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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Characterization of Arsenic and Selenium in Coal Fly Ash to Improve Evaluations for Disposal and Reuse Potential (Final Technical Report)

Coal fly ash is a high volume waste material that is discarded in landfills and surface water impoundments across the U.S. and is also widely recycled for a variety of applications. The leaching of potential of contaminants of concern, such as arsenic (As) and selenium (Se), is often the driver of risk assessments for coal ash disposal and reuse. The extent of leachable As and Se depends on several factors related to environmental conditions and fly ash characteristics. Previous studies employed various methods to delineate the concentration, chemical form, and distribution of As and Se in fly ash materials. However, few studies have attempted to directly correlate these properties to mobilization parameters relevant to disposal and reuse. Instead, the coal residuals industries often rely upon standardized leaching protocols that can be laborious or involve hazardous chemicals. The goals of the project were to: 1) Develop and evaluate a characterization protocol that can be used to screen fly ash samples for leachability of As and Se; 2) Characterize As, Se, and associated constituents of fly ash particles at multiple length scales (nanometer to micrometer) to determine if elemental associations differ as a function of the resolution of characterization; and 3) Establish a predictive model for the chemical composition of coal ash produced annually at major U.S. coal fired power facilities on 50-year national coal supply records. For the first objective, we performed leaching experiments with 52 fly ash samples collected from 15 different U.S. power plants and representing coal feedstocks from the three major domestic coal regions. For this work, we assessed the mobilization potential of As and Se in fly ash based on standardized leaching protocols and performed multivariate and lasso regression analyses to explore correlations of leachable As and Se contents with characteristics such as major element contents, loss on ignition (LOI) and pH. The results of regression models indicated that major elements (Fe, Ca, Al) for a wide range of fly ashes can serve as predictor variables for the leaching potential of As, but not for Se. LOI and pH were not important predictive variables in the models. Both regression approaches resulted in relatively strong fits for leachable As (correlation coefficient R 2 = 0.78 for both models) compared to models for leachable Se (R 2 = 0.49). Overall, these results suggest that correlation models combined with on-site elemental analysis with portable analyzers may enable a screening method for leachable As in coal ash. For the second objective, we utilized nanoscale 2-D imaging (30-50 nm spot size) with the Hard X-ray Nanoprobe (HXN) in combination with microprobe X-ray capabilities (~5 µm resolution) to determine As and Se elemental associations in fly ash particles. Speciation of As and Se was also measured at the nano- to microscale with X-ray absorption spectroscopy. The enhanced resolution of HXN showed As and Se that were diffusely located around or comingled with Ca- and Fe-rich particles. The results also showed nanoparticles of Se attached to the surface of fly ash grains. Overall, a comparison of As and Se species across scales highlights the heterogeneity and complexity of chemical associations for these trace elements of concern in coal fly ash. For the final objective, we developed a predictive model for major element composition of coal ash in reserve at disposal sites of major U.S. coal fired power plants. This model was constructed from coal purchase records of 705 power stations from 1973-2022 and was trained on coal ash composition data showing that coal ash elemental composition is strongly associated with the source of feedstock coal. The model showed regional shifts in the major element contents of ash produced by power plants in the last 50 years, particularly for calcium and iron (expressed as %CaO and %Fe 2 O 3 ), as coal-fired power stations changed their source of coal over this time frame. Our approach enables an estimation of coal ash chemical composition that is stored in waste impoundments at individual power stations. Such information can help delineate the regional market potential for material applications that would utilize coal ash harvested from disposal sites across the U.S.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS1999

MRI Measurements and Granular Dynamics Simulation of Segregation of Granular Mixture

A counter intuitive axial segregation phenomenon in a rotating horizontal cylinder has recently captured attention of many researchers in different disciplines. There is a growing consensus that the interplay between the particle dynamics and the evolution of the internal structure during the segregation process must be carefully investigated. Magnetic resonance imaging (MRI) has been used to non-invasively obtain much needed dynamic/static information such as velocity and concentration profiles, and it has proven to be capable of depicting the evolution of segregation processes. Segregation in a rotating cylinder involves two processes: the first is to transport small particles in the radial direction to form a radial core, and the second is to transform the radial core into axially segregated bands. Percolation and/or "stopping" have been proposed as mechanisms for the radial segregation. As to mechanisms for axial band formation, much less is known. The difference in the dynamic angle of repose has been proposed to segregate different components in the axial direction. Recently, Hill and Kakalios have reported that particles mix or demix depending upon the competition between diffusion and preferential drift whose order can be determined by the dynamic angle of repose through the adjustment of the rotation rate. We claim that the dynamic angle of repose could be one of the causes, however, it fails to offer reasonable explanations for certain aspects of the axial migration. For example, we always observe that the radial segregation precedes the axial segregation and small particles migrate in the radial direction to form an axially extended radial core. It then transforms into axially segregated bands. By definition, the effects of the dynamic angle of repose are restricted near the free surface where the flowing layer is present. However, during the process of transforming from the radially segregated core to axially segregated bands, small particles located in the deep core region, which is untouched by the flowing layer, also completely disappear. Usually, the dynamics angle of repose are uniquely defined for individual species to characterize particle properties, and the dynamic angle of repose thus defined provides little information for the dynamic angle of repose of the mixture since the concentration ratio and the internal packing structure do not remain the same during the segregation processes. Under microgravity environment, the dynamics angle of repose argument does not hold since there is simply no flowing layer to influence/determine the preferred directions of segregation. We have thus designed an experiment so that the effects of the dynamic angle of repose can be minimized by filling the cylinder almost completely full. Small particles still formed a radial core and also migrated to form axial bands. As ground based experiments we have designed and conducted both 2D and 3D segregation experiments. The 2D experiments are performed using a thin cylinder (the gap between two end caps is about 5 mm) filled with different combinations of particles. The 3D experiments are conducted with a long cylinder of its length and diameter of 27cm and 7cm, respectively. Results of 2D experiments indicate that different mechanisms govern particle motion in regions near and far from the axis of rotation. Results of 3D experiments indicate that a series of collapses of microstructures of particle packing (micro-collapses) may be responsible for the creation of voids for small particles to migrate through in the axial direction. We have successfully eliminated the dynamic angle of repose as a cause for segregation, however, by almost completely filling the cylinder with the particles, we have lost an opportunity to investigate a possibility of particle "mobility" being a cause for segregation which requires a flowing surface but not the difference in the angle of repose. This is currently being investigated.

Nakagawa, M.↗
NASA NTRS2000

Over-Expression, Purification and Crystallization of Human Dihydrolipoamide Dehydrogenase

Dehydrolipoamide dehydrogenase (E3; dihydrolipoan-tide:NAD+ oxidoreductase, EC 1.8.1.4) is a common catalytic component found in pyruvate dehydrogenase complex, alpha-ketoglutarate dehydrogenase complex, and branched-chain cc-keto acid dehydrogenase complex. E3 is also a component (referred to as L protein) of the glycine cleavage system in bacterial metabolism (2). Active E3 forms a homodimer with four distinctive subdomain structures (FAD binding, NAD+ binding, central and interface domains) with non-covalently but tightly bound FAD in the holoenzyme. Deduced amino acids from cloned full-length human E3 gene showed a total of 509 amino acids with a leader sequence (N-terminal 35 amino acids) that is excised (mature form) during transportation of expressed E3 into mitochondria membrane. So far, three-dimensional structure of human E3 has not been reported. Our effort to achieve the elucidation of the X-ray crystal structure of human E3 will be presented. Recombinant pPROEX-1 expression vector (from GIBCO BRL Life Technologies) having the human E3 gene without leader sequence was constructed by Polymerase Chain Reaction (PCR) and subsequent ligation, and cloned in E.coli XL1-Blue by transformation. Since pPROEX-1 vector has an internal His-tag (six histidine peptide) located at the upstream region of a multicloning site, one-step affinity purification of E3 using nickelnitriloacetic acid (Ni-NTA) agarose resin, which has a strong affinity to His-tag, was feasible. Also a seven-amino-acid spacer peptide and a recombinant tobacco etch virus protease recognition site (seven amino acids peptide) found between His-tag and first amino acid of expressed E3 facilitated the cleavage of His-tag from E3 after the affinity purification. By IPTG induction, ca. 15 mg of human E3 (mature form) was obtained from 1L LB culture with overnight incubation at 25C. Over 98% of purity of E3 from one-step Ni-NTA agarose affinity purification was confirmed by SDS-PAGE analysis. For crystallization, E3 samples were prepared with and without His-tag. To minimize the aggregation of E3, apo- and holo- forms of E3s were tested, as well as a mutated E3. Dynamic light scattering measurements revealed that the E3 preparations without His-tag and substrate are highly monodispersive with regard to homodimers. Consequent crystallization trials of this E3 preparation led to single crystals of E3 grown by the vapor diffusion method. Crystals were obtained within a few days from solution containing poly (ethylene glycol) monomethyl ether 5000 as a precipitant. Autoindexing and integration of the X-ray diffraction data showed that E3 crystals belong to an orthorhombic system with unit cell parameters a-- 123. 1, b= 165.3 and c=214.3A. Further optimization of protein preparation and crystallization experiments for the structural determination will be discussed.

Hong, Y. S.↗
DOE OSTI2023

Role of Intradomain Heterogeneity on Ion and Polymer Dynamics in Block Polymer Electrolytes: Investigating Interfacial Mobility and Ion-Specific Dynamics and Transport

Block polymers show promise as solid-state battery electrolytes due to the optimization of conductive and mechanical properties enabled via tuning of block chemistry and length. We investigate a polystyrene-block-poly(oligo-oxyethylene methacrylate) (PS-b-POEM) electrolyte doped with various lithium salts to investigate the role of molecular structure on ion transport properties and on local ion dynamics and associations. Anion charge becomes more delocalized with increasing size, reducing the coupling between salt ions while increasing coupling between ion and polymer chain motions and creating a more mobile overall environment. We observe support for this ion-polymer coupling via 1 H, 7 Li and 19 F NMR spectroscopy, from which we obtain ion-specific mobility transition temperatures that differ from the polymer glass transition temperature. We also note faster transport and weaker local energetic interactions with anion size using temperature-dependent NMR diffusometry. 1 H NMR spectroscopy further elucidates polymer chain dynamics and enables quantification of the temperature-dependent fraction of the conducting block that is immobile near the PS-POEM domain interface. As a result, NMR thus represents a species-specific and timescale-specific platform to quantify phase and interface behavior, and to correlate ion-specific transport with polymer chain dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Chain Dynamics in Magnetorheological Suspensions

Magnetorheological (MR) suspensions are composed of colloidal particles which acquire dipole moments when subjected to an external magnetic field. At sufficient field strengths and concentrations, the dipolar particles rapidly aggregate to form long chains. Subsequent lateral cross-linking of the dipolar chains is responsible for a rapid liquid-to-solid-like rheological transition. The unique, magnetically-activated rheological properties of MR suspensions make them ideal for interfacing mechanical systems to electronic controls. Additionally, the ability to experimentally probe colloidal suspensions interacting through tunable anisotropic potentials is of fundamental interest. Our current experimental work has focused on understanding the fluctuations of dipolar chains. It has been proposed by Halsey and Toor (HT) that the strong Landau-Peierls thermal fluctuations of dipolar chains could be responsible for long-range attractions between chains. Such interactions will govern the long-time relaxation of MR suspensions. We have synthesized monodisperse neutrally buoyant MR suspensions by density matching stabilized ferrofluid emulsion droplets with D2O. This allows us to probe the dynamics of the dipolar chains using light scattering without gravitational, interfacial, and polydispersity effects to resolve the short-wavelength dynamics of the dipolar chains. We used diffusing wave spectroscopy to measure these dynamics. The particle displacements at short times that show an independence to the field strength, but at long times exhibit a constrained, sub-diffusive motion that slows as the dipole strength is increased. The experiments are in good qualitative agreement with Brownian dynamics simulations of dipolar chains. Although there have been several important and detailed studies of the structure and interactions in MR suspensions, there has not been conclusive evidence that supports or contradicts the HT model prediction that long-range interactions exist between fluctuating chains of dipolar particles. Resolving this issue would contribute greatly to the understanding of these interesting and important materials. We have begun to test the predictions of the HT model by both examining the dynamics of individual chains and by measuring the forces between dipolar chains directly to accurately and quantitatively assess the interactions that they experience. To do so, we employ optical trapping techniques and video-microscopy to manipulate and observe our samples on the microscopic level. With these techniques, it is possible to observe chains that are fluctuating freely in three-dimensions, independent of interfacial effects. More importantly, we are able to controllably observe the interactions of two chains at various separations to measure the force-distance profile. The techniques also allow us to study the mechanical properties of individual chains and chain clusters. Our work to this point has focused on reversibly-formed dipolar chains due to field induced dipoles where the combination of this chaining, the dipolar forces, and the hydrodynamic interactions that dictate the rheology of the suspensions. One can envision, however, many situations where optical, electronic, or rheological behavior may be optimized with magneto-responsive anisotropic particles. Chains of polarizable particles may have the best properties as they can coil and flex in the absence of a field and stiffen and orient when a field is applied. We have recently demonstrated a synthesis of stable, permanent paramagnetic chains by both covalently and physically linking paramagnetic colloidal particles. The method employed allows us to create monodisperse chains of controlled length. We observed the stability, field-alignment, and rigidity of this new class of materials. The chains may exhibit unique rheological properties in an applied magnetic field over isotropic suspensions of paramagnetic particles. They are also useful rheological models as bead-spring systems. These chains form the basis for our current experiments with optical traps.

Gast, A. P.↗
DOE OSTI2020

N-Terminal Decarboxylation as a Probe for Intramolecular Contact Formation in $γ$-Glu-(Pro) n -Met Peptides

The kinetics of intramolecular-contact formation between remote functional groups in peptides with restricted conformational flexibility were examined using designed peptides with variable-length proline bridges. As probes for this motion, free radicals were produced using the • OH-induced oxidation at the C-terminal methionine residue of γ-Glu-(Pro) n -Met peptides ( n = 0–3). The progress of the radicals’ motion along the proline bridges was monitored as the radicals underwent reactions along the peptides’ backbones. Of particular interest was the reaction between the sulfur atom located in the side chain of the oxidized Met residue and the unprotonated amino group of the glutamic acid moiety. Interactions between them were probed by the radiation-chemical yields (expressed as G values) of the formation of C-centered, α-aminoalkyl radicals (αN) on the Glu residue. These radicals were monitored directly or via their reaction with p -nitroacetophenone (PNAP) to generate the optically detected PNAP •– radical anions. The yields of these αN radicals were found to be linearly dependent on the number of Pro residues. A constant decrease by 0.09 μM J –1 per spacing Pro residue of the radiation-chemical yields of G (αN) was observed. Previous reports support the conclusion that the αN radicals in these cases would have to result from (S$\therefore$N) + -bonded cyclic radical cations that arose as a result from direct contact between the ends of the peptides. Furthermore, by analogy with the rate constants for the formation of intramolecularly (S$\therefore$S) + -bonded radical cations in Met-(Pro) n -Met peptides ( J. Phys. Chem. B 2016 , 120 , 9732), the rate constants for the formation of intramolecularly (S$\therefore$N) + -bonded radical cations are activated to the same extent for all of the γ-Glu-(Pro) n -Met peptides. Thus, the continuous decrease of G (αN) with the number of Pro residues (from 0 to 3) suggests that the formation of a contact between the S-atom in the C-terminal Met residue and the N-atom of a deprotonated N-terminal amino group of Glu is controlled in peptides with 0 to 3 Pro residues by the relative diffusion of the S •+ and unoxidized N-atom. The overall rate constants of cyclization to form the (S$\therefore$N)-bonded radical cations were estimated to be 3.8 × 10 6 , 1.8 × 10 6 , and 8.1 × 10 5 s –1 for peptides with n = 0, 1, and 2 Pro residues, respectively. If activation is the same for all of the peptides, then these rate constants are a direct indication for the end-to-end dynamics along the chain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2010

Stability of Basalt plus Anhydrite plus Calcite at HP-HT: Implications for Venus, the Earth and Mars

"Canali" observed at Venus surface by Magellan are evidence for very long melt flows, but their composition and origin remain uncertain. The hypothesis of water-rich flow is not reasonable regarding the temperature at Venus surface. The length of these channels could not be explained by a silicate melt composition but more likely, by a carbonate-sulfate melt which has a much lower viscosity (Kargel et al 1994). One hypothesis is that calcite CaCO3 and anhydrite CaSO4 which are alteration products of basalts melted during meteorite impacts. A famous example recorded on the Earth (Chicxulub) produced melt and gas rich in carbon and sulfur. Calcite and sulfate evaporites are also present on Mars surface, associated with basalts. An impact on these materials might release C- and S-rich melt or fluid. Another type of planetary phenomenon (affecting only the Earth) might provoke a high pressure destabilization of basalt+anhydrite+calcite. Very high contents of C and S are measured in some Earth s magmas, either dissolved or in the form of crystals (Luhr 2008). As shown by the high H content and high fO2 of primary igneous anhydrite-bearing lavas, the high S content in their source may be explained by subduction of an anhydrite-bearing oceanic crust, either directly (by melting followed by eruption) or indirectly (by release of S-rich melt or fluid that metasomatize the mantle) . Calcite is a major product of oceanic sedimentation and alteration of the crust. Therefore, sulfate- and calcite-rich material may be subducted to high pressures and high temperatures (HP-HT) and release S- and C-rich melts or fluids which could influence the composition of subduction zone lavas or gases. Both phenomena - meteorite impact and subduction - imply HP-HT conditions - although the P-T-time paths are different. Some HP experimental/theoretical studies have been performed on basalt/eclogite, calcite and anhydrite separately or on a combination of two. In this study we performed piston-cylinder experiments at 1 GPa between 950 and 1700 C using a mixture of 70wt% tholeiitic basalt + 15wt% anhydrite + 15wt% calcite. Up to ~1440 C, an ultracalcic (CaO>13.5 wt%; CaO/Al2O3>1 wt%) picrobasaltic (SiO2~40-45 wt%; Na2O+K2O<2 wt%) melt containing up to 5 wt% SO3 and up to 5.3 wt% CO2+H2O (calculated by difference) is present in equilibrium with clinopyroxene, anhydrite, spinel-chromite, a CAS-phase and a gas composed mainly of CO and an aliphatic thiol (CH2)4SH. Hydrogen was incorporated either by contact between the starting material and air or by diffusion through the capsule during the experiments. The S content in the gas increases with temperature and run duration, implying that gases with various C/S ratios might be released during an impact or at subduction zones, depending on the P-T-t path and on the H content. Above approx.1440 C, a Ca-rich carbonate-sulfate melt forms (in equilibrium with the picrobasaltic melt) which contains a few percents of Na and K. Such melt is not expected to form at Earth s subduction temperatures. If it forms by meteorite impact, it might crystallize too fast to explain long flows like Venus canali. A different basalt/anhydrite/calcite ratio might, however, decrease its formation temperature.

Martin, A. M.↗
NASA NTRS1994

The Balmer-dominated northeast limb of the Cygnus loop supernova remnant

We present a comprehensive investigation of the Balmar-dominated northeast limb of the Cygnus Loop supernova remnant. Data presented include H alpha (O III), and X-ray images, UV and visible spectrophotometry, and high-resolution spectroscophy. The two relatively bright Balmer-dominated filaments visible on the POSS prints are seen to be part of a very smooth and regular complex of filaments. These filaments mark the current location of the blast wave and are seen to bound the sharply limb-brightened X-ray emission, including the previously reported X-ray, 'halo.' The (O III)/h beta ratio throughout the region is approximately 0.1, except for regions in which the shock is undergoing a transition from nonradiative to incomplete radiative to incomplete radiative conditions. At these locations (O III) emission from the cooling region is quite strong, while collisionally excited Balmer-line emission can be weak because of photoionization of the preshock medium by UV from the nascent cooling region. As a result (O III)/H beta is greater than 100 in some locations. The nonradiative/radiative transition is best studied along the length of the northwestern of the two brightest filaments, where the shock velocity and swept-up column go from approximately 180 km/s and 10(exp 17)/sq cm at one end to approximately 140 km/s and 8 x 10(exp 17)/cm at the other. There are also a number of locations of such incomplete radiative emission where the shock has recently encountered denser regions with characteristic sizes of approximately 10(exp 18) cm. There is a considerable amount of evidence that the shock has decelerated from approximately 400 km/s to less than 200 km/s in the last 1000 yr. We interpret this as the result of the blast wave hitting the wall of a cavity which surround the supernova precursor and succeed in matching a wide range of data with a reflected shock model in which the density ofthe cavity wall is approximately 1.2/cu cm and the density in the interior of the cavity is about 0.09/cu cm. This analysis supports previous suggestions that the Cygnus Loop was a cavity explosion. We opredict that the X-ray shell will continue to brighten for the next 1000 years or so, during which time the shock front will become radiative throughout the northeast region. The similarity of the time scales for post-shock cooling, shock deceleration, and the 1ressure evolution of the region violates assumptions of steady flow, and greatly complicated interpretation of shock specptra in the region. This may be a common and important effect in many supernova remnants. High-resolutoin spectroscopy of the H alpha line profile shows that the broad component is surprisingly narrow (approximately 130 km/s). Consistency between this line width and the shock velocity inferred from spectrophotometry requires either rapid postshock equilibration of T(sub i) and T(sub e), or that the shock front has declerated from 180 km/s to 150 km/s in the last approximately 200 yr. While we cannot unambiguously distinquish between these models, the required deceleration is consistent with extrapolation of the shock decleration rate inferred over the last 1000 years. The width of the narrow component of the h alpha line profile is approximately 3 km/s, which indicates that the preshock medium has been heated to approximately 25,000 K by a shock precursor. The most promising types of precursor are heating either by fast neutrals which overtake the shock or by cosmic rays. In the latter case the observed properties of the precursor constrain the cosmic-ray diffusion coefficient to be between about 10(exp 23) sq cm/s. The characteristics of the precursor seem to be about right to explain the presence of weak (S II) and (N II) emission previously reported by Fesen & Itoh (1985).

Hester, J. Jeff↗
NASA NTRS1999

Carbon Fiber Reinforced/Silicon Carbide Turbine Blisk Testing in the SIMPLEX Turbopump

A program designed to implement a ceramic matrix composite integrally bladed disk (blisk) into rocket engine style turbomachinery has successfully completed testing. The Marshall Space Flight Center (MSFC) program, utilizing the MSFC turbomachinery design, analysis, and testing capabilities along with materials development capabilities from both Glenn Research Center (GRC) and MSFC, has tested two carbon fiber reinforced silicon carbide blisks in the Simplex Turbopump at MSFC's Test Stand 500. One blisk contained a polar woven fiber preform, while the second blisk tested utilized a quasi-isotropic preform. Vhile earlier papers have chronicled the program's design, material testing, and torque testing efforts, this paper focuses on the testing of the blisks in the Simplex turbopump. Emphasis will be placed on the actual condition of the blisks before and after the testing test program design methodology, and conclusions that can be drawn from the test data and blisk final conditions. The program performed three separate test series. The first series was needed to validate that the Simplex turbopump was correctly re-built following a major incident to the turbopump. The turbopump had two major differences from the original design. The most obvious difference was the sleeve required throughout the bore of the main housing. The second major difference was modifications to the pump diffuser to improve performance. Several areas were burnt during the incident and were either repaired by weld repair (pump inlet housing) or simply smoothed out (turbine nozzle discharge). The test series was designed to weed out any turbopump design and manufacturing flaws or fatigue issues prior to putting the C/SiC blisks into it. The second and third series were the C/SiC blisk test series. The primary goal of these series was to expose the blisks to as much fatigue causing dynamic stress as possible to examine the material's capability. Initially, the test plan was to put equal time on the two blisks, however, as the test series progressed, the funding allowed additional testing to occur. The additional test time was placed on the polar weave blisk. The total test time accrued on the polar blisk was 2550 seconds with 860 seconds near the turbopump design speed of 25,000 rpm. This testing included 6 tests / 775 seconds pumping liquid nitrogen and 7 tests / 1775 seconds pumping liquid oxygen. The drive gas for all of the tests was gaseous nitrogen due to the lack of hot gas source for the Simplex turbopump. The quasi-isotropic blisk was tested for XX total tests and XXXX seconds with X tests/XXXX seconds pumping liquid nitrogen and X tests/XXXX seconds pumping liquid \oxygen.During the test series, the blisks were inspected following each test. Inspections initially were viewed from the downstream side of the blisks only. Midway through the testing, a method of borescoping the leading edges of the blades was devised, and subsequently, both sides of the blades were inspected following each test. The leading and trailing edges of the polar blisk held up better than the quasi-isotropic blisk. This was a known possibility due to the varying fiber direction in the blades as the rectangular preform weave is cut in a circular pattern. The surprising fact about the testing was that there was no measurable performance loss due to the inaccuracies in the blade manufacturing in the C/SiC blisks, the surface roughness C/SiC of the blades, or the loss of the material in the polar blisk. A performance shift was seen in the quasi-isotropic blisk as portions of the leading and trailing edges were lost. After the testing was completed, detailed inspections of the blisks were performed. The largest surprise was the polar blisk had a obvious crack in a single blade that was located nearly midspan which was not detected in test. The crack ran completely through the blade circumferenciary and through the radial length of the blade. However, the crack does not appear to extend into the blisk hub. Although the cause of the crack is still under investigation, the material appears to be tolerant of this crack, and other hairline cracks discovered under higher magnification. This bodies well for eventual use of this material in actual flight turbopumps where monolithic fracture toughness issues limit its use.

Genge, Gary G.↗
NASA NTRS2012

Metrology of Large Parts

As discussed in the first chapter of this book, there are many different methods to measure a part using optical technology. Chapter 2 discussed the use of machine vision to measure macroscopic features such as length and position, which was extended to the use of interferometry as a linear measurement tool in chapter 3, and laser or other trackers to find the relation of key points on large parts in chapter 4. This chapter looks at measuring large parts to optical tolerances in the sub-micron range using interferometry, ranging, and optical tools discussed in the previous chapters. The purpose of this chapter is not to discuss specific metrology tools (such as interferometers or gauges), but to describe a systems engineering approach to testing large parts. Issues such as material warpage and temperature drifts that may be insignificant when measuring a part to micron levels under a microscope, as will be discussed in later chapters, can prove to be very important when making the same measurement over a larger part. In this chapter, we will define a set of guiding principles for successfully overcoming these challenges and illustrate the application of these principles with real world examples. While these examples are drawn from specific large optical testing applications, they inform the problems associated with testing any large part to optical tolerances. Manufacturing today relies on micrometer level part performance. Fields such as energy and transportation are demanding higher tolerances to provide increased efficiencies and fuel savings. By looking at how the optics industry approaches sub-micrometer metrology, one can gain a better understanding of the metrology challenges for any larger part specified to micrometer tolerances. Testing large parts, whether optical components or precision structures, to optical tolerances is just like testing small parts, only harder. Identical with what one does for small parts, a metrologist tests large parts and optics in particular to quantify their mechanical properties (such as dimensions, mass, etc); their optical prescription or design (i.e. radius of curvature, conic constant, vertex location, size); and their full part shape. And, just as with small parts, a metrologist accomplishes these tests using distance measuring instruments such as tape measures, inside micrometers, coordinate measuring machines, distance measuring interferometers; angle measuring instruments such as theodolites, autocollimators; and surface measuring instruments including interferometers, stylus profilers, interference microscopes, photogrammetric cameras, or other tools. However, while the methodology may be similar, it is more difficult to test a large object for the simple reason that most metrologists do not have the necessary intuition. The skills used to test small parts or optics in a laboratory do not extrapolate to testing large parts in an industrial setting any more than a backyard gardener might successfully operate a farm. But first, what is a large part? A simple definition might be the part's size or diameter. For optics and diffuse surface parts alike, the driving constraint is ability to illuminate the part's surface. For reflective convex mirrors, large is typically anything greater than 1 meter. But, for refractive optics, flats or convex mirrors, large is typically greater than 0.5 meter. While a size definition is simple, it may be less than universal. A more nuanced definition might be that a large part is any component which cannot be easily tested in a standard laboratory environment, on a standard vibration isolated table using standard laboratory infrastructure. A micro-switch or a precision lens might be easily measured to nanometer levels under a microscope in a lab, but a power turbine spline or a larger telescope mirror will not fit under that microscope and may not even fit on the table.

Stahl, H. Philip↗
DOE OSTI2025

Structure–Activity Relationships for Ethanol Dehydrogenation to Acetaldehyde by Silica-Supported Zinc Oxide Catalysts

Silica-supported ZnO efficiently catalyzes the nonoxidative dehydrogenation of ethanol to acetaldehyde, which is relevant for production of 1,3-butadiene from bioethanol. Characterization with in situ spectroscopies under dehydrated conditions (high sensitivity-low energy ion scattering (HS-LEIS), diffuse reflectance (DR) UV–vis, X-ray absorption spectroscopy (XAS), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), inelastic neutron scattering (INS), and UV Raman), and ammonia adsorption probed by temperature-programmed desorption followed by DRIFTS and mass spectrometry (DRIFTS-MS NH 3 -TPD), and DFT calculations revealed that the supported ZnO x phase was present as isolated surface ZnO x sites on SiO 2 , with the vast majority coordinated by two siloxane bonds and one silicon atom with two nonbridging oxygens ((≡SiO) 2 Zn 2+ O 2 Si=), anchored at 4-, 5-, and 6-membered siloxane rings. A minor fraction of surface ZnO x sites possessed Lewis acidity, and even fewer sites possessed a Bro̷nsted acidic Zn(OH) + Si moiety. Ethanol temperature-programmed surface reaction-mass spectrometry (TPSR-MS) with various oxidative or ethanol reaction pretreatments indicated that only sites with Lewis and Bro̷nsted acidic character (Zn(OH) + Si) were active for ethanol dehydrogenation, while the majority surface (≡SiO) 2 Zn 2+ O 2 Si= sites were inactive. Greater heterogeneity among all surface ZnO x sites, as assessed by in situ DR UV–vis spectroscopy, was associated with a greater number of ZnO x sites that were active for ethanol dehydrogenation as well as lower enthalpic barriers for acetaldehyde production among the most active surface ZnO x sites. Turnover frequencies and the apparent activation energy for ethanol dehydrogenation were determined from steady-state kinetics. Together, these findings suggested that anchoring inactive surface (≡SiO) 2 Zn 2+ O 2 Si= sites on the silica support caused a greater number of active surface ZnO x sites to adopt a more strained configuration, promoting ethanol dehydrogenation catalysis. Pretreatments and catalysts that promoted desorption of ethanol during TPSR, taken as a marker of surface dehydroxylation, were associated with an increased number of the most active surface (Zn(OH) + Si) sites. Such findings suggested that inactive surface ZnO x sites were activated for ethanol dehydrogenation by dehydroxylation of the support and/or decreased coordination to hemilabile siloxane ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗