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Improved silicon carbide for advanced heat engines. I - Process development for injection molding

Alternate processing methods have been investigated as a means of improving the mechanical properties of injection-molded SiC. Various mixing processes (dry, high-sheer, and fluid) were evaluated along with the morphology and particle size of the starting beta-SiC powder. Statistically-designed experiments were used to determine significant effects and interactions of variables in the mixing, injection molding, and binder removal process steps. Improvements in mechanical strength can be correlated with the reduction in flaw size observed in the injection molded green bodies obtained with improved processing methods.

Whalen, Thomas J.↗

Tribological and microstructural comparison of HIPped PM212 and PM212/Au self-lubricating composites

The feasibility of replacing the silver with the volumetric equivalent of gold in the chromium carbide-based self-lubricating composite PM212 (70 wt. percent NiCo-Cr3C2, 15 percent BaF2/CaF2 eutectic) was studied. The new composite, PM212/Au has the following composition: 62 wt. percent NiCo-Cr3C2, 25 percent Au, 13 percent BaF2/CaF2 eutectic. The silver was replaced with gold to minimize the potential reactivity of the composite with possible environmental contaminants such as sulfur. The composites were fabricated by hot isostatic pressing (HIPping) and machined into pin specimens. The pins were slid against nickel-based superalloy disks. Sliding velocities ranged from 0.27 to 10.0 m/s and temperatures from 25 to 900 C. Friction coefficients ranged from 0.25 to 0.40 and wear factors for the pin and disk were typically low 10(exp -5) cu mm/N-m. HIPped PM212 measured fully dense, whereas PM212/Au had 15 percent residual porosity. Examination of the microstructures with optical and scanning electron microscopy revealed the presence of pores in PM212/Au that were not present in PM212. Though the exact reason for the residual porosity in PM212/Au was not determined, it may be due to particle morphology differences between the gold and silver and their effect on powder metallurgy processing.

Bogdanski, Michael S.↗

Tribological and microstructural comparison of HIPped PM212 and PM212/Au self-lubricating composites

The feasibility of replacing the silver with the volumetric equivalent of gold in the chromium carbide-based self-lubricating composite PM212 (70 wt percent NiCo-Cr3C2, 15 percent BaF2/CaF2 eutectic) was studied. The new composite, PM212/Au has the following composition: 62 wt percent NiCo-Cr3C2, 25 percent Au, 13 percent BaF2/CaF2 eutectic. The silver was replaced with gold to minimize the potential reactivity of the composite with possible environmental contaminants such as sulfur. The composites were fabricated by hot isostatic pressing (HIPping) and machined into pin specimens. The pins were slid against nickel-based superalloy disks. Sliding velocities ranged from 0.27 to 10.0 m/s and temperatures from 25 to 900 C. Frictions coefficients ranged from 0.25 to 0.40 and wear factors for the pin and disk were typically low 10(exp -5) cu mm/N-m. HIPped PM212 measured fully dense, whereas PM212/Au had 15 percent residual porosity. Examination of the microstructures with optical and scanning electron microscopy revealed the presence of pores in PM212/Au that were not present in PM212. Though the exact reason for the residual porosity PM212/Au was not determined, it may be due to practice morphology differences between the gold and silver and their effect on powder metallurgy processing.

Bogdanski, Michael S.↗

Ceramic Inclusions In Powder Metallurgy Disk Alloys: Characterization and Modeling

Powder metallurgy alloys are increasingly used in gas turbine engines, especially as the material chosen for turbine disks. Although powder metallurgy materials have many advantages over conventionally cast and wrought alloys (higher strength, higher temperature capability, etc.), they suffer from the rare occurrence of ceramic defects (inclusions) that arise from the powder atomization process. These inclusions can have potentially large detrimental effect on the durability of individual components. An inclusion in a high stress location can act as a site for premature crack initiation and thereby considerably reduce the fatigue life. Because these inclusions are exceedingly rare, they usually don't reveal themselves in the process of characterizing the material for a particular application (the cumulative volume of the test bars in a fatigue life characterization is typically on the order of a single actual component). Ceramic inclusions have, however, been found to be the root cause of a number of catastrophic engine failures. To investigate the effect of these inclusions in detail, we have undertaken a study where a known population of ceramic particles, whose composition and morphology are designed to mimic the 'natural' inclusions, are added to the precursor powder. Surface connected inclusions have been found to have a particularly large detrimental effect on fatigue life, therefore the volume of ceramic 'seeds' added is calculated to ensure that a minimum number will occur on the surface of the fatigue test bars. Because the ceramic inclusions are irregularly shaped and have a tendency to break up in the process of extrusion and forging, a method of calculating the probability of occurrence and expected intercepted surface and embedded cross-sectional areas were needed. We have developed a Monte Carlo simulation to determine the distributions of these parameters and have verified the simulated results with observations of ceramic inclusions found in macro slices from extrusions and forgings. The ultimate goal of this study will be to use probabilistic methods to determine the reliability detriment that can be attributed to these ceramic inclusions.

Bonacuse, Pete↗

Ceramic Inclusions in Powder Metallurgy Disk Alloys: Characterization and Modeling

Powder metallurgy alloys are increasingly used in gas turbine engines, especially in turbine disk applications. Although powder metallurgy materials have many advantages over conventionally cast and wrought alloys (higher strength, higher temperature capability, etc.), they suffer from the rare occurrence of ceramic defects (inclusions) that are inherent to the powder atomization process. These inclusions can have a potentially large detrimental effect on the durability of individual components. An inclusion in a high stress location can act as a site for premature crack initiation and thereby considerably reduce the fatigue life. Because these inclusions are exceedingly rare, they typically do not reveal themselves in the process of characterizing the material for a particular application (the cumulative volume of the test bars in a fatigue life characterization is typically on the order of a single actual component). Ceramic inclusions have, however, been found to be the root cause of a number of catastrophic engine failures. To investigate the effect of these inclusions in detail, we have undertaken a study where known populations of ceramic particles, whose composition and morphology are designed to mimic the "natural" inclusions, are added to the precursor powder. Surface-connected inclusions have been found to have a particularly large detrimental effect on fatigue life; therefore, the quantity of ceramic "seeds" added is calculated to ensure that a minimum number will intersect the surface of the fatigue test bars. Because the ceramic inclusions are irregularly shaped and have a tendency to break up in the process of extrusion and forging, a method of calculating the probability of occurrence and expected intercepted surface area was needed. We have developed a Monte Carlo simulation to determine the distributions of these parameters and have verified the simulated results with observations of ceramic inclusions found in macroscopic slices from extrusions and forgings. Fatigue specimens have been machined from Udimet 720 (a powder metallurgy superalloy) forgings, to determine the effects of the inclusions on fatigue life. The ultimate goal of this study will be to use probabilistic methods to determine the reliability detriment that can be attributed to these ceramic inclusions. This work has been supported by the Ultra Safe and Ultra- Efficient Engine Technologies programs.

Bonacuse, Peter J.↗

Monte Carlo Simulation of Nanoparticle Encapsulation in Flames

Gas-phase combustion (flame) synthesis has been an essential industrial process for producing large quantities of powder materials such as carbon black, titanium dioxide, and silicon dioxide. Flames typically produce simple oxides, with carbon black being the noted exception because the oxides of carbon are gaseous and are easily separated from the particulate matter that is formed during fuel pyrolysis. Furthermore, the powders produced in flames are usually agglomerated, nanometer-sized particles (nanoparticles). This composition and morphology is acceptable for many applications. However, the present interest in nanoparticles for advanced materials application has led to efforts to employ flames for the synthesis of unagglomerated nanoparticles (2 to 100 nm) of metals and non-oxide ceramics. Sodium-halide chemistry has proven to be viable for producing metals and non-oxide ceramics in flames. Materials that have been produced to date include Si (Calcote and Felder, 1993), TiN, TiB2, TiC, TiSi2, SiC, B4C (Glassman et al, 1993) Al, W, Ti, TiB2, AlN, and W-Ti and Al-AlN composites (DuFaux and Axelbaum, 1995, Axelbaum et al 1996,1997). Many more materials are possible. The main challenge that faces application of flame synthesis for advanced materials is overcoming formation of agglomerates in flames (Brezinsky, 1997). The high temperatures and high number densities in the flame environment favor the formation of agglomerates. Agglomerates must be avoided for many reasons. For example, when nanopowders are consolidated, agglomerates have a deleterious effect on compaction density, leading to voids in the final part. Efforts to avoid agglomeration in flames without substantially reducing particle number density and, consequently, production rate, have had limited success. Another critical challenge that faces all synthesis routes for nanopowders is ensuring that the powders are high purity and that the process is scaleable. Though the containerless, high temperature environment of a flame is excellent for producing high-purity simple compounds, ultrafine metals and non-oxide ceramic powders are inherently reactive in the presence of oxygen and/or moisture. Thus, the handling of these powders after synthesis poses a challenging problem. Impurities acquired during handling of nanoparticles have plagued the advancement of nanostructured materials technology.

Sun, Z.↗

Comparison of the tribological properties of fluorinated cokes and graphites

The friction, wear, endurance life, and surface morphology of rubbed (burnished) fluorinated graphite and fluorinated coke materials were studied. Two different coke powders, a graphitic carbon powder, and a graphite powder were fluorinated and then tribologically investigated. In addition, one of the coke powders was reduced in size before fluorinating to evaluate the effect of a finer particle size on the tribological properties. For comparison, graphite and coke powders which were not fluorinated were also tribologically evaluated. Elemental analysis by emission spectroscopy was performed on each sample to determine the impurity content and X-ray diffraction analysis was performed to determine the crystallinity. Coke was found to have very little lubricating ability, but fluorinated coke did possess good lubricating properties. However, the fluorinated graphite and fluorinated graphitic carbon (which gave equivalent results) gave superior results to those obtained with the fluorinated cokes. No tribological benefit was found for using small versus a larger particle size of coke, at least when evaluated as a rubbed film.

Fusaro, Robert L.↗

Comparison of the tribological properties of fluorinated cokes and graphites

The friction, wear, endurance life, and surface morphology of rubbed (burnished) fluorinated graphite and fluorinated coke materials were studied. Two different coke powders, a graphitic carbon powder, and a graphite powder were fluorinated and then tribologically investigated. In addition, one of the coke powders was reduced in size before fluorinating to evaluate the effect of a finer particle size on the tribological properties. For comparison, graphite and coke powders which were not fluorinated were also tribologically evaluated. Elemental analysis by emission spectroscopy was performed on each sample to determine the impurity content and X-ray diffraction analysis was performed to determine the crystallinity. Coke was found to have very little lubricating ability, but fluorinated coke did possess good lubricating properties. However, the fluorinated graphite and fluorinated graphitic carbon (which gave equivalent results) gave superior results to those obtained with the fluorinated cokes. No tribological benefit was found for using small versus a larger particle size of coke, at least when evaluated as a rubbed film.

Fusaro, Robert L.↗

Tailoring of Boehmite-Derived Aluminosilicate Aerogel Structure and Properties: Influence of Ti Addition

Aluminosilicate aerogels offer potential for extremely low thermal conductivities at temperatures greater than 900 C, beyond where silica aerogels reach their upper temperature limits. Aerogels have been synthesized at various Al:Si ratios, including mullite compositions, using Boehmite (AlOOH) as the Al source, and tetraethoxy orthosilicate as the Si precursor. The Boehmite-derived aerogels are found to form by a self-assembly process of AlOOH crystallites, with Si-O groups on the surface of an alumina skeleton. Morphology, surface area and pore size varies with the crystallite size of the starting Boehmite powder, as well as with synthesis parameters. Ternary systems, including Al-Si-Ti aerogels incorporating a soluble Ti precursor, are possible with careful control of pH. The addition of Ti influences sol viscosity, gelation time pore structure and pore size distribution, as well as phase formation on heat treatment.

Hurwitz, Frances I.↗

The kinetics of composite particle formation during mechanical alloying

The kinetics of composite particle formation during attritor milling of insoluble binary elemental powders have been examined. The effects of processing conditions (i.e., mill power, temperature, and charge ratio) on these kinetics were studied. Particle size distributions and fractions of elemental and composite particles were determined as functions of milling time and processing conditions. This allowed the deduction of phenomenological rate constants describing the propensity for fracture and welding during processing. For the mill-operating conditions investigated, the number of particles in the mill generally decreased with milling time, indicating a greater tendency for particle welding than fracture. Moreover, a bimodal size distribution is often obtained as a result of preferential welding. Copper and chromium 'alloy' primarily by encapsulation of Cr particles within Cu. This form of alloying also occurs in Cu-Nb alloys processed at low mill power and/or for short milling times. For other conditions, however, Cu-Nb alloys develop a lamellar morphology characteristic of mechanically alloyed two-phase ductile metals. Increasing mill power or charge (ball-to-powder weight) ratio (CR) increases the rate of composite particle formation.

Aikin, B. J. M.↗

Solidification of undercooled metals

The present investigation is concerned with the subject of undercooling (i.e., supercooling) in the case of metal alloys, taking into account the effects of undercooling on microstructure and microsegregation in alloys which solidify in a crystalline manner. Techniques for obtaining a large degree of undercooling are discussed. These techniques make it possible to eliminate heterogeneous nucleants from the melt and to remove container nucleation effects. The nucleation behavior of small metal droplets is considered along with the formation of a dispersion of fine droplets in a suitable inert medium, the mixing of fine metal powders with glass powder, and the levitation melting technique. Attention is given to solidification with rapid interface velocity, aspects of dendritic morphology, and thermal measurements during solidification of undercooled droplets.

Flemings, M. C.↗

Enhanced TiO2 Photocatalytic Processing of Organic Wastes for Green Space Exploration

The effect of transition metal co-catalysts on the photocatalytic properties of TiO2 was investigated. Ruthenium (Ru), palladium, platinum, copper, silver, and gold, were loaded onto TiO2 powders (anatase and mixed-phase P25) and screened for the decomposition of rhodamine B (RhB) under broad-band irradiation. The morphology and estimated chemical composition of photocatalysts were determined by scanning electron microscopy and energy dispersive spectroscopy, respectively. Brunhauer, Emmett and Teller (BET) analysis measured mass-specific surface area(s). X-ray diffraction analysis was performed to confirm the identity of titania phase(s) present. The BET surface area of anatase TiO2/Ru 1% (9.2 sq m/gm) was one of the highest measured of all photocatalysts prepared in our laboratory. Photolyses conducted under air-saturated and nitrogen-saturated conditions revealed photodegradation efficiencies of 85 and 2 percent, respectively, after 60 min compared to 58 percent with no catalyst. The cause of low photocatalytic activity under an inert atmosphere is discussed. TiO2/Ru 1% showed a superior photocatalytic activity relative to P25-TiO2 under broad-band irradiation. A potential deployment of photocatalytic technologies on a mission could be a reactor with modest enhancement in solar intensity brought about by a trough-style reactor, with reactants and catalyst flowing along the axis of the trough and therefore being illuminated for a controlled duration based on the flow rate.

Udom, I.↗

Effect of surface moisture on dielectric behavior of ultrafine BaTiO3 particulates.

The effects of adsorbed H2O on the dielectric properties of ultrafine BaTiO3 particulates of varying particle size and environmental history were determined. The dielectric behavior depends strongly on surface hydration. No particle size dependence of dielectric constant was found for dehydroxylated surfaces in ultrafine particulate (unsintered) BaTiO3 materials. For equivalent particle sizes, the ac conductivity is sensitive to surface morphology. Reactions with H2O vapor appear to account for the variations in dielectric properties. Surface dehydration was effectively accomplished by washing as-received powders in isopropanol.

Mountvala, A. J.↗

Preparation of pigments for space-stable thermal control coatings

The identification and control of vapor phase reaction kinetics to produce pigments by homogeneous nucleation were achieved. A vapor phase apparatus was designed, fabricated, and calibrated through 1800 C. Vapor phase reactions were analyzed, calculations made, and powders of alumina, rutile, zinc orthotitanate (in a mixed phase), calcium tungstate, and lanthana were produced by homogeneous nucleation. Electron microscopy shows uniform particle morphology and size, and supports anticipated advantages of vapor-phase homogeneous nucleation; namely, purity, freedom from defects, and uniform particle sizing without grinding.

Campbell, W. B.↗

Improved catalysts by low-G processing

The advantages of space for manufacturing more perfect microcrystalline morphologies and structures will be investigated. Production of smaller silver and palladium crystals with enhanced catalytic properties is discussed. The elimination of convection accompanying electrodeposition of fine metallic powders at high overvoltages in a low gravity environment is outlined.

Grodzka, P. G.↗

Quick and Correlative TOF-SIMS Analysis of Dispersoid Content in Powder Feedstock and Printed Oxide Dispersion Strengthened Alloys

Oxide dispersion strengthening (ODS) of metal alloys, when combined with additive manufacturing (AM), can be used to solve high-temperature material application problems. The performance of ODS materials is dependent on nano-scale oxide being distributed uniformly throughout the metal matrix; a homogenous distribution is critical to the creep and yield strength. Therefore, quantifying and analyzing these oxide nanoparticles is essential for ODS alloy development. Assessing the chemistry and morphology of dispersoids in a material can be conducted using a variety of X-ray and electron-based methods. Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS), which assesses chemical concentrations from ion masses, provides the necessary spatial resolution and avoids potential spectral overlap of all elements present. In this work, preparing ODS powder feedstock and Laser Powder Bed Fusion AM was conducted with a NiCoCr alloy and yttria dispersoid, mixed with a Resodyn resonance mixer and printed on an EOS M100 3D printer at NASA Glenn. TOF-SIMS was performed on a Physical Electronics NanoTOF TRIFT V TOF-SIMS at Case Western Reserve University. The TOF-SIMS results collected on the feedstock powder samples correspond to the qualitative interpretation of the homogeneity of the oxide coating on the metal powder from SEM images. This provides quantitative support to the qualitative microscopy images collected earlier in the process design phase. The variance in the yttrium distribution on the powder feedstock samples also correlated with the variance of the yttrium distribution detected in the printed samples. This correlation supported the hypothesis that an even coating of yttria on the metal powders contributes to an even distribution of yttria in the printed material.

Laura G. Wilson↗

Advantages of barium peroxide in the powder synthesis of perovskite superconductors

This paper compares reaction chemistry, material processing, and material characteristics for the solid state reaction using BaCO3 or BaO2 in the synthesis of perovskite superconductors. Results are presented for weight loss and X-ray diffraction, sample morphology and homogeneity as monitored by SEM and EDS, and the superconductivity critical temperature and ac susceptibility. Greater mass density, increased sample homogeneity, lower resistance, and improved reproducibility for material are found when BaO32 is used.

Hepp, A. F.↗

Characterization of ceramics and intermetallics fabricated by self-propagating high-temperature synthesis

Three efforts aimed at investigating the process of self-propagating high temperature synthesis (SHS) for the fabrication of structural ceramics and intermetallics are summarized. Of special interest was the influence of processing variables such as exothermic dopants, gravity, and green state morphology in materials produced by SHS. In the first effort directed toward the fabrication of SiC, exothermic dopants of yttrium and zirconium were added to SiO2 or SiO2 + NiO plus carbon powder mix and processed by SHS. This approach was unsuccessful since it did not produce the desired product of crystalline SiC. In the second effort, the influence of gravity was investigated by examining Ni-Al microstructures which were produced by SHS combustion waves traveling with and opposite the gravity direction. Although final composition and total porosities of the combusted Ni-Al compounds were found to be gravity independent, larger pores were created in those specimens which were combusted opposite to the gravity force direction. Finally, it was found that green microstructure has a significant effect on the appearance of the combusted piece. Severe pressing laminations were observed to arrest the combustion front for TiC samples.

Hurst, Janet B.↗