewer edge and defect sites in the surface crystallites. In addition, sizings commercially supplied on most carbon fibers are not compatible with polyimides. In this study, the surface chemistry and energy of high modulus carbon fibers (M40J and M60J, Torray) and typical fluorinated polyimide resins, such as PMR-11-50 were characterized. A continuous desizing system that uses an environmentally friendly chemical- mechanical process was developed for tow level fiber. Composites were fabricated with fibers containing the manufacturer's sizing, desized, and further treated with a reactive finish. Results of room temperature tests show that desizing reduces interface sensitive properties compared to the manufacturer's sizing and that subsequent surface re-treatment with reactive finish increases interface sensitive properties. Properties of thermally aged composites and composites with varying finish concentrations will also be discussed.

Allred, Ronald E.↗
NASA NTRS2003

Thermomechanical Properties of M40J Carbon/PMR-II-50 Composites

To increase performance and durability of high-temperature composites for potential rocket engine components, it is necessary to optimize wetting and interfacial bonding between high modulus carbon fibers and high-temperature polyimide resins. It has been previously demonstrated that the electro-oxidative shear treatments used by fiber manufacturers are not effective on higher modulus fibers that have fewer edge and defect sites in the surface crystallites. In addition, sizings commercially supplies on most carbon fibers are not compatible with polyimides. In this study, the surface chemistry and energy of high modulus carbon fibers (M40J and M60J, Torray) and typical fluorinated polyimide resins, such as PMR-II-50 were characterized. A continuous desizing system that uses an environmentally friendly chemical-mechanical process was developed for tow level fiber. Composites were fabricated with fibers containing the manufacturer's sizing, desized, and further treated with a reactive finish. Results of room temperature tests show that desizing reduces interface sensitive properties compared to the manufacturer's sizing and that subsequent surface re-treatment with reactive finish increases interface sensitive properties. Properties of thermally aged composites and composites with varying finish concentrations are also discussed.

Ronald E. Allred↗
NASA NTRSDate not supplied

Simulation of etch pit formation through active sites in carbon fiber micro-structures

Erosion of carbon due to oxidation does not occur uniformly but through localized etch pit formation as a result of active surface sites. In this work we demonstrate a newly developed capability to capture pitting of carbon fiber microstructures such as FiberForm, which is commonly used as the base material for NASA’s spacecraft ablative thermal protection systems (TPS). The simulations are performed at the meso-scale in order to capture the pit formation and growth using direct simulation Monte Carlo (DSMC), specifically using the Stochastic PArallel Rarefied-gas Time-accurate Analyzer (SPARTA) code. Legacy and latest models both assume uniform reactivity of carbon surface sites with oxygen even at the meso-scale level. However, in reality the carbon surface has locally different reaction rates due to the presence of defects at the atomic scale. The defective nature of these sites enhances their reactivity with atmospheric gases compared to the non-defective sites (2-3 orders of magnitude) and are termed as “active sites”. Thus, these sites tend to be the first to react and eventually get removed through the formation of gasses such as CO, CO2, and CN. Their removal results in all the neighboring atoms becoming defective, thus leading to chain reaction of localized carbon removal and formation of etch pits. Capturing the formation of pits during the ablation simulation of carbon micro-structures is critical to predicting their structural failure. Recently a detailed surface chemistry framework was developed in SPARTA, capable of incorporating various reaction mechanisms such as adsorption, desorption, Eley-Rideal (ER) and Langmuir-Hinshelwood (LH) mechanisms. We have implemented the capability of a single surface having multiple site sets with different reactivities within this framework. We have used this feature to model the presence of active sites on carbon surfaces, whose reactivity is orders of magnitude higher than that of the passive sites due to the presence of defects. The active site fraction is a property of surface elements within SPARTA and is directly proportional to the local reactivity of each surface element. By introducing an initial distribution of the active site fraction across the carbon surface and propagating it in a manner that mimics the evolution of real reacting carbon surfaces, we can capture the formation and growth of etch pits as a result of surface consumption reactions such as oxidation.

DSMC↗
NASA NTRS2017

Correlations Among Microstructure, Morphology, Chemistry, and Isotopic Systematics of Hibonite in CM Chondrites

Introduction: Hibonite is a primary refractory phase occurring in many CAIs, typically with spinel and perovskite. Our microstructural studies of CAIs from carbonaceous chondrites reveal a range of stacking defect densities and correlated non-stoichiometry in hibonite. We also conducted a series of annealing experiments, demonstrating that the Mg-Al substitution stabilized the formation of defect-structured hibonite. Here, we continue a detailed TEM analysis of hibonite-bearing inclusions from CM chondrites that have been well-characterized isotopically. We examine possible correlations of microstructure, morphology, mineralogy, and chemical and isotopic systematics of CM hibonites in order to better understand the formation history of hibonite in the early solar nebula. Methods: Fifteen hibonite-bearing inclusions from the Paris CM chondrite were analyzed using a JEOL 7600F SEM and a JEOL 8530F electron microprobe. In addition to three hibonite-bearing inclusions from the Murchison CM chondrite previously reported, we selected three inclusions from Paris, Pmt1-6, 1-9, and 1-10, representing a range of 26Al/27Al ratios and minor element concentrations for a detailed TEM study. We extracted TEM sections from hibonite grains using a FEI Quanta 3D field emission gun SEM/FIB. The sections were then examined using a JEOL 2500SE field-emission scanning TEM equipped with a Thermo-Noran thin window EDX spectrometer. Results and Discussion: A total of six hibonite-bearing inclusions, including two platy hibonite crystals (PLACs) and four spinel-hibonite inclusions (SHIBs), were studied. There are notable differences in chemical and isotopic compositions between the inclusions (Table 1), indicative of their different formation environment or timing. Our TEM observations show perfectly-ordered, stoichiometric hibonite crystals without stacking defects in two PLACs, 2-7-1 and 2-8-2, and in three SHIBs, Pmt1-6, 1-9, and 1-10. In contrast, SHIB 1-9-5 hibonite grains contain a low density of stacking defects linked to an increase in MgO contents, indicating complex, disordered intergrowths of stoichiometric and MgO-enriched hibonites. From the data collected to date, we find no clear correlation between the microstructures of hibonite and its morphological and mineralogical types that reflect distinct chemical and isotopic systematics [6-8,10]. Interestingly, the presence of no or few stacking defects in hibonite from the PLACs and SHIBs are in contrast to our experimental studies that produced very high densities of stacking defects in hibonite [3-5]. Unlike our experi-ments, electron microprobe data from the PLACs and SHIBs hibonite grains show a strong correlation between (Ti4++Si4+) and Mg2+ cations, suggesting that coupled substitutions of (Ti4++Mg2+) and (Si4++Mg2+) for 2Al3+ inhibit the formation of defect-structured hibonite. However, our experimental studies suggest that kinetics (e.g., cooling rate) or other thermal effects also exert a strong control on the microstructures and chemical compositions of hibonite. In Pmt1-6, elongated perovskite grains present at the hibonite grain boundaries display (121) twinning, indicative of a fast cooling (>50degC/min) after high-temperature events. Therefore, the nebular microstructural characteristics of hibonite, at least in this inclusion, would not have destroyed by subsequent high-temperature annealing. Conclusions: Our TEM observations thus far show no clear correlation in microstructures, morphological and mineralogical characteristics, and chemical and isotopic systematics of hibonites from CM chondrites. The observed variation in stacking defect densities in the hibonites may be controlled by thermal processes in the early solar nebula. A detailed TEM analysis of additional CM hibonite samples is underway to evaluate this hypothesis.

Han, J.↗
NASA NTRS1974

Evaluation of tantalum-alloy-clad uranium mononitride fuel specimens from 7500-hour, 1040 C pumped-lithium-loop test

Simulated nuclear fuel element specimens, consisting of uranium mononitride (UN) fuel cylinders clad with tungsten-lined T-111, were exposed for up to 7500 hr at 1040 C (1900 F) in a pumped-lithium loop. The lithium flow velocity was 1.5 m/sec (5 ft/sec) in the specimen test section. No evidence of any compatibility problems between the specimens and the flowing lithium was found based on appearance, weight change, chemistry, and metallography. Direct exposure of the UN to the lithium through a simulated cladding crack resulted in some erosion of the UN in the area of the defect. The T-111 cladding was ductile after lithium exposure, but it was sensitive to hydrogen embrittlement during post-test handling.

Watson, G. K.↗
NASA NTRS2002

Properties of M40J Carbon/PMR-II-50 Composites Fabricated with Desized and Surface Treated Fibers. Characterization of M40J Desized and Finished Fibers

To increase performance and durability of high temperature composites for potential rocket engine components, it is necessary to optimize wetting and interfacial bonding between high modulus carbon fibers and high temperature polyimide resins. It has been previously demonstrated that the electro-oxidative shear treatments used by fiber manufacturers are not effective on higher modulus fibers that have fewer edge and defect sites in the surface crystallites. In addition, sizings commercially supplied on most carbon fibers are not compatible with polyimides. This study was an extension of prior work characterizing the surface chemistry and energy of high modulus carbon fibers (M40J and M60J, Torray) with typical fluorinated polyimide resins, such as PMR-II-50. A continuous desizing system which utilizes environmentally friendly chemical- mechanical processes was developed for tow level fiber and the processes were optimized based on weight loss behavior, surface elemental composition (XPS) and morphology (FE-SEM) analyses, and residual tow strength of the fiber, and the similar approaches have been applied on carbon fabrics. Both desized and further treated with a reactive finish were investigated for the composite reinforcement. The effects of desizing and/or subsequent surface retreatment on carbon fiber on composite properties and performance including fiber-matrix interfacial mechanical properties, thermal properties and blistering onset behavior will be discussed in this presentation.

Allred, Ronald E.↗
NASA NTRS1996

Selecting NiCd flight cells for the NOAA/TIROS program

Data from Standard NiCd battery cell vendors is found to be useful for identifying defective cells. A method has been developed to screen cells for flight battery use and identify prime candidate cells for life-cycle testing. Specific points from the cell vendor's data, which are related to fundamentals of NiCd cell chemistry (primarily oxygen recombination) and electrical performance (voltage and capacity), when sampled at key points, are found to be related to long-term LEO life-cycle performance.

Toft, Mark R.↗
NASA NTRS1999

Development of an Advanced Computational Model for OMCVD of Indium Nitride

An advanced computational model is being developed to predict the formation of indium nitride (InN) film from the reaction of trimethylindium (In(CH3)3) with ammonia (NH3). The components are introduced into the reactor in the gas phase within a background of molecular nitrogen (N2). Organometallic chemical vapor deposition occurs on a heated sapphire surface. The model simulates heat and mass transport with gas and surface chemistry under steady state and pulsed conditions. The development and validation of an accurate model for the interactions between the diffusion of gas phase species and surface kinetics is essential to enable the regulation of the process in order to produce a low defect material. The validation of the model will be performed in concert with a NASA-North Carolina State University project.

Cardelino, Carlos A.↗
NASA NTRS1993

Quartz dissolution. I - Negative crystal experiments and a rate law. II - Theory of rough and smooth surfaces

The range of the measured quartz dissolution rates, as a function of temperature and pOH, extent of saturation, and ionic strength, is extended to cover a wider range of solution chemistries, using the negative crystal methodology of Gratz et al. (1990) to measure the dissolution rate. A simple rate law describing the quartz dissolution kinetics above the point of zero charge of quartz is derived for ionic strengths above 0.003 m. Measurements were performed on some defective crystals, and the mathematics of step motion was developed for quartz dissolution and was compared with rough-face behavior using two different models.

Gratz, Andrew J.↗