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At least 145 records · Page 8

The Center for Performance and Design of Nuclear Waste Forms and Containers (WastePD) Energy Frontier Research Center (Final Report)

The DOE Office of Environmental Management is responsible for high level nuclear waste that must be safely isolated from humans and the environment for extremely long periods. The waste forms and containers are made of glass, ceramics, and metals. Verified safe disposal requires understanding the fundamental mechanisms of waste form degradation and the design of new waste forms with improved performance, which comprise the goals of the Energy Frontier Research Center known as the Center for the Performance and Design of Nuclear Waste Forms and Containers, WastePD. WastePD was constructed to develop innovative approaches and solutions to those goals through the synergistic interactions of individuals who are experts in the degradation behavior, modeling, and design of glasses, ceramics and metal alloys. WastePD is the first center ever created to address this diverse group of materials in a comprehensive and coordinated manner. The science goals are grouped into three common topics: corrosion mechanisms via advanced characterization, environmental impacts, and materials design. Synergistic interactions in these areas were a key component of WastePD. The fundamental understanding of the degradation mechanisms of the waste forms and containers as well as the development of new materials with improved properties will allow DOE to prevent environmental contamination and to explore totally new repository concepts. WastePD was operational from August 2016 through July 2022, but the DOE support was drastically reduced for the last two years. This final technical report covers the full period of performance. However, much of what was accomplished in the first four years is nicely summarized in a review paper published in 2021, which is appended to this report. Therefore, this final report focuses on the technical findings from the last two years of WastePD activities. Considerable progress was made in the areas of a) the environmental and compositional impacts on the corrosion of borosilicate and aluminosilicate glasses, b) the mechanism of glass corrosion and the structure and evolution of the surface alteration layer, c) the effects of environment and composition on the corrosion of pyrochlore, perovskite, hollandite, and other oxide ceramics, d) the corrosion mechanism of multi-principal element metallic alloys, and e) a new framework for understanding the pitting corrosion of metals.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Tailoring Cementitious Materials Towards Value-Added Use of Large CO 2 Volumes

Hydraulic cements with alternative chemistries were developed for large-volume and value-added use of carbon dioxide. The hydraulic cements were processed using the energy-efficient mechanochemical technique at room temperature and atmospheric pressure. Carbon dioxide was captured directly from combustion emissions during processing. For this purpose, mechanochemical processing of hydraulic cements was accomplished under a flow of combustion emissions prior to the release of emissions to the atmosphere. The process removed a significant fraction of carbon dioxide from combustion emissions. The hydraulic cements captured carbon dioxide at about 10% of their weight. Two hydraulic cement chemistries were developed, and their mechanochemical processing was successfully scaled-up. The characteristic feature of one chemistry was its relatively low (near-neutral) pH where the integration of carbon dioxide yielded clear value. The second cement chemistry was based on alkali activation of industrial wastes. This chemistry could make value-added use of carbon dioxide, but it had to be refined to control the pH drop caused by CO 2 integration. These two cements render binding effects upon hydration by forming a combination of stable carbonates and aluminosilicates or phosphates. Efforts to develop cement chemistries based solely on carbonates were not successful. The mechanochemical process was found to integrate carbon dioxide into the alternative cement chemistries in the form of disordered and metastable carbonates. During hydration reactions, the disordered/metastable carbonates are either transformed into stable carbonate phases with desired binding efforts, or carbonates get integrated into the primary inorganic binders (hydrates). When compared with mechanochemical processing in pure carbon dioxide, mechanochemical processing in combustion emissions produced hydraulic cements with improved engineering properties. The mechanochemical process was scaled-up, and its variables as well as the raw materials formulations were optimized for implementation at pilot scale. Scale-up was found to enhance the carbon capture potential and the engineering qualities of the resulting hydraulic cements. This was because scale-up raises the intensity of mechanical energy input to raw materials. Certain mechanochemical phenomena cannot be induced, irrespective of the cumulative mechanical energy input, unless the intensity of impact is raised above a minimum level that cannot be achieved in laboratory-scale implementation of the process. Due to this effect, the duration of the mechanochemical process as well as its energy demand could be reduced significantly (by an order of magnitude) upon transition from laboratory to pilot scale, with the hydraulic cements produced at pilot scale offering engineering properties that were superior to those realized in laboratory-scale mechanochemical processing. The hydraulic cements produced at pilot scale via mechanochemical processing under a flow of combustion emissions were thoroughly characterized. They were found to meet standard requirements for ‘General Use’ hydraulic cements. They were compatible with the industrial-scale concrete production and construction practices that are used with the currently prevalent hydraulic cements. The new hydraulic cements with integrated carbon dioxide were found to offer distinct advantages over the currently prevalent Portland cement in terms of net carbon footprint and energy content. The combined raw materials and energy costs of the new hydraulic cements are competitive, and major cost savings can be realized because of the simplified production process that significantly lowers the capital investment in cement production plants. Mechanochemical processing of the new hydraulic cements under a flow of combustion emissions can be implemented using some existing components of cement manufacturing plants; this facilitates adoption of the technology by the cement industry.

36 MATERIALS SCIENCE↗

Milestone Report on Microstructure of Irradiated Sensors and Coupling Adhesive Bonds

This report describes the ORNL aspects of an NSUF project in collaboration between EPRI, ORNL, and NCSU. Preliminary characterizations at ORNL LAMDA laboratory on piezoelectric sensors and bonds before and after NCSU PULSTAR reactor irradiation. Five pre-irradiation and seven post-irradiation samples have been examined by scanning electron microscopy and related methods so far. Samples consisted of (Pb,Bi)(Sc,Ti)O 3 or LiNbO 3 ceramics. Bonding layers consisted of epoxy, zirconia, alumina, aluminosilicate, or a complex soda-lime type slurry.

36 MATERIALS SCIENCE↗

Low-Temperature Architected Cementation Agents (LAMINAE)

The cement industry contributes 5-9% of all anthropogenic CO 2 . At the same time, current concrete curing processes are passive, with little-to-no control over microstructure. The LAMINAE process offers the potential for a low-temperature pathway for producing cementitious aluminosilicate hydrate (zeolite) structures which: (a) reduces the energy burden of cement production by 30%, (b) reduces CO 2 emissions by 60%, and (c) offers microstructure control as was implicitly ensured in Roman concrete. This project generated data and engineering correlations to support further scale up and design of initial commercial processes.

36 MATERIALS SCIENCE↗

Analysis of Solids Obtained from 201O, 201P, 202A, and 202B Contactors in the Salt Waste Processing Facility

In December 2022, Savannah River Mission Completion personnel recovered solids samples from four contractors (EXT-001, EXT-007, EXT-031, and EXT-040) employed at the Salt Waste Processing Facility (SWPF). These solids were submitted to Savannah River National Laboratory for analysis and characterization. This Technical Report outlines the analytical findings and observations associated with these samples and explores the potential source of solid generation within the SWPF. The following conclusions are offered as a result of this work: the light color solids recovered from EXT-007 are consistent with crystallized, soluble salt components (such as sodium nitrate, sodium hydroxide, and sodium carbonate), all of which can be easily re-dissolved in process water and do not represent a threat to SWPF CSSX processing. While the light solids from the top of EXT-040 were not analyzed, it is believed that they share similar characteristics to those recovered from EXT-007; The dark color solids recovered from EXT-001, EXT-031, and the inside of EXT-040 appear to be complex, consisting of several different types of solids: High concentrations of mercury (Hg, 40-75% by mass) partially present as elemental Hg are consistent with the precipitation of Hg 0 /Hg 2+ from disproportionation of Hg + species in pH swing conditions; Moderate concentrations of titanium (Ti) (2-7%, by mass) are also present, often co-located with Hg. This is consistent with co-precipitation, entrainment, and/or amalgamation of Ti and Hg; Moderate concentrations of iron (Fe) (1-3%, by mass) are observed in SWPF solids and are likely attributable to erosion of stainless-steel components within the CSSX process; Small concentrations of tungsten (W) and cobalt (Co) (<1%, by mass) are observed in SWPF solids. The presence of these solids is consistent with the erosion of components coated with W and Co (e.g., Stellite); Small concentrations of aluminum (Al) (<1%, by mass) are observed in the form of gibbsite and potentially sodium aluminosilicate. The presence of these compounds is likely attributable to the pH swing observed between the scrub and extraction cycles within the CSSX process. The following recommendations are made as a result of this work: Testing should be performed to determine the chemical drivers, process, and mechanism of Hg precipitation in CSSX processing. Special care should be taken to include titanium in tests to evaluate the potential for co-precipitation, entrainment, and amalgamation; Hg-mitigation options that would minimize or eliminate risks of Hg precipitation and solids accumulation (e.g., Hg-absorption techniques, ion exchange/adsorbents, flowsheet changes, etc.) should be assessed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Narrow-Channel, Fluidized Beds for Effective Particle Thermal Energy Transport and Storage

Colorado School of Mines (Mines) led this program in collaboration with Sandia National Laboratories (Sandia) to characterize narrow-channel fluidized beds of aluminosilicate particles – supplied by Carbo Ceramics – as a means for releasing high-temperature thermal energy in particle heat exchangers and for capturing concentrated solar energy in indirect particle receivers. Single-channel, heat transfer experiments at Mines and reduced-order 1-D models and 3-D two-fluid, CFD models explored many aspects of counterflow, bubbling fluidized beds (net downward particle flow and upward gas flow) for enhancing particle-wall heat transfer at elevated temperatures. Results at Mines on single-channel test sections consistently showed that mild bubbling fluidization increases particle-wall heat transfer coefficients (h T,w ) regularly by more than 4.0x over h T,w values without fluidization at similar conditions (mean particle diameter d p , bed depth Δz b , and bed particle temperatures T p ). Insights from lab-scale tests and modeling studies provided Nusselt number correlations for h T,w and informed the design and fabrication (by Vacuum Process Engineering) of a nominal 40-kWth, particle-sCO 2 plate heat exchanger (HX) with 12 parallel narrow-channel, fluidized beds bounded by stainless-steel walls with embedded microchannels for high-pressure sCO 2 flows. Tests of the 40-kW th HX at the particle-sCO 2 HX test stand at Sandia's National Solar Thermal Test Facility (NSTTF) were limited, due to HX design, to particle inlet temperatures T p,in ≤ 520°C with maximum sCO 2 outlet temperatures T sCO2,out ≈ 440°C, which are well below design conditions for a primary HX in a sCO 2 power cycle for a Gen-3 concentrating solar power (CSP) plant. Total heat transfer $\dot{Q}_{HX}$ remains relatively constant with increased fluidization for fixed particle and sCO 2 inlet conditions because higher h T,w due to fluidization is offset by increased axial dispersion, which suppresses temperature differences between the particles and sCO 2 in the counterflow configuration. The axial dispersion reduces the effective overall heat transfer coefficient U based on T p,in to values around 200 W m -2 K -1 .

14 SOLAR ENERGY↗

Rapid AI-based Dissection of Ashes using Raman and XRF Spectroscopy (RADAR-X)

Waste-to-energy (WTE) facilities incinerate ~35 million tons of municipal solid waste annually in the United States. The incineration process reduces the mass and the volume of the waste fraction by over 75 and 95%, respectively. The fraction left after incineration remains as ash residues and is referred to as WTE ash, compromising of bottom and fly ash. In the United States, ~10 million tons of WTE ashes are generated annually and predominantly landfilled because of the lack of secondary end-use pathways. This incurs a significant financial burden (landfilling costs) on U.S. WTE facilities and also results in the loss of materials to the landfill. The primary objective of this research is to understand better the elemental and mineralogical composition of WTE ashes from diverse origins and find composition dependent upcycling pathways for diverting these ashes from landfills. This primary objective was addressed through three research tasks –(Task I) An AI-led Multi-Modal Approach for Compositional Analysis, (Task II) Developing a Dissolution-Based Test for Real Time Analysis, and (Task III) Establishing composition-dependent end uses. The chemical composition of WTE ash is dependent on two factors, i.e., the input waste composition and the operational parameters of a WTE facility (combustion conditions). Amongst these two factors, the input waste composition will likely show spatial and temporal variation. As a result, the chemical composition of WTE ash will also fluctuate. To understand the spatial and temporal variation in WTE ash composition, in Task I, we collected 128 ash samples (62 bottom ash and 66 fly ash samples) from 11 WTE facilities located in 11 U.S. states and characterized them via X-ray Fluorescence, powder X-ray Diffraction, and Raman Spectroscopy. The findings from this extensive characterization work indicated that the key elements in WTE fly ashes are Ca, Cl (greater than 10 wt. %), Si, S, K, Zn ( between 1 and 10 wt. %), Mg, Al, P, Ti, Fe, Cu, Br, and Pb (between 0.1 and 1 wt. %). Similarly, the key elements in WTE bottom ash fraction finer than 45μm are Ca (greater than 10 wt. %), Mg, Al, Si, S, Cl, K, Ti, Fe, Zn (between 1 and 10 wt. %), P, V, Cr, Mn, Cu, Br, and Pb (between 0.1 and 1 wt. %). Here, we note that the dominant fraction of WTE bottom ash is the coarse fraction. The coarse WTE bottom ash fraction (rich in silicon) was not characterized in this study because of excessive grinding requirements and their unsuitability as a supplementary cementitious material due to their coarse nature. The elements in WTE bottom ashes are present as calcite, anhydrite, vaterite, hydroxyapatite, quartz, bassanite, gehlenite, akermanite, hydrocalumite, and portlandite. Similarly, the mineralogical species present in WTE fly ashes are calcium chloride hydroxide, halite, calcite, anhydrite, sylvite, hydrocalumite, vaterite, hannebachite, quartz, and bassanite. Temporal variation in ash composition may also result in significant fluctuations in chemical compositions. Therefore, a WTE facility may need to monitor the ash composition (elemental and mineralogical composition) in real time. In Task I, we evaluated the possibility of using a portable X-ray fluorescence (XRF) spectrometer to monitor the elemental composition in real-time. Specifically, we collected XRF data on identical specimens via a portable XRF spectrometer (low-end) and a lab-based benchtop XRF spectrometer (high-end). The collected data was used to train an A.I. algorithm (portable XRF data as an input and benchtop XRF data as an output) to predict accurate elemental composition using portable XRF data. Finally, we developed a 2-minute photobleaching protocol to monitor the mineralogical characteristics of WTE ashes via Raman spectroscopy. Overall, the activities in Task I improved our understanding of ash composition and developed techniques to monitor elemental and mineralogical composition in near real-time. Based on the findings of Task I, we find that WTE ashes exhibit wide variability in mineralogy. For ICP-based elemental analysis, all the mineralogical species in WTE ashes must be brought into solution. This is traditionally accomplished with acid digestion using a combination of multiple acids. However, acid digestion with multiple acids is time-consuming and often fails to ensure complete digestion of the ash matrix. To address this limitation, in Task II, we developed an alkali-fusion-based digestion protocol using a combination of lithium tetraborate, lithium metaborate, and their combinations as possible alkali fluxes for digesting WTE ashes entirely and rapidly. The validity of the developed method was evaluated on two standard ash specimens, i.e., SRM 1633c coal fly ash and BCR-176R incineration fly ash specimen. The findings suggest that the developed protocol can ensure complete digestion of elements such as Al, Ba, Ca, Cr, Cu, Mg, Mn, P, Sr, V, Zn, Be, K, and rare earth elements. The recent changes in the energy market towards renewables and increased metal recycling have resulted in reduced supplies of supplementary cementitious materials (coal fly ash and slag). Therefore, in Task III, we evaluated the possibility of employing WTE ashes as SCMs. As the chemical composition of WTE ashes varies temporally (on an hourly basis), there was also a need to develop tests that can evaluate the suitability of material to act as supplementary cementitious material rapidly, i.e., in a few minutes. Therefore, in Task II, we also developed a rapid test to assess the suitability of a material to act as an SCM in 5 minutes. This represents a significant advance over the state-of-the-art R 3 test, which takes ~144 hours. This test was initially validated on amorphous aluminosilicates, such as calcined clays, and could be extended to evaluate other industrial by-products, such as WTE ashes. In Task III, we evaluated the possibility of employing WTE ashes for two applications, i.e., as an SCM and a lime substitute for clay stabilization. The findings from Task I indicated that WTE ashes are enriched in chlorine and, therefore, cannot be used directly as an SCM due to corrosion-related risks and altered hydration kinetics. Accordingly, we developed an ash treatment protocol to reduce the solubility of chlorine-containing species in WTE ashes. The developed treatment protocol also immobilized lead in certain mineral forms. As a result of the treatment, WTE ashes can be used as SCMs without any corrosion or heavy metal leaching concerns. The second application examined in this study was clay stabilization. WTE ashes are calcium-rich and can be an adequate lime replacement for clay stabilization. Our findings reveal that the sum of the concentrations of Ca(OH) 2 and CaClOH controls the clay stabilization capability of WTE ashes. In summary, in this work, we evaluated the elemental and mineralogical characteristics of U.S. WTE ashes from diverse origins and developed tests to evaluate the chemical characteristics of these ashes in real time through a portable XRF and a benchtop Raman spectrometer. Based on the chemical characteristics of these ashes, we developed an ash treatment process to enable the use of WTE ashes as an SCM and also evaluated the possibility of employing these ashes for clay stabilization. Overall, the findings from this work enables the diversion of WTE ashes from landfills for multiple end-uses, i.e., as an SCM or a lime substitute for clay stabilization.

36 MATERIALS SCIENCE↗

Full Submersion Water Testing of SAVY-4000 Nuclear Material Storage Containers

SAVY-4000 (SAVY) containers are the primary container used at Technical Area (TA) TA-55 plutonium facility for the prevention of water ingress to mitigate against a criticality event. The basis for water resistance of these containers has long been attributed to the Polytetrafluoroethylene (PTFE) membrane that is assembled on the outermost surface of the filter assembly. On August 22nd a test of a container used inside of a glovebox was performed that brought into question this long-standing-basis. This test was performed by inverting a SAVY-lid onto a specialized piece of equipment for evaluating the integrity of the PTFE membrane. During the test water was observed passing through the filter indicating that the filter membrane was no longer preventing the ingress of water through the filter. The assumption after making this observation was that alpha-particles were rapidly degrading the membrane creating a leak path through the underlying aluminosilicate media (Fiberfrax®). The apparatus used was designed to only test the lid rather than the entire SAVY assembly. A test plan, PA-PLAN-01921, was developed to investigate whether a fully assembled container with a fully degraded PTFE membrane would be capable of meeting the criteria defined in PA-RD-1009 of not allowing more than 200 ml of water to enter the container with a water column of 6-inches applied over a 2-hour period. This report provides the results of the testing performed against PA-PLAN-01921.

36 MATERIALS SCIENCE↗

Iron dissolution from Patagonian dust in the Southern Ocean: under present and future conditions

Although the input of desert dust as a key source of trace metals in the Southern Ocean (SO) has been previously studied, the dissolution process of metals in surface waters, particularly iron (Fe), remain poorly understood. Given the crucial role of Fe in primary production and the biological carbon pump in the SO, we focused on experimental estimations of Fe dissolution from Patagonian dust, the primary natural dust source in the SO. Our study considered both current and projected future conditions, encompassing sea-surface warming, acidification, increased photosynthetically active radiation, and doubled dust inputs. Through controlled laboratory experiments using filtered SO seawater, conducted over 7 days, we assessed changes in particulate Fe (pFe) concentrations, Fe redox speciation (Fe(II)/Fe(III)), and in the mineralogy of Fe-bearing dust in abiotic condition. The predominant minerals in the dust included quartz and aluminosilicates, with silicon (Si), aluminum (Al), and Fe as the major elements. No significant alterations in the mineralogy and the elemental composition of the dust were recorded during the dissolution experiments, neither under present nor under projected future conditions. The particulate Fe(II)/Fe(III) ratio remained consistently at 0.25 during the experiments, unaffected by changed conditions. Consequently, changes in environmental conditions in the SO would therefore not significantly alter the mineralogy and redox speciation of pFe in the Patagonian dust. On the contrary, pFe exhibited a dissolution rate of 3.8% and 1.6% per day under present and future conditions, respectively. The environmental changes anticipated for 2100 in the SO will likely to result in a decrease in the dissolution rate of pFe. Thus, even though a doubling of dust input by 2100 is anticipated, it will unlikely provide significantly more dissolved Fe (dFe) in seawater in the SO. Consequently, the future intensification of Patagonian dust inputs may not alleviate the Fe limitation in the SO.

54 ENVIRONMENTAL SCIENCES↗

Monolithic microcircuit techniques and processes

Brief discussions of the techniques used to make dielectric and metal thin film depositions for monolithic circuits are presented. Silicon nitride deposition and the properties of silicon nitride films are discussed. Deposition of dichlorosilane and thermally grown silicon dioxide are reported. The deposition and thermal densification of borosilicate, aluminosilicate, and phosphosilicate glasses are discussed. Metallization for monolithic circuits and the characteristics of thin films are also included.

Kennedy, B. W.↗

Rationale for windshield glass system specification requirements for shuttle orbiter

A preliminary procurement specification for the space shuttle orbiter windshield pane, and some of the design considerations and rationale leading to its development are presented. The windshield designer is given the necessary methods and procedures for assuring glass pane structural integrity by proof test. These methods and procedures are fully developed for annealed and thermally tempered aluminosilicate, borosilicate, and soda lime glass and for annealed fused silica. Application of the method to chemically tempered glass is considered. Other considerations are vision requirements, protection against bird impact, hail, frost, rain, and meteoroids. The functional requirements of the windshield system during landing, ferrying, boost, space flight, and entry are included.

Hayashida, K.↗

Improved ceramic heat exchange material

Improved corrosion resistant ceramic materials that are suitable for use as regenerative heat exchangers for vehicular gas turbines is reported. Two glass-ceramic materials, C-144 and C-145, have superior durability towards sulfuric acid and sodium sulfate compared to lithium aluminosilicate (LAS) Corning heat exchange material 9455. Material C-144 is a leached LAS material whose major crystalline phase is silica keatite plus mullite, and C-145 is a LAS keatite solid solution (S.S.) material. In comparison to material 9455, material C-144 is two orders of magnitude better in dimensional stability to sulfuric acid at 300 C, and one order of magnitude better in stability to sodium sulfate at 1000 C. Material C-145 is initially two times better in stability to sulfuric acid, and about one order of magnitude better in stability to sodium sulfate. Both C-144 and C-145 have less than 300 ppm delta L/L thermal expansion from ambient to 1000 C, and good dimensional stability of less than approximately 100 ppm delta L/L after exposure to 1000 C for 100 hours. The glass-ceramic fabrication process produced a hexagonal honeycomb matrix having an 85% open frontal area, 50 micrometer wall thickness, and less than 5% porosity.

Mccollister, H. L.↗

Improved ceramic heat exchanger materials

The development and evaluation of materials for potential application as heat exchanger structures in automotive gas turbine engines is discussed. Test specimens in the form of small monolithic bars were evaluated for thermal expansion and dimensional stability before and after exposure to sea salt and sulfuric acid, followed by short and long term cycling at temperatures up to 1200 C. The material finally selected, GE-7808, consists of the oxides, ZrO2-MgO-Al2O3-S1O2, and is described generically as ZrMAS. The original version was based on a commercially available cordierite (MAS) frit. However, a clay/talc mixture was demonstrated to be a satisfactory very low cost source of the cordierite (MAS) phase. Several full size honeycomb regenerator cores, about 10.2 cm thick and 55 cm diameter were fabricated from both the frit and mineral versions of GE-7808. The honeycomb cells in these cores had rectangular dimensions of about 0.5 mm x 2.5 mm and a wall thickness of approximately 0.2 mm. The test data show that GE-7808 is significantly more stable at 1100 C in the presence of sodium than the aluminosilicate reference materials. In addition, thermal exposure up to 1100 C, with and without sodium present, results in essentially no change in thermal expansion of GE-7808.

Rauch, H. W.↗

Early development of ceramic fiber insulation for the Space Shuttle

The evolution of reusable surface insulation is described, with attention to the mullite and other aluminosilicates, zirconia, and silicon carbide-coated carbon compositions experimented with in the late 1960s and early 1970s. Evaluation and development concentrated in this period on such aspects of design and material properties as cold soak performance, attachment, shock impingement, surface coating cracks, and tile gap design and heating. In addressing the central problem of heat-shield thermal conductivity, it was found that for a given density, silica fibers had a lower conductivity than those of mullite. This was due to the one-micron, as opposed to 4.7-micron, diameter of the silica fibers, which resulted in smaller pores and therefore less convective and radiative heat transfer. Attention is also given to tile coating materials and the high-temperature processes by which they were applied.

Buckley, J. D.↗

Clay-mediated reactions of HCN oligomers - The effect of the oxidation state of the clay

Montmorillonite clays which contain Fe(III) inhibit the oligomerization of aqueous solutions of HCN. The inhibitory effect is due to the rapid oxidation of diaminomaleonitrile, a key intermediate in HCN oligomerization, by the Fe(III) incorporated into the aluminosilicate lattice of the clay. The Fe(III) oxidizes diaminomaleonitrile to diiminosuccinonitrile, a compound which is rapidly hydrolyzed to HCN and oxalic acid derivatives. Diaminomaleonitrile is not oxidized when Fe(III) in the montmorillonite is reduced with hydrazine. The oxidation state of the clay is an important variable in experiments designed to simulate clay catalysis on the primitive earth.

Ferris, J. P.↗

Primordial retention of nitrogen by terrestrial planets and meteorites

Thermodynamic calculations of the amount of dissolved nitrogen in Fe-Ni alloy in a solar composition gas were done over a wide range of temperatures and pressures. The stabilities of the nitride minerals found in meteorites, a large number of other nitrides, and ammonium aluminosilicates were also calculated in a solar gas. This thorough study indicates that equilibrium mechanisms cannot account for the nitrogen contents of the terrestrial planets and meteorites. The best available data indicate that the observed nitrogen contents of planets and meteorites are several orders of magnitude greater than the predicted nitrogen contents of condensed material in a solar gas. It is suggested that the nitrogen in meteorites was originally retained as organic compounds produced by disequilibrium mechanisms. Nitrogen retention by the terrestrial planets could be due to homogeneous accretion or to accretion of a volatile-rich veneer. However, the actual mode of nitrogen accretion cannot yet be determined.

Fegley, B., Jr.↗

A note on the Raman spectra of water-bearing albite glasses

The Raman spectra of albite glasses with 4.5 and 6.6 weight percent water have been obtained, and are compared with that of a dry sample. The hydrous glasses show bands near 3600/cm due to O-H stretching, and a previously unreported weak band near 1600/cm due to bending of molecular H2O. Other weak spectral features are discussed, and the effect of dissolved water on the aluminosilicate framework vibrations is considered.

Mcmillan, P. F.↗

Steps toward eight-meter honeycomb mirror blanks. I Rationale and approach

The best form for 8-m telescope mirrors is discussed. It is concluded that honeycomb sandwich structure can meet the most exacting demand goals for subarcsecond image quality in optical and infrared astronomy. These structures are light, have good stiffness against gravitational and wind loading, and have low thermal inertia. The latter permits them to be operated at the ambient air temperature to avoid local seeing problems. Borosilicate and aluminosilicate glasses are adequate materials for ventilated honeycombs, which do not require low expansion materials.

Angel, J. R. P.↗