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At least 955 records · Page 53

Ion Exchange Equilibrium and Kinetic Properties of Polyacrylate Films and Applications to Chemical Analysis and Environmental Decontamination

One of the goals of the original proposal was to study how cross-linking affects the properties of an ion exchange material(IEM) developed at Lewis Research Center. However, prior to the start of this work, other workers at LERC investigated the effect of cross-linking on the properties of this material. Other than variation in the ion exchange capacity, the chemical characteristics were shown to be independent of the cross-linking agent, and the degree of cross-linking. New physical forms of the film were developed (film, supported film, various sizes of beads, and powder). All showed similar properties with respect to ion exchange equilibria but the kinetics of ion exchange depended on the surface area per unit mass; the powder form of the IEM exchanging much more rapidly than the other forms. The research performed under this grant was directed towards the application of the IEM to the analysis of metal ions at environmental concentrations.

Tanner, Stephen P.↗

Chemical and Thermal Analysis

Work during the past three years has included significant research in several areas aimed at further clarification of the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) for pipes. Among the areas investigated were the crystallinity changes associated with both the Coflon and Tefzel after various simulated environmental exposures using X-Ray diffraction analysis. We have found that significant changes in polymer crystallinity levels occur as a function of the exposures. These crystallinity changes may have important consequences on the fracture, fatigue, tensile, and chemical resistance of the materials. We have also noted changes in the molecular weight distribution and the increased crosslinking of the Coflon material using Gel Permeation Chromatographic Analysis. Again these changes may result in variations in the mechanical and chemical properties in the material. We conducted numerous analytical studies with methods including X-ray Diffraction, Gel Permeation Chromatography, Fourier Transform Infrared Spectroscopy, and Differential Scanning Calorimetry. We investigated a plethora of aged samples of both Tefzel and Coflon that were forwarded from MERL. Pressurized tests were performed on powdered PVDF in a modified Fluid A, which we will call A-2. In this case the ethylene diamine concentration was increased to 3 percent in methanol. Coflon pipe sections and powdered Coflon were exposed in pressure cells at 1700 psi at three separate test temperatures.

Bulluck, J. W.↗

Polyimide Fibers

A polyimide fiber having textile physical property characteristics and the process of melt extruding same from a polyimide powder. Polyimide powder formed as the reaction product of the monomers 3.4'-ODA and ODPA, and endcapped with phthalic anhydride to control the molecular weight thereof, is melt extruded in the temperature range of 340? C. to 360? C. and at heights of 100.5 inches, 209 inches and 364.5 inches. The fibers obtained have a diameter in the range of 0.0068 inch to 0.0147 inch; a mean tensile strength in the range of 15.6 to 23.1 ksi; a mean modulus of 406 to 465 ksi; and a mean elongation in the range of 14 to 103%.

St.Clair, Terry L.↗

1200 K Compressive Properties of N-Containing Nial

As part of a series of experiments to understand the role of N on the strength of NiAl, a heat of NiAl was enriched with N by melting and atomization to powder in a nitrogen atmosphere. Following consolidation of the powder by hot extrusion, 1200 K compressive properties were measured in air. Within the range of strain rates examined, 10 exp -3 to 10 exp -9/s, the strength of the N-enriched NiAl was greater than that of a simple 15 micron grain size polycrystalline, binary NiAl alloy. For the most part the overall improvement in strength is ascribed to the fine grain size of the N-doped NiAl rather than the alloy chemistry; however, the alloy displayed a complex behavior exhibiting both weakening effects as well as strengthening ones.

Whittenberger, J. D.↗

Recent Developments in Gun Operating Techniques at the NASA Ames Ballistic Ranges

This paper describes recent developments in gun operating techniques at the Ames ballistic range complex. This range complex has been in operation since the early 1960s. Behavior of sabots during separation and projectile-target impact phenomena have long been observed by means of short-duration flash X-rays: new versions allow operation in the lower-energy ("soft") X-ray range and have been found to be more effective than the earlier designs. The dynamics of sabot separation is investigated in some depth from X-ray photographs of sabots launched in the Ames 1.0 in and 1.5 in guns; the sabot separation dynamics appears to be in reasonably good agreement with standard aerodynamic theory. Certain sabot packages appear to suffer no erosion or plastic deformation on traversing the gun barrel, contrary to what would be expected. Gun erosion data from the Ames 0.5 in, 1.0 in, and 1.5 in guns is examined in detail and can be correlated with a particular non- dimensionalized powder mass parameter. The gun erosion increases very rapidly as this parameter is increased. Representative shapes of eroded gun barrels are given. Guided by a computational fluid dynamics (CFD) code, the operating conditions of the Ames 0.5 in and 1.5 in guns were modified. These changes involved: (1) reduction in the piston mass, powder mass and hydrogen fill pressure and (2) reduction in pump tube volume, while maintaining hydrogen mass. These changes resulted in muzzle velocity increases of 0.5-0.8 km/sec, achieved simultaneously with 30-50 percent reductions in gun erosion.

Bogdanoff, D. W.↗

CFD Modelling of Bore Erosion in Two-Stage Light Gas Guns

A well-validated quasi-one-dimensional computational fluid dynamics (CFD) code for the analysis of the internal ballistics of two-stage light gas guns is modified to explicitly calculate the ablation of steel from the gun bore and the incorporation of the ablated wall material into the hydrogen working cas. The modified code is used to model 45 shots made with the NASA Ames 0.5 inch light gas gun over an extremely wide variety of gun operating conditions. Good agreement is found between the experimental and theoretical piston velocities (maximum errors of +/-2% to +/-6%) and maximum powder pressures (maximum errors of +/-10% with good igniters). Overall, the agreement between the experimental and numerically calculated gun erosion values (within a factor of 2) was judged to be reasonably good, considering the complexity of the processes modelled. Experimental muzzle velocities agree very well (maximum errors of 0.5-0.7 km/sec) with theoretical muzzle velocities calculated with loading of the hydrogen gas with the ablated barrel wall material. Comparison of results for pump tube volumes of 100%, 60% and 40% of an initial benchmark value show that, at the higher muzzle velocities, operation at 40% pump tube volume produces much lower hydrogen loading and gun erosion and substantially lower maximum pressures in the gun. Large muzzle velocity gains (2.4-5.4 km/sec) are predicted upon driving the gun harder (that is, upon using, higher powder loads and/or lower hydrogen fill pressures) when hydrogen loading is neglected; much smaller muzzle velocity gains (1.1-2.2 km/sec) are predicted when hydrogen loading is taken into account. These smaller predicted velocity gains agree well with those achieved in practice. CFD snapshots of the hydrogen mass fraction, density and pressure of the in-bore medium are presented for a very erosive shot.

Bogdanoff, D. W.↗

Polyimide Fibers

A polyimide fiber having textile physical property characteristics and the process of melt extruding same from a polyimide powder. Polyimide powder formed as the reaction product of the monomers 3.4'-ODA and ODPA, and end- capped with phthalic anhydride to control the molecular weight thereof, is melt extruded in the temperature range of 340 C. to 360 C. and at heights of 100.5 inches. 209 inches and 364.5 inches. The fibers obtained have a diameter in the range of 0.0068 inch to 0.0147 inch; a mean tensile strength in the range of 15.6 to 23.1 ksi; a mean modulus of 406 to 465 ksi, and a mean elongation in the range of 14 to 103%.

St.Clair, Terry L.↗

Imide Oligomers Containing Pendent and Terminal Phenylethynyl Groups-2

As part of a program to develop high-performance/high-temperature structural resins for aeronautical applications, imide oligomers containing pendent and terminal phenylethynyl groups were prepared, characterized and the cured resins evaluated as composite matrices. The oligomers were prepared at a calculated number-average molecular weight of 5000 g/mol and contained 15-20 mol% pendent phenylethynyl groups. In previous work, an oligomer containing pendent and terminal phenylethynyl groups exhibited a high glass transition temperature (approximately 313 C), and laminates therefrom exhibited high compressive properties, but processability, fracture toughness, microcrack resistance and damage tolerance were less than desired. In an attempt to improve these deficiencies, modifications in the oligomeric backbone involving the incorporation of 1,3-bis(3-aminophenoxy)benzene were investigated as a means of improving processability and toughness without detracting from the high glass transition temperature and high compressive properties. The amide acid oligomeric solutions were prepared in N-methyl-2-pyrrolidinone and were subsequently processed into imide powder, thin films, adhesive tape and carbon fiber prepreg. Neat resin plaques were fabricated from imide powder by compression moulding. The maximum processing pressure was 1.4 MPa and the cure temperature ranged from 350 to 371 C for 1 h for the mouldings, adhesives, films and composites. The properties of the 1,3-bis(3-aniinophenoxy)benzene modified cured imide oligomers containing pendent and terminal phenylethynyl groups are compared with those of previously prepared oligomers containing pendent and terminal phenylethynyl groups of similar composition and molecular weight.

Connell, J. W.↗

Monolithic Cu-Cr-Nb Alloys for High Temperature, High Heat Flux Applications

Work during the prior four years of this grant has resulted in significant advances in the development of Cu-8 Cr4 Nb and related Cu-Cr-Nb alloys. The alloys are nearing commercial use in the Reusable Launch Vehicle (RLV) where they are candidate materials for the thrust cell liners of the aerospike engines being developed by Rocketdyne. During the fifth and final year of the grant, it is proposed to complete development of the design level database of mechanical and thermophysical properties and transfer it to NASA Glenn Research Center and Rocketdyne. The database development work will be divided into three main areas: Thermophysical Database Augmentation, Mechanical Testing and Metallography and Fractography. In addition to the database development, work will continue that is focussed on the production of alternatives to the powder metallurgy alloys currently used. Exploration of alternative alloys will be aimed at both the development of lower cost materials and higher performance materials. A key element of this effort will be the use of Thermo-Calc software to survey the solubility behavior of a wide range of alloying elements in a copper matrix. The ultimate goals would be to define suitable alloy compositions and processing routes to produce thin sheets of the material at either a lower cost, or, with improved mechanical and thermal properties compared to the current Cu-Cr-Nb powder metallurgy alloys.

Ellis, David L.↗

X-Ray Diffraction Techniques for a Field Instrument: Patterns of Lithologic Provences

Future exploration of Mars will attempt to shed light on the mineralogy of surface materials. Instruments deployed from remote platforms should have the capability to conduct both intensive analyses as well as rapid, reconnaissance surveys while they function in the martian environment as surrogate geologists. In order to accommodate the reconnaissance mode of analysis and to compensate for analytical limitations imposed by the space-flight conditions, data analysis methods are being developed that will permit interpretation of data by recognition of signatures or "fingerprints". Specifically, we are developing a technique which will allow interpretation of diffraction patterns by recognition of characteristic signatures of different lithologic provences. This technique allows a remote vehicle to function in a rapid-scan mode using the lithologic signature to determine where a more thorough analysis is needed. An x-ray diffraction pattern is characterized by the angular positions of diffracted x-rays, x-ray intensity levels and background radiation levels. These elements may be used to identify a generalized x-ray signature. Lithologic signatures are being developed in two ways. A signature is composed using the ideal powder diffraction indices from the mineral assembledge common to a specific lithologic provence. This is then confirmed using a laboratory diffraction pattern of a whole rock powder. Preliminary results comparing the diffraction signatures of the major mineral assembledges common to basalt, carbonate, and evaporite basin deposits indicate that lithologies are differentiable as a "fingerprint". Statistical analyses are being performed to establish the confidence levels of this technique.

Marshall, J.↗

Constraints on the Nature and Distribution of Iridium Host Phases at the Cretaceous-Tertiary Boundary: Implications for Projectile Identity and dispersal on impact

Among Cretaceous-Tertiary boundary sites worldwide, variations in the concentrations and ratios of elements commonly enriched in meteorites complicate traditional geochemical attempts at impactor identification. Yet they may provide constraints on the physical and chemical processes associated with large-body disruption and dispersal, as well as with diagenesis of projectile components. To this end, we continue our efforts to identify the mineral host-phases of projectile-derived elements, particularly for Ir, and to document their partitioning between crater deposits and ejecta resulting from the Chicxulub basin-forming impact. Building on earlier work, we used INAA to measure Ir concentrations in successively smaller splits of finely powdered impact melt breccia from the Chicxulub Crater in Mexico (sample Y6Nl9-R(b)), and K/T boundary fish clay from Stevns Klint, Denmark (sample FC-1, split from 40 kg of homogenized material intended as an analytical standard). Results for the Chicxulub sample show a heterogeneous Ir distribution and document that at least five discrete Ir-bearing host phases were isolated in subsequent splits, having Ir masses equivalent to pure Ir spheres from about 0.8 to about 3.5 mm in diameter. Three of these are within a sufficiently reduced mass of powder to warrant searching for them using backscattered electron microscopy. In contrast, successively smaller splits of the Stevns Klint fish clay show no statistically significant deviation from the reported value of 32 +/- 2 ng/g Ir, suggesting a uniform Ir host-phase distribution. For the smallest split obtained thus far (100 +/- 40 ng/g Ir), a pure Ir sphere of equivalent Ir mass would be <0.05 min in diameter. (n.b. Although homogenizing and sieving of FC-1 to <75 min obviously obscured variations in stratigraphic distribution, it is unlikely to have affected the size-frequency distribution of Ir host phases.) We previously identified micrometer-scale Ir host phases by electron microscopy in melt-rock samples from two widely separated drill holes at the Chicxulub Basin, including a replicate split of Y6-NI9-R. One is an aggregate of subhedral Ir metal grains enclosed in silicate, in which no other Pt group elements (PGE) were detected. A second particle with twice the mass as the first, concentrated predominantly in a single grain, is associated with minor concentrations of Os, Ru, and Pt, and with adhering particles of corundum and perovskite. A third Ir-rich particle, with a greater apparent Os concentration, was identified before being lost as a result of charging under the electron beam. In addition to demonstrating the preservation of projectile components within the Chicxulub Crater, analogous phase associations in Ca- and Al-rich inclusions (CAI) from C2 and C3 chondrites suggest to us that these melt-rock Ir host phases are relics from a carbonaceous chondrite K/T boundary impactor Although the obviously low Ru/Ir ratios of the Chicxulub Ir host phases are qualitatively consistent with suggested PGE fractionation with distance during condensation in an ejecta cloud, it seems difficult to explain the accumulation of the about 3 x 10(exp 11) Ir atoms required to form a about 10(exp -10) g nugget of pure Ir metal within a jet of vaporized projectile expanding at 1-4 km/s, or to effectively exclude or remove commonly alloyed PGE and siderophile elements by fractionation processes resulting from condensation, oxidation, sulfidization, exsolution, or autometamorphism during cooling of the melt. We do not dismiss the importance of these processes entirely; on the contrary, other geochemical and mineralogical aspects of the melt rocks require them, and condensation from the expanding ejecta cloud appears to best explain the primary Ir host-phase distribution in the fish clay, as well as the high Ir concentrations associated with spinel-bearing spheroids at the K/T boundary in the Pacific Ocean . If the "relict" hypothesis is correct, micronuggets of other PGEs and alloys, not detected by our INAA screening, should also occur in the melt rocks. Possibly, the discrete host phases with lesser Ir masses are such alloys with subordinate Ir, rather than simply smaller, predominantly Ir-bearing particles. A CAI source for the relics would be consistent with either a comet or an asteroid K/T impact at Chicxulub. (Additional information contained in the original.)

Schuraytz, B. C.↗

Laser Brazing of High Temperature Braze Alloy

The Space Shuttle Main Engine (SSME) consists of 1080 conical tubes, which are furnace brazed themselves, manifolds, and surrounding structural jacket making almost four miles of braze joints. Subsequent furnace braze cycles are performed due to localized braze voids between the coolant tubes. SSME nozzle experiences extremely high heat flux (180 mW/sq m) during hot fire. Braze voids between coolant tubes may result in hot combustion gas escape causing jacket bulges. The nozzle can be disqualified for flight or result in mission failure if the braze voids exceed the limits. Localized braze processes were considered to eliminate braze voids, however, damage to the parent materials often prohibited use of such process. Being the only manned flight reusable rocket engine, it has stringent requirement on the braze process. Poor braze quality or damage to the parent materials limits the nozzle service life. The objective of this study was to develop a laser brazing process to provide quality, localized braze joints without adverse affect on the parent materials. Gold (Au-Cu-Ni-Pd-Mn) based high temperature braze alloys were used in both powder and wire form. Thin section iron base superalloy A286 tube was used as substrate materials. Different Laser Systems including CO2 (10.6 micrometers, 1kW), ND:YAG (1.06 micrometers, 4kW). and direct diode laser (808nm. 150W) were investigated for brazing process. The laser process variables including wavelength. laser power, travel speed and angle of inclination were optimized according to bead geometry and braze alloy wetting at minimum heat input level, The properties of laser brazing were compared to that of furnace brazing. Microhardness profiles were used for braze joint property comparison between laser and furnace brazing. The cooling rate of laser brazing was compared to furnace brazing based on secondary dendritic arm spacing, Both optical and Scanning Electron Microscope (SEM) were used to evaluate the microstructures of the braze materials and tube substrate. Metallography of the laser braze joint was compared to the furnace braze. SEM Energy Disperse X-Ray Spectra (EDX) and back scattered imaging were used to analyze braze alloy segregation. Although all of the laser systems, CO2, ND:YAG, and direct diode laser produced good braze joint, the direct diode laser was selected for its system simplicity, compactness and portability. Excellent laser and braze alloy coupling is observed with powder alloy compared to braze alloy wire. Good wetting is found with different gold based braze alloys. The laser brazing process can be optimized so that the adverse affect on the parent materials can be eliminated. Metallography of the laser braze joint has shown that quality braze joint was produced with laser brazing process. Penetration of the laser braze to the substrate is at neglectable level. Zero penetration is observed. Microstructure examinations shown that no observable changes of the microstructure (grain structure and precipitation) in the HAZ area between laser braze and furnace braze. Wide gaps can be laser brazed with single pass for up to 0.024 inches. Finer dendritic structure is observed in laser brazing compared with equiaxial and coarser grain of the furnace brazing microstructure. Greater segregation is also found in the furnace braze. Higher hardness of the laser braze joint comparing to furnace braze is observed due to the fast cooling rate and Finer microstructure in the laser brazing. Laser braze joint properties meet or exceed the furnace joint properties. Direct diode laser for thin section tube brazing with high temperature braze alloys have been successfully demonstrated. The laser's high energy density and precise control has shown significant advantages in reducing process heat input to the substrates and provide high quality braze joints comparing to other localized braze process such as torch, TIG, and MPTA processes. Significant cost savings can be realized particularly with localized braze comparing to a full furnace braze cycle.

Gao, Y. P.↗

Solid Freeform Fabrication of Continuous Fiber Reinforced Composites for Propulsion Applications

For propulsion related applications, materials must be able to demonstrate excellent ablation and oxidation resistance at temperature approaching 3500'C, adequate load bearing capabilities, non-catastrophic failure modes, and ability to withstand transient thermal shock. A potential list of propulsion-material property requirements includes, low density, high elastic modulus, low thermal-expansion coefficient, high thermal conductivity, excellent erosion and oxidation/corrosion resistance, and flaw-insensitivity. In many cases, they will also need to be able to be joined, survive thermal cycling and multi-axial stress states, and for reusable applications, the materials must maintain the above attributes after prolonged exposure to extremely harsh chemical environments. The final and possibly most important attribute for these materials are the need to be lower cost and readily available in large quantities. Recently, Advanced Ceramics Research, Inc. (ACR) has developed low cost, flexible- manufacturing processes for Zr & Hf-based carbon fiber reinforced composites, materials with good oxidation and ablation resistance up to 3500 C. This process, called Continuous Composite Co-extrusion (C(sup 3)), incorporates carbon fibers to fabricate 'in-situ' carbide and boride-matrix/carbon fiber composites. This is a variation of ACR's manufacturing process for low-cost structural ceramic materials called Fibrous Monoliths With carbon fiber reinforcements. Fibrous Monolithic materials have a distinct fibrous texture, consist of intertwined cells of a primary phase, separated by cell boundaries of a tailored secondary phase and show very high fracture energies, damage tolerance, and graceful failure. Since they are monolithic powder based composites-, they can be manufactured by conventional powder processing techniques using inexpensive raw materials. This combination of high performance and low cost is a breakthrough that could enable wider application of ceramics in high temperature applications. Typical volume fractions of the two phases are 80 to 95% for the cell phase and 5 to 20% for the interpenetrating cell boundary phase. ACR is currently developing an innovative solid freeform form fabrication (SFF) approach to produce Hf and Zr based ceramic composite components reinforced with continuous carbon fiber tows for critical structural components such as tubes and blisks. The process is simple, robust and will be widely applicable to a number of material systems. This technique was originally developed at the University of Delaware Center for Composite Materials (UD-CCM) for rapid fabrication of polymer matrix composites by a technique called automated tow placement or ATP. The current process is being developed in collaboration with UD-CCM. The paper will detail the freeform fabrication process to create low-cost ceramic fiber reinforced composites for high-temperature applications. The results of mechanical properties and microstructural characterization will be presented, together with examples of complex shapes and parts. It is believed that the process will be able to create complex shaped parts for propulsion applications at an order of magnitude lower cost than current CVI and PIP process.

Vaidyanathan, R.↗

Detection of Crystalline Hematite Mineralization on Mars by the Thermal Emission Spectrometer: Evidence for Near-surface Water

The Thermal Emission Spectrometer (TES) instrument on the Mars Global Surveyor (MGS) mission has discovered a remarkable accumulation of crystalline hematite ((alpha-Fe2O3) that covers an area with very sharp boundaries approximately 350 by 350-750 km in size centered near 2 S latitude between 0 and 5 W longitude (Sinus Meridiani). Crystalline hematite is uniquely identified by the presence of fundamental vibrational absorption features centered near 300, 450, and >525/cm, and by the absence of silicate fundamentals in the 1000/cm region. Spectral features resulting from atmospheric CO2, dust, and water ice were removed using a radiative transfer model. The spectral properties unique to Sinus Meridiani were emphasized by removing the average spectrum of the surrounding region. The depth and shape of the hematite fundamental bands show that the hematite is crystalline and relatively coarse grained (>5-10 micron). Diameters up to and greater than 100s of micrometers are permitted within the instrumental noise and natural variability of hematite spectra. Hematite particles <5-10 micron in diameter (either as an unpacked or hard-packed powders) fail to match the TES spectra. The spectrally-derived areal abundance of hematite varies with particle size from approximately 10% for particles >30 micron in diameter to 40-60% for unpacked 10 micron powders. The hematite in Sinus Meridiani is thus distinct from the fine-grained (diameter <5-10 micron), red, crystalline hematite considered, on the basis of visible, near-IR data, to be a minor spectral component in Martian bright regions like Olympus-Amazonis. Sinus Meridiani hematite is closely associated with a smooth, layered, friable surface that is interpreted to be sedimentary in origin. This material may be the uppermost surface in the region, indicating that it could be a late-stage sedimentary unit, or it could be a layered portion of the heavily cratered plains units. We consider five possible mechanisms for the formation of coarse-grained, crystalline hematite. These processes fall into two classes depending on whether they require a significant amount of near-surface water: (1) chemical precipitation that includes origin by (a) precipitation from oxygenated, Fe-rich water (iron formations), (b) hydrothermal extraction and crystal growth.

Christensen, P. R.↗

SEM Characterization of Extinguished Grains from Plasma-Ignited M30 Charges

M30 propellant grains that had been ignited in interrupted closed bomb experiments were characterize by scanning electron microscopy (SEM). Previous chemical analysis of extinguished grains had given no indications of plasma-propellant chemical interactions that could explain the increased burning rates that had been previously observed in full-pressure closed bomb experiments. (This does not mean that there is no unique chemistry occurring with plasma ignition. It may occur very early in the ignition event and then become obscured by the burning chemistry.) In this work, SEM was used to look at grain morphologies to determine if there were increases in the surface areas of the plasma-ignited grains which would contribute to the apparent increase in the burning rate. Charges were made using 30 propellant grains (approximately 32 grams) stacked in two tiers and in two concentric circles around a plastic straw. Each grain was notched so that, when the grains were expelled from the bomb during extinguishment, it could be determined in which tier and which circle each grain was originally packed. Charges were ignited in a closed bomb by either a nickel wire/Mylar-capillary plasma or black powder. The bomb contained a blowout disk that ruptured when the pressure reached 35 MPa, and the propellant was vented into a collection chamber packed with polyurethane foam. SEM analysis of the grains fired with a conventional black powder igniter showed no signs of unusual burning characteristics. The surfaces seemed to be evenly burned on the exteriors of the grains and in the perforations. Grains that had been subjected to plasma ignition, however, had pits, gouges, chasms, and cracks in the surfaces. The sides of the grains closest to the plasma had the greatest amount of damage, but even surfaces facing the outer wall of the bomb had small pits. The perforations contained gouges and abnormally burned regions (wormholes) that extended into the web. The SEM photos indicated that a grain from the top tier, which was farther away from the plasma ignition source, sustained more plasma-induced damage to the perforations and the web than did the grains on the bottom tier.

Kinkennon, A.↗

Laser Materials Processing for NASA's Aerospace Structural Materials

Lasers are useful for performing operations such as joining, machining, built-up freeform fabrication, and surface treatment. Due to the multifunctional nature of a single tool and the variety of materials that can be processed, these attributes are attractive in order to support long-term missions in space. However, current laser technology also has drawbacks for space-based applications. Specifically, size, power efficiency, lack of robustness, and problems processing highly reflective materials are all concerns. With the advent of recent breakthroughs in solidstate laser (e.g., diode-pumped lasers) and fiber optic technologies, the potential to perform multiple processing techniques in space has increased significantly. A review of the historical development of lasers from their infancy to the present will be used to show how these issues may be addressed. The review will also indicate where further development is necessary to realize a laser-based materials processing capability in space. The broad utility of laser beams in synthesizing various classes of engineering materials will be illustrated using state-of-the art processing maps for select lightweight alloys typically found on spacecraft. Both short- and long-term space missions will benefit from the development of a universal laser-based tool with low power consumption, improved process flexibility, compactness (e.g., miniaturization), robustness, and automation for maximum utility with a minimum of human interaction. The potential advantages of using lasers with suitable wavelength and beam properties for future space missions to the moon, Mars and beyond will be discussed. The laser processing experiments in the present report were performed using a diode pumped, pulsed/continuous wave Nd:YAG laser (50 W max average laser power), with a 1064 nm wavelength. The processed materials included Ti-6AI-4V, Al-2219 and Al-2090. For Phase I of this project, the laser process conditions were varied and optimized to see the effects on melt-quenching, cladding/alloying (using the pre-placed powder technique), and cutting. Key parameters such laser power, pulse repetition frequency, process speed, and shield gas flow and the observed process characteristics such as plasma formation during laser/material interaction, have been reported for all experimental runs. Preliminary materials characterization of select samples was carried out using various microscopy, diffraction, spectroscopy and microhardness test methods, and reported. Select nitridation results of Ti-6AI-4V using nitrogen assist gas indicated the successful formation of hard titanium nitrides with much higher hardness (2180 kg/sq mm). A cost-effective and simple powder delivery system has been successfully fabricated for the further experimentation in Phase H.

Nagarathnam, Karthik↗

Solid Free-Form Fabrication of Continuous Fiber Reinforced Composites for Propulsion Application

For propulsion related applications, materials must be able to demonstrate excellent ablation and oxidation resistance at temperature approaching 3500 C, adequate load bearing capabilities, non-catastrophic failure modes, and ability to withstand transient thermal shock. A potential list of propulsion-material property requirements includes, low density, high elastic modulus, low thermal-expansion coefficient, high thermal conductivity, excellent erosion and oxidation/corrosion resistance, and flaw-insensitivity. In many cases, they will also need to be able to be joined, survive thermal cycling and multi-axial stress states, and for reusable applications, the materials must maintain the above attributes after prolonged exposure to extremely harsh chemical environments. The final and possibly most important attribute for these materials are the need to be lower cost and readily available in large quantities. Recently, Advanced Ceramics Research, Inc. (ACR) has developed low cost, flexible-manufacturing processes for Zr & Hf-based carbon fiber reinforced composites, materials with good oxidation and ablation resistance up to 3500 C. This process, called Continuous Composite Co-extrusion (C(sup 3)), incorporates carbon fibers to fabricate 'in-situ' carbide and boride-matrix/carbon fiber composites. M is a variation of ACR's manufacturing process for low-cost structural ceramic materials called Fibrous Monoliths with carbon fiber reinforcements. Fibrous Monolithic materials have a distinct fibrous texture, consist of intertwined cells of a primary phase, separated by cell boundaries of a tailored secondary phase and show very high fracture energies, damage tolerance, and graceful failure. Since they are monolithic powder based composites; they can be manufactured by conventional powder processing techniques using inexpensive raw materials. This combination of high performance and low cost is a breakthrough that could enable wider application of ceramics in high temperature applications. Typical volume fractions of the two phases are 80 to 95% for the cell phase and 5 to 20% for the interpenetrating cell boundary phase. ACR is currently developing an innovative solid freeform form fabrication (SFF) approach to produce Hf and Zr based ceramic composite components reinforced with continuous carbon fiber tows for critical structural components such as tubes and blisks. The process is simple, robust and will be widely applicable to a number of material systems. This technique was originally developed at the University of Delaware Center for Composite Materials (UD-CCM) for rapid fabrication of polymer matrix composites by a technique called automated tow placement or ATP. The current process is being developed in collaboration with UD-CCM. The paper will detail the freeform fabrication process to create low-cost ceramic fiber reinforced composites for high-temperature applications. The results of mechanical properties and microstructural characterization will be presented, together with examples of complex shapes and parts. It is believed that the process will be able to create complex shaped parts for propulsion applications at an order of magnitude lower cost than current CVI and PIP processes.

Vaidyanathan, R.↗

Freely Suspended Smectic Filaments and the Structure of the B7 Phase of MHOBOW

Our recent discovery of the spontaneous formation of chiral domains in fluid smectic phases of achiral bow-shaped molecules opens up a wide variety of possibilities for new liquid crystal phases and phenomena. The basic, spontaneously chiral layer structure of the highest temperature fluid smectic phases, the B2 and B7, are shown. One of the most intriguing aspects of this structure is the plethora of possible phases coming from different stacking sequences of the polar ordering and tilt directions. The four possibilities of next-nearest neighbor alternation are shown. In the original material studied, NOBOW, the ground states found are antiferroelectric, either the racemic SmC(sub S)P(sub A) or the chiral SmC(sub A)P(sub A). We are currently studying MHOBOW, synthesized by D. Walba which, by virtue of its methyl hexyloxy tail has a tendency to form anticlinic layer interfaces, in the hope of finding a phase with a ferroelectric ground state, either SmC(sub A)P(sub S) or SmC(sub S)P(sub A), which can be obtained in NOBOW only by applying a field. Preliminary observations of MHO-BOW have made its study, from the point of view of understanding novel LC structures, extremely high priority. The following truly remarkable characteristics have been revealed: (i) The smectic phase grows out of the isotropic in the form of helical ribbons. The resulting planar aligned textures of focal conics with layers normal to glass plates exhibit bizarre modulations, including stripes and checker-boards. These have also been seen in other materials suggesting that this is a new phase (tentatively called B7), which is a fluid smectic with some kind of in-layer structure. (ii) It is virtually impossible to make freely suspended films of MHOBOW. Rather it makes the freely suspended filaments which preliminary x-ray scattering experiments reveal to have the nested cylinder layer structure indicated; (iii) The powder x-ray diffraction exhibits four resolution-limited smectic layering peaks, very close in layer spacing, which vary continuously with T. This is further evidence for a more complex three dimensional structure than NOBOW, which has a typical single layering reflection. (iv) The x-ray structure factor of the layering peak of the filaments is extraordinarily complex and rich. Varying in qL (the scattering vector component along the filament axis) from a double slit-like pattern to modulated layer-like patterns, as qH (the scattering vector component normal to the filament axis) is varied over the range where the four powder peaks are located. These results suggest some kind of mosaic structure, perhaps with different layer spacings corresponding to the different stacking sequences. Recent x-ray diffraction experiments show that the peaks are modulated in intensity upon translation along a filament, in domains of several hundred microns dimension. These preliminary experiments suggest that the B7 is a fluid smectic with extremely unusual and fascinating structures. Of all of the many hundreds of fluid smectic materials we have attempted to study in the freely suspended film geometry over the years, only a few have failed to form films, and none showed any great tendency to form filaments, although this clearly should be a possible freely suspended smectic LC morphology. On several occasions in the past we have intentionally tried to make filaments from a variety of smectics without success. Thus the smectic filament formation property makes the B7 phase unique. It seems quite likely that the stability of filaments is related to the in-plane structure. The filaments exhibit other interesting structural and optical features. They are birefringent with a local optic axis which is oblique and which can vary continuously along filament and which can be manipulated with an electric field applied normal to the fiber, as if the field were causing a rotation of the optic axis about the fiber axis. Rapid displacement of the ends of the fiber toward one another causes a macroscopic helixing at low T and causes thick regions to transiently appear at high T, a 1D analog of island formation on a rapidly compressed film.

Clark, N.↗