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NASA NTRS1998

Thermal Protection Materials Development

The main portion of this contract year was spent on the development of materials for high temperature applications. In particular, thermal protection materials were constantly tested and evaluated for thermal shock resistance, high-temperature dimensional stability, and tolerance to hostile environmental effects. The analytical laboratory at the Thermal Protection Materials Branch (TPMB), NASA-Ames played an integral part in the process of materials development of high temperature aerospace applications. The materials development focused mainly on the determination of physical and chemical characteristics of specimens from the various research programs.

Selvaduray, Guna↗

NASA NTRS2000

Space Environmentally Stable Polyimides and Copolyimides

Polyimides with a unique combination of properties including low color in thin films, atomic oxygen (AO), ultra-violet (UV) radiation resistance, solubility in organic solvents in the imide form, high glass transition (T(sub g)) temperatures and high thermal stability have been prepared and characterized. The polymers were prepared by reacting a novel aromatic diamine with aromatic dianhydrides in a polar aprotic solvent. The solubility of the polymers in the imide form as well as the color density of thin films were dependent upon the chemical structure of the dianhydride. Several thin films (25-50 mm thick) prepared by solution casting of amide acid or imide solutions exhibited very low color and high optical transparency (approximately 90%) as determined by UV/visible spectroscopy. The polymers exhibited T(sub g)s >200 C depending upon the structure of the dianhydride and temperatures of 5% weight loss approximately 500C in air as determined by dynamic thermogravimetric analysis. Thin films coated with silver/inconel were exposed to a high fluence of AO and 1000 equivalent solar hours of UV radiation. The effects of these exposures on optical properties were minor. These space environmentally durable polymers are potentially useful in a variety of applications on spacecraft such as thin film membranes on antennas, second-surface mirrors, thermal/optical coatings and multi-layer thermal insulation (MLI) blanket materials. The chemistry, physical and mechanical properties of the polymers as well as their responses to AO and UV exposure will be discussed.

Watson, Kent A.↗

NASA NTRS1994

Structure and stability of hydrous minerals at high pressure

The presence of even small amounts of hydrogen in the Earth's deep interior may have profound effects on mantle melting, rheology, and electrical conductivity. The recent discovery of a large class of high-pressure H-bearing silicates further underscores the potentially important role for hydrous minerals in the Earth's mantle. Hydrogen may also be a significant component of the Earth's core, as has been recently documented by studies of iron hydride at high pressure. In this study, we explore the role of H in crystal structures at high pressure through detailed Raman spectroscopic and x ray diffraction studies of hydrous minerals compressed in diamond anvil cells. Brucite, Mg(OH)2, has a simple structure and serves as an analogue for the more complex hydrous silicates. Over the past five years, this material has been studied at high pressure using shock-compression, powder x ray diffraction, infrared spectroscopy, Raman spectroscopy, and neutron diffraction. In addition, we have recently carried out single-crystal synchrotron x-ray diffraction on Mg(OH)2 and Raman spectroscopy on Mg(OD)2 at elevated pressure. From all these studies, an interesting picture of the crystal chemical behavior of this material at high pressure is beginning to emerge. Some of the primary conclusions are as follows: First, hydrogen bonding is enhanced by the application of pressure. Second, layered minerals which are elastically anisotropic at low pressure may not be so at high pressure. Furthermore, the brucite data place constraints on the effect of hydrogen on seismic velocities and density at very high pressure. Third, the stability of hydrous minerals may be enhanced at high P by subtle structural rearrangements that are difficult to detect using traditional probes and require detailed spectroscopic analyses. Finally, brucite appears to be unique in that it undergoes pressure-induced disordering that is confined solely to the H-containing layers of the structure.

Duffy, T. S.↗

NASA NTRS1991

Improving the Reliability and Modal Stability of High Power 870 nm AlGaAs CSP Laser Diodes for Applications to Free Space Communication Systems

The operating characteristics (power-current, beam divergence, etc.) and reliability assessment of high-power CSP lasers is discussed. The emission wavelength of these lasers was optimized at 860 to 880 nm. The operational characteristics of a new laser, the inverse channel substrate planar (ICSP) laser, grown by metalorganic chemical vapor deposition (MOCVD), is discussed and the reliability assessment of this laser is reported. The highlights of this study include a reduction in the threshold current value for the laser to 15 mA and a degradation rate of less than 2 kW/hr for the lasers operating at 60 mW of peak output power.

Connolly, J. C.↗

NASA NTRS1989

Surface acoustic-wave piezoelectric crystal aerosol mass microbalance

The development of a particulate mass-sensing instrument based on a quartz-crystal microbalance and enhanced with the new surface acoustic-wave (SAW) technology is reported. Mass sensitivity comparisons of a 158-MHz SAW piezoelectric microbalance and a conventional 10-MHz quartz-crystal microbalance show that the SAW crystal is 266 times more sensitive, in good agreement with the theoretical value of 250. The frequency stability of a single SAW resonator is 6 parts in 10 to the 8th over 1 min. The response to temperature changes is found to be very linear over the range +30 to -30 C. A strong response to 15 ppm SO2 has been demonstrated on a chemically coated SAW crystal.

Bowers, W. D.↗

NASA NTRS2004

Advanced Constituents and Processes for Ceramic Composite Engine Components

The successful replacement of metal alloys by ceramic matrix composites (CMC) in hot-section engine components will depend strongly on optimizing the processes and properties of the CMC microstructural constituents so that they can synergistically provide the total CMC system with improved temperature capability and with the key properties required by the components for long-term structural service. This presentation provides the results of recent activities at NASA aimed at developing advanced silicon carbide (Sic) fiber-reinforced hybrid Sic matrix composite systems that can operate under mechanical loading and oxidizing conditions for hundreds of hours at 2400 and 2600 F, temperatures well above current metal capability. These SiC/SiC composite systems are lightweight (-30% metal density) and, in comparison to monolithic ceramics and carbon fiber-reinforced ceramic composites, are able to reliably retain their structural properties for long times under aggressive engine environments. It is shown that the improved temperature capability of the SiC/SiC systems is related first to the NASA development of the Sylramic-iBN Sic fiber, which displays high thermal stability, creep resistance, rupture resistance, and thermal conductivity, and possesses an in-situ grown BN surface layer for added environmental durability. This fiber is simply derived from Sylramic Sic fiber type that is currently produced at ATK COI Ceramics. Further capability is then derived by using chemical vapor infiltration (CVI) to form the initial portion of the hybrid Sic matrix. Because of its high creep resistance and thermal conductivity, the CVI Sic matrix is a required base constituent for all the high temperature SiC/SiC systems. By subsequently thermo- mechanical-treating the CMC preform, which consists of the S ylramic-iBN fibers and CVI Sic matrix, process-related defects in the matrix are removed, further improving matrix and CMC creep resistance and conductivity.

Yun, H. M.↗

NASA NTRS1992

Dehydroxylated clay silicates on Mars: Riddles about the Martian regolith solved with ferrian saponites

Clay silicates, resulting from the chemical weathering of volcanic glasses and basaltic rocks of Mars, are generally believed to be major constituents of the martian regolith and atmospheric dust. Because little attention has been given to the role, if any, of Mg-bearing clay silicates on the martian surface, the crystal chemistry, stability, and reactivity of Mg-Fe smectites are examined. Partially dehydroxylated ferrian saponites are suggested to be major constituents of the surface of Mars, regulating several properties of the regolith.

Burns, Roger G.↗

NASA NTRS2000

Constitutive and Stability Behavior of Soils in Microgravity Environment

All aspects of soil stability, bearing capacity, slope stability, the supporting capacity of deep foundations, and penetration resistance depend on soil strength. The stress-deformation and stress-deformation-time behavior of soils are of importance in any problem where ground movements are of interest. In most engineering materials, the strength is derived from internal chemical and physico-chemical forces of interaction, which bond the atoms, molecules, and particles together. In soils, the constitutive relations are mainly derived from interparticle friction between particles and particle groups and dilatancy, and to a lesser extent from particle bonding by weak electrostatic, physico-chemical, and coulomb forces. For engineering purposes, soils are classified as cohesive (clays and silts; typical particle sizes range from 10 nm to 10 micrometers) and cohesionless (sand and gravel; typical particle sizes range from 10 micrometers to 75 mm). The mechanical or constitutive properties of cohesionless soils or granular materials are highly fabric-dependent, highly non-linear, and non-conservative with engineering properties primarily depending on the effects of gravity through self-weight and on the tractions or forces applied to the soil mass. Under moderate-to-high stress levels, the influence of gravity on the behavior of laboratory test specimens may not be pronounced and, therefore, the test results in terrestrial (1-g) environment may be sufficiently conclusive. However at low interparticle stresses, which can result either from low applied (confining) stresses or from excess pore fluid pressures developed within the soil mass without corresponding changes in the applied stresses, the presence of gravitational body forces acting on solid particles and interstitial fluids exerts a pronounced influence on movement of individual particles or particle groups. Such motions, in turn, cause changes in soil fabric which results in significant changes in the interparticle friction forces contributing to the soil's strength and deformation characteristics.

Alshibli, Khalid A.↗

NASA NTRS2002

High Temperature Si-doped BN Interphases for Woven SiC/SiC Composites

The hydrolytic stability of high-temperature deposited Si-doped BN has been shown in the past to be superior in comparison to "pure" BN processed at similar or even higher temperatures. This type of material would be very desirable as a SiC/SiC composite interphase that is formed by chemical infiltration into multi-ply woven preform. However, due to rapid deposition on the preform outer surface at the high processing temperature, this has proven very difficult. To overcome this issue, single plies of woven fabric were infiltrated with Si-doped BN. Three composite panels of different SiC fiber types were fabricated with Si-doped BN interphases including Sylramic, Hi-Nicalon Type S and Sylramic-iBN fiber-types. The latter fiber-type possesses a thin in-situ grown BN layer on the fiber surface. High Si contents (approx. 7 to 10 a/o) and low oxygen contents (less than 1 a/o) were achieved. All three composite systems demonstrated reasonable debonding and sliding properties. The coated Sylramic fabric and composites were weak due to fiber degradation apparently caused during interphase processing by the formation of TiN crystals on the fiber surface. The Hi-Nicalon Type S composites with Si-doped BN interphase were only slightly weaker than Hi-Nicalon Type S composites with conventional BN when the strength on the load-bearing fibers at failure was compared. On the other hand, the Sylramic-iBN fabric and composites with Si-doped BN showed excellent composite and intermediate temperature stress-rupture properties. Most impressive was the lack of any significant interphase oxidation on the fracture surface of stress-ruptured specimens tested well above matrix cracking at 815C.

Morscher, Gregory N.↗

NASA NTRS2004

Advanced SiC/SiC Ceramic Composites For Gas-Turbine Engine Components

NASA Glenn Research Center (GRC) is developing a variety of advanced SiC/SiC ceramic composite (ASC) systems that allow these materials to operate for hundreds of hours under stress in air at temperatures approaching 2700 F. These SiC/SiC composite systems are lightweight (approximately 30% metal density) and, in comparison to monolithic ceramics and carbon fiber-reinforced ceramic composites, are able to reliably retain their structural properties for long times under aggressive gas-turbine engine environments. The key for the ASC systems is related first to the NASA development of the Sylramic-iBN Sic fiber, which displays higher thermal stability than any other SiC- based ceramic fibers and possesses an in-situ grown BN surface layer for higher environmental durability. This fiber is simply derived from Sylramic Sic fiber type that is currently produced at ATK COI Ceramics (COIC). Further capability is then derived by using chemical vapor infiltration (CVI) and/or polymer infiltration and pyrolysis (PIP) to form a Sic-based matrix with high creep and rupture resistance as well as high thermal conductivity. The objectives of this study were (1) to optimize the constituents and processing parameters for a Sylramic-iBN fiber reinforced ceramic composite system in which the Sic-based matrix is formed at COIC almost entirely by PIP (full PIP approach), (2) to evaluate the properties of this system in comparison to other 2700 F Sylramic-iBN systems in which the matrix is formed by full CVI and CVI + PIP, and (3) to examine the pros and cons of the full PIP approach for fabricating hot-section engine components. A key goal is the development of a composite system with low porosity, thereby providing high modulus, high matrix cracking strength, high interlaminar strength, and high thermal conductivity, a major property requirement for engine components that will experience high thermal gradients during service. Other key composite property goals are demonstration at high temperatures of high environmental resistance and high creep resistance, which in turn will result in long component life. Data are presented from a variety of laboratory tests on simple two-dimensional panels that examine these properties and compare the performance of the optimized full PIP system with those of the full CVI and CVI + PIP hybrid systems. Underlying mechanisms for performance differences in the various systems are discussed. Remaining issues for further property enhancement and for application of the full PIP approach for engine components are also discussed, as well as on-going approaches at NASA to solve these issues.

H. M. Yun↗

NASA NTRS1991

Navier-Stokes simulation of the supersonic combustion flowfield in a ram accelerator

A computational study of the ram accelerator, a ramjet-in-tube device for accelerating projectiles to ultrahigh velocities, is presented. The analysis is performed using a fully implicit TVD scheme that efficiently solves the Reynolds-averaged Navier-Stokes equations and the species continuity equations associated with a finite rate combustion model. Previous analyses of this concept were based on inviscid assumptions. The present results indicate that viscous effects are of primary importance; in all the cases studied, shock-induced combustion always started in the boundary layer. The effects of Mach number, mixture composition, pressure, and turbulence are investigated for various configurations. Two types of combustion processes, one stable and the other unstable, were observed depending on the inflow conditions. In the unstable case, a detonation wave is formed, which propagates upstream and unstarts the ram accelerator. In the stable case, a solution that converges to steady-state is obtained, in which the combustion wave remains stationary with respect to the ram accelerator projectile. The possibility of stabilizing the detonation wave by means of a backward facing step is also investigated. In addition to these studies, two numerical techniques were tested. These two techniques are vector extrapolation to accelerate convergence, and a diagonal formulation that eliminates the expense of inverting large block matrices that arise in chemically reacting flows.

Yungster, Shaye↗

NASA NTRS1991

Space R/T base: Propulsion (high thrust chemical)

The topics presented are covered in viewgraph form. The programmatic objective is to provide a technology base and maintain an institutional capability for continued advances in the development of advanced space propulsion systems to support launch, upper stage, orbit transfer and ascent/descent engines. The technical objectives are to study: (1) validated design and analytical codes for cryogenic turbopump bearings and seals; (2) design methodologies and diagnostic capabilities for combustion stability; and (3) reduced operations cost, increase life, safety, higher energy density propellants, and in-situ engine concepts.

Gorland, S.↗

NASA NTRS2009

The Formation and Stability of Carbonic Acid on Outer Solar System Bodies

The radiation chemistry, thermal stability, and vapor pressure of solid-phase carbonic acid (H2CO3) have been studied with mid-infrared spectroscopy. A new procedure for measuring this molecule's radiation stability has been used to obtain intrinsic IR band strengths and half-lives for radiolytic destruction. Results are compared to literature values. We report, for the first time, measurements of carbonic acid's vapor pressure and its heat of sublimation. We also report the first observation of a chemical reaction involving solid-phase carbonic acid. Possible applications of these findings are discussed, with an emphasis on the outer Solar System.

Peeters, Z.↗

NASA NTRS1984

Quantum chemical studies of a model for peptide bond formation. 3. Role of magnesium cation in formation of amide and water from ammonia and glycine

The SN2 reaction between glycine and ammonia molecules with magnesium cation Mg2+ as a catalyst has been studied as a model reaction for Mg(2+)-catalyzed peptide bond formation using the ab initio Hartree-Fock molecular orbital method. As in previous studies of the uncatalyzed and amine-catalyzed reactions between glycine and ammonia, two reaction mechanisms have been examined, i.e., a two-step and a concerted reaction. The stationary points of each reaction including intermediate and transition states have been identified and free energies calculated for all geometry-optimized reaction species to determine the thermodynamics and kinetics of each reaction. Substantial decreases in free energies of activation were found for both reaction mechanisms in the Mg(2+)-catalyzed amide bond formation compared with those in the uncatalyzed and amine-catalyzed amide bond formation. The catalytic effect of the Mg2+ cation is to stabilize both the transition states and intermediate, and it is attributed to the neutralization of the developing negative charge on the electrophile and formation of a conformationally flexible nonplanar five-membered chelate ring structure.

Magnesium/chemistry↗

NASA NTRS1989

Structural materials for space applications

The long-term performance of structural materials in the space environment is a key research activity within NASA. The primary concerns for materials in low Earth orbit (LEO) are atomic oxygen erosion and space debris impact. Atomic oxygen studies have included both laboratory exposures in atomic oxygen facilities and flight exposures using the Shuttle. Characterization of atomic oxygen interaction with materials has included surface recession rates, residual mechanical properties, optical property measurements, and surface analyses to establish chemical changes. The Long Duration Exposure Facility (LDEF) is scheduled to be retrieved in 1989 and is expected to provide a wealth of data on atomic oxygen erosion in space. Hypervelocity impact studies have been conducted to establish damage mechanisms and changes in mechanical properties. Samples from LDEF will be analyzed to determine the severity of space debris impact on coatings, films, and composites. Spacecraft placed in geosynchronous Earth orbit (GEO) will be subjected to high doses of ionizing radiation which for long term exposures will exceed the damage threshold of many polymeric materials. Radiation interaction with polymers can result in chain scission and/or cross-linking. The formation of low molecular weight products in the epoxy plasticize the matrix at elevated temperatures and embrittle the matrix at low temperatures. This affects both the matrix-dominated mechanical properties and the dimensional stability of the composite. Embrittlement of the matrix at low temperatures results in enhanced matrix microcracking during thermal cycling. Matrix microcracking changes the coefficient of thermal expansion (CTE) of composite laminates and produces permanent length changes. Residual stress calculations were performed to estimate the conditions necessary for microcrack development in unirradiated and irradiated composites. The effects of UV and electron exposure on the optical properties of transparent polymer films were also examined to establish the optimum chemical structure for good radiation resistance. Thoughts on approaches to establishing accelerated testing procedures are discussed.

Tenney, Darrel R.↗

NASA NTRS2016

Satellite-Surface Perspectives of Air Quality and Aerosol-Cloud Effects on the Environment: An Overview of 7-SEAS BASELInE

The objectives of 7-SEASBASELInE (Seven SouthEast Asian Studies Biomass-burning Aerosols and Stratocumulus Environment: Lifecycles and Interactions Experiment) campaigns in spring 2013-2015 were to synergize measurements from uniquely distributed ground-based networks (e.g., AERONET (AErosol RObotic NETwork)), MPLNET ( NASA Micro-Pulse Lidar Network)) and sophisticated platforms (e.g.,SMARTLabs (Surface-based Mobile Atmospheric Research and Testbed Laboratories), regional contributing instruments), along with satellite observations retrievals and regional atmospheric transport chemical models to establish a critically needed database, and to advance our understanding of biomass-burning aerosols and trace gases in Southeast Asia (SEA). We present a satellite-surface perspective of 7-SEASBASELInE and highlight scientific findings concerning: (1) regional meteorology of moisture fields conducive to the production and maintenance of low-level stratiform clouds over land; (2) atmospheric composition in a biomass-burning environment, particularly tracers-markers to serve as important indicators for assessing the state and evolution of atmospheric constituents; (3) applications of remote sensing to air quality and impact on radiative energetics, examining the effect of diurnal variability of boundary-layer height on aerosol loading; (4) aerosol hygroscopicity and ground-based cloud radar measurements in aerosol-cloud processes by advanced cloud ensemble models; and (5) implications of air quality, in terms of toxicity of nanoparticles and trace gases, to human health. This volume is the third 7-SEAS special issue (after Atmospheric Research, vol. 122, 2013; and Atmospheric Environment, vol. 78, 2013) and includes 27 papers published, with emphasis on air quality and aerosol-cloud effects on the environment. BASELInE observations of stratiform clouds over SEA are unique, such clouds are embedded in a heavy aerosol-laden environment and feature characteristically greater stability over land than over ocean, with minimal radar surface clutter at a high vertical spatial resolution. To facilitate an improved understanding of regional aerosol-cloud effects, we envision that future BASELInE-like measurement modeling needs fall into two categories: (1) efficient yet critical in-situ profiling of the boundary layer for validating remote-sensing retrievals and for initializing regional transport chemical and cloud ensemble models; and (2) fully utilizing the high observing frequencies of geostationary satellites for resolving the diurnal cycle of the boundary layerheight as it affects the loading of biomass-burning aerosols, air quality and radiative energetics.

AERONET↗

NASA NTRS2003

Creep Resistance of ZrO2 Ceramic Improved by the Addition of a Small Amount of Er2O3

Zirconia (ZrO2) has great technological importance in structural, electrical, and chemical applications. It is the crucial component for state-of-the art thermal barrier coatings and an enabling component as a solid electrolyte for solid-oxide fuel cell systems. Pure ZrO2 is of limited use for industrial applications because of the phase transformations that occur. Upon the addition of stabilizers, cubic (c-ZrO2) and tetragonal (t-ZrO2) forms can be preserved. It is the stabilized and partially stabilized forms of zirconia that function as thermal barrier coatings, solid electrolytes, and oxygen sensors and that have numerous applications in the electrochemical industry. The cubic form of ZrO2 is typically stabilized through Y2O3 additions. However, Y2O3-stabilized zirconia is susceptible to deformation at high temperatures (greater than 900 C) because of the large number of slip systems and the high oxygen diffusion rates, which result in high creep rates at high temperatures. Successful use of ZrO2 at high temperatures requires that new dopant additives be found that will retain or enhance the desirable properties of cubic ZrO2 and yet produce a material with lower creep rates. At the NASA Glenn Research Center, erbium oxide (Er2O3) was identified as a promising dopant for improving the creep resistance of. ZrO2. The selection of Er2O3 was based on the strong interactions of point defects and dislocations. Single crystals of 5 mol% Er2O3- doped ZrO2 rods (4 mm in diameter) and monofilaments (200 to 300 mm in diameter and 30 cm long) were grown using the laser-heated float zone technique, and their creep behavior was measured as a function of temperature. The addition of 5 mol% Er2O3 to single-crystal ZrO2 improved its creep resistance at high temperatures by 2 to 3 orders of magnitude over state-of-the-art Y2O3-doped crystals. Detailed microstructural characterization of ZrO2-Er2O3 single crystals has identified new mechanisms for improving the creep resistance of this class of materials. Adding Er2O3 to ZrO2 results in microstructure of stable and metastable tetragonal precipitates that with thermal treatment evolve to a tweed structure of nanosize tetragonal lamellae. The superior high-temperature creep resistance of Er2O3-doped ZrO2 is attributed to nanoscale precipitation hardening. Doping with Er2O3 will significantly increase the upper-use temperature limit of ZrO2. Potential applications include using Er2O3-doped ZrO2 as a high-temperature fiber for structural applications and adding Er2O3 to reduce the sintering rates of ZrO2 thermal barrier coatings. This work was conducted at Dpto. de F sica de la Materia Condensada, Universidad de Sevilla, Spain, and at NASA Glenn.

Martinez-Fernandez, Julian↗

NASA NTRS1995

Rates of Decomposition of Ribose and other Sugars: Implications for Chemical Evolution

The existence of the RNA world, in which RNA acted as a catalyst as well as an informational macromolecule, assumes a large prebiotic source of ribose or the existence of pre-RNA molecules with backbones different from ribose-phosphate. The generally accepted prebiotic synthesis of ribose, the formose reaction, yields numerous sugars without any selectivity. Even if there were a selective synthesis of ribose, there is still the problem of stability. Sugars are known to be unstable in strong acid or base, but there are few data for neutral solutions. Therefore, we have measured the rate of decomposition of ribose between pH 4 and pH 8 from 40 C to 120 C. The ribose half-lives are very short (73 min at pH 7.0 and 100 C and 44 years at pH 7.0 and 0 C). The other aldopentoses and aldohexoses have half-lives within an order of magnitude of these values, as do 2-deoxyribose, ribose 5-phosphate, and ribose 2,4bisphosphate. These results suggest that the backbone of the first genetic material could not have contained ribose or other sugars because of their instability.

Larralde, Rosa↗