Adaptation of the GRAAL model of Glass Reactivity to accommodate non-linear diffusivity
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Rieke, Peter C.↗
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Potential-Induced Degradation of Cu(In,Ga)Se 2 Solar Cells: Alkali Metal Drift and Diffusion Effects
Potential-induced degradation (PID) of photovoltaic modules is due to transport of alkali metal ions (Na + ) from the soda-lime glass (SLG) into the semiconductors. For the most efficient polycrystalline absorbers, Na and K in the Cu(In,Ga)(Se,S) 2 (CIGS) absorber often benefit performance, so a more detailed mechanism for PID is needed. To that end, CIGS solar cells have been encapsulated, stressed with high voltage, and cored to extract the active regions for characterization. SLG substrates led to 14.9% efficiency on average, which reduced to 0% after 25 h of -1000 V bias. This was accompanied by increased Na in the CIGS layer, particularly at the buffer interface, as well as decreased carrier concentrations. On the other hand, borosilicate glass substrates with low Na and high K content led to 13.6% efficiency on average, which only reduced to 12.1% after 25 h of stress. This was accompanied by slightly increased K content in the CIGS layer. As K has led to recent world record efficiency CIGS devices, understanding Na and K similarities and differences may help to enhance initial efficiency and reduce PID.
14 SOLAR ENERGY↗
Corrosion Behavior of Developmental Iron Phosphate Waste Forms: FY20 Status Report
Corrosion tests were performed to assess the dissolution behaviors of developmental iron phosphate materials that are being evaluated as an alternative to the glass-bonded sodalite ceramic waste form to immobilize salt wastes from electrochemical separation operations. Production of the iron phosphate waste form results in dehalogenation of the waste salt that increases potential waste loading. Ferric oxide is added to the waste form to increase the chemical durability. Tests conducted to optimize the amount of ferric oxide used to make the waste form are summarized in this report. Specimens prepared from materials made with between 17 and 34 mole % ferric oxide were subjected to two test methods to assess the effects of the iron content on the relative durability and retention of immobilized salt cations including cesium, strontium, and neodymium. Modified ASTM C1308 test results show the intrinsic durability was significantly higher for materials made with 27 mol % ferric oxide. Further additions generated iron-rich inclusion phases and did not improve durability. Modified ASTM C1285 test results show that solution feedback attenuates the dissolution rate similar to what is observed for borosilicate glasses within seven days. Analyses of test specimens after 42 days show no evidence that surface layers formed. Combined with previous studies addressing the salt loading, a composition region of the ammonium (di)hydrogen phosphate-waste salt-ferric oxide ternary has been defined for durable waste form compositions. Materials with that composition can be used to determine optimal processing conditions, assess long-term performance, and parameterize a degradation model.
Stariha, S. A.↗
Preliminary assessment of stable nitrogen and oxygen isotopic composition of USGS51 and USGS52 nitrous oxide reference gases and perspectives on calibration needs
Rationale: Despite a long history and growing interest in isotopic analyses of N 2 O, there is a lack of isotopically characterized N 2 O isotopic reference materials (standards) to enable normalization and reporting of isotope-delta values. Here, in this paper we report the isotopic characterization of two pure N 2 O gas reference materials, USGS51 and USGS52, which are now available for laboratory calibration (https://isotopes.usgs.gov/lab/referencematerials.html). Methods: A total of 400 sealed borosilicate glass tubes of each N 2 O reference gas were prepared from a single gas filling of a high vacuum line. We demonstrated isotopic homogeneity via dual-inlet isotope-ratio mass spectrometry. Isotopic analyses of these reference materials were obtained from eight laboratories to evaluate interlaboratory variation and provide preliminary isotopic characterization of their δ 15 N, δ 18 O, δ 15 N α , δ 15 N β and site preference (S P ) values. Results: The isotopic homogeneity of both USGS51 and USGS52 was demonstrated by one-sigma standard deviations associated with the determinations of their δ 15 N, δ 18 O, δ 15 N α , δ 15 N β and S P values of 0.12 mUr or better. The one-sigma standard deviations of SP measurements of USGS51 and USGS52 reported by eight laboratories participating in the interlaboratory comparison were 1.27 and 1.78 mUr, respectively. Conclusions: The agreement of isotope-delta values obtained in the interlaboratory comparison was not sufficient to provide reliable accurate isotope measurement values for USGS51 and USGS52. Lastly, we propose that provisional values for the isotopic composition of USGS51 and USGS52 determined at the Tokyo Institute of Technology can be adopted for normalizing and reporting sample data until further refinements are achieved through additional calibration efforts.
54 ENVIRONMENTAL SCIENCES↗
Iodosodalite synthesis with hot isostatic pressing of precursors produced from aqueous and hydrothermal processes
Iodosodalite powders were synthesized using aqueous and hydrothermal methods, with or without sodium borosilicate glass binders, and then hot isostatically pressed (HIP) at 900 ? and 175 MPa for 3 h to convert into waste forms. After HIPing, the structures, compositions, morphologies, porosities, and leach rates of the aqueous and hydrothermally produced iodosodalite samples were compared. X-ray diffraction patterns of HIPed samples showed that iodosodalite remained as the dominant phase. However, the fraction of the iodosodalite phase decreased after HIPing, indicating decomposition of the iodosodalite structure during the HIP process. Scanning electron microscopy and chemical imaging on the cross sections of HIPed samples showed homogeneous elemental distribution for aqueous-grown iodosodalite, whereas hydrothermally grown iodosodalite samples had more heterogeneity and porosity. The densities of HIPed samples with more glass binder were generally higher than sampled HIPed without binder. The leach tests on samples containing 20 mass% glass binder showed that the iodine dissolution rate of HIPed hydrothermally grown iodosodalite was about 4 times higher than iodosodalite by aqueous method. This study provides alternative techniques for immobilizing iodine-streams in iodosodalite waste forms.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Pilot production & commercialization of LAPPD ™
We present a progress update on plans to establish pilot production and commercialization of Large Area (400 cm2) Picosecond Photodetector (LAPPD™). Steps being taken to commercialize this MCP and LAPPD™ technology and begin tile pilot production are presented including (1) the manufacture of 203 mm×203 mm borosilicate glass capillary arrays (GCAs), (2) optimization of MCP performance and creation of an ALD coating facility to manufacture MCPs and (3) design, construction and commissioning of UHV tile integration and sealing facility to produce LAPPDs. Taken together these plans provide a “pathway toward commercialization”.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Methane generation from low-maturity coals and shale source rocks at low temperatures (80–120 °C) over 14–38 months
This study contributes long-term (14 to 38 months) experimental evidence for geocatalytically mediated methanogenesis in immature to early mature shale and coal source rocks at temperatures from 80 to 120 °C. Borosilicate glass tubes with pre-outgassed coal and shale source rock chips and water were sealed under vacuum, sterilized, heated isothermally, and finally opened in connection with a vacuum line where headspace gases methane (CH 4 ) and carbon dioxide (CO 2 ) were collected. The possibility of admitting pre-existing CH 4 from closed pores into product gases during heating experiments was evaluated by comparative ball milling of original and heated rock chips, followed by quantitation of released gases with a novel closed-circuit laser-based SARAD RTM2200 gas detector system with sub-µmol sensitivity. The yields of produced CH 4 from individual source rocks were corrected by subtracting the amounts of pre-existing CH 4 from formerly closed pores in original source rocks that had leaked during long-term heating. Different shales and coals express contrasting propensities to geocatalytically generate CH 4 and CO 2 , with CH 4 yields ranging from 0.1 to 5.5 µmol g-1 total organic carbon (TOC). CH 4 yields from two petrographically different samples of Springfield Coal with comparable thermal maturity suggest that liptinite expresses a far higher propensity for methanogenesis, but liberates less CO 2 than vitrinite. Shale from the Second White Specks Formation generated approximately 10 times more CH 4 than New Albany Shale per g of TOC, further suggesting complex controls on CH 4 generation during catalytic methanogenesis. Higher temperature can enhance the activities of catalytic methanogenesis. Here, the extrapolation of laboratory-based reaction rates to natural conditions in organic-rich buried sediments suggests that geocatalytic methanogenesis can be fast enough in some source rocks to generate economically sizeable gas plays from immature to early mature source rocks over geologic time.
03 NATURAL GAS↗
Radioactive waste immobilization of Hanford sludge in magnesium potassium phosphate ceramic forms
Here, this paper evaluates immobilization of Hanford K-Basin tank sludge in magnesium potassium phosphate ceramic forms. The waste forms were produced using two simulated non-radioactive sludge streams, each with distinct characteristics and composition. Ceramicrete with wollastonite as filler was used as the matrix for this purpose. The resulting waste forms were tested for their mechanical properties, radiation stability, and leaching resistance. In another series of tests, the samples were vitrified in borosilicate glass and glass waste forms were produced. The Product Consistency Test, the American Nuclear Society's ANS 16.1 test, and the Toxicity Characteristic Leaching Procedure, which are used to develop waste acceptance criteria in the United States for permanent storage of treated waste, were used for evaluation of the leaching resistance of all waste forms.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Efficient Capture of Perrhenate and Pertechnetate by a Mesoporous Zr Metal–Organic Framework and Examination of Anion Binding Motifs
At the Hanford Site in southeastern Washington state, the U.S. Department of Energy intends to treat 56 million gallons of legacy nuclear waste by encasing it in borosilicate glass via vitrification. This process ineffectively captures radioactive pertechnetate (TcO 4 –) because of the ion’s volatility, thereby requiring a different remediation method for this long-lived (t 1/2 = 2.1 × 10 5 years), environmentally mobile species. Currently available sorbents lack the desired combination of high uptake capacity, fast kinetics, and selectivity. Here, we evaluate the ability of the chemically and thermally robust Zr 6 -based metal–organic framework (MOF), NU-1000, to capture perrhenate (ReO 4 –), a pertechnetate simulant, and pertechnetate. Our material exhibits an excellent perrhenate uptake capacity of 210 mg/g, reaches saturation within 5 min, and maintains perrhenate uptake in the presence of competing anions. Additionally, experiments with pertechnetate confirm perrhenate is a suitable surrogate. Single-crystal X-ray diffraction indicates both chelating and nonchelating perrhenate binding motifs are present in both the small pore and the mesopore of NU-1000. Postadsorption diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) further elucidates the uptake mechanism and powder X-ray diffraction (PXRD) and Brunauer–Emmett–Teller (BET) surface area analysis confirm the retention of crystallinity and porosity of NU-1000 throughout adsorption.
36 MATERIALS SCIENCE↗
High-Field Magic Angle Spinning Dynamic Nuclear Polarization Using Radicals Created by γ-Irradiation
High-field magic angle spinning dynamic nuclear polarization (MAS DNP) is often used to enhance the sensitivity of solid-state nuclear magnetic resonance experiments by transferring spin polarization from electron spins to nuclear spins. In this work, we demonstrate that γ-irradiation induces the formation of stable radicals in inorganic solids, such as fused quartz and borosilicate glasses, as well as organic solids, such as glucose, cellulose, and a urea/polyethylene polymer. The radicals were then used to polarize 29 Si or 1 H spins in the core of some of these materials. Significant MAS DNP enhancements (ε) of more than 400 and 30 were obtained for fused quartz and glucose, respectively. For other samples, negligible values of ε were obtained, likely due to low concentrations of radicals or the presence of abundant quadrupolar spins. These results demonstrate that ionizing radiation is an enticing alternative method for generating stable radicals that are suitable for high-field MAS DNP experiments.
36 MATERIALS SCIENCE↗
A Case for Molecular Recognition in Nuclear Separations: Sulfate Separation from Nuclear Wastes
In this paper, we present the case for molecular-recognition approaches for sulfate removal from radioactive wastes via the use of anion-sequestering systems selective for sulfate, using either liquid liquid extraction or crystallization. Potential benefits of removing sulfate from the waste include improved vitrification of the waste, reduced waste-form volume, and higher waste-form performance, all of which lead to potential cleanup schedule acceleration and cost savings. The need for sulfate removal from radioactive waste, especially legacy tank wastes stored at the Hanford site, is reviewed in detail and primarily relates to the low solubility of sulfate in borosilicate glass. Traditional methods applicable to the separation of sulfate from radioactive wastes are also reviewed, with the finding that currently no technology has been identified and successfully demonstrated to meet this need. Fundamental research in the authors laboratories targeting sulfate as an important representative of the class of oxoanions is based on the hypothesis that designed receptors may provide the needed ability to recognize sulfate under highly competitive conditions, in particular where the nitrate anion concentration is high. Receptors that have been shown to have promising affinity for sulfate, either in extraction or in crystallization experiments, include hexaurea tripods, tetraamide macrocycles, cyclo[8]pyrroles, calixpyrroles, and self-assembled urea-lined cages. Good sulfate selectivity observed in the laboratory provides experimental support for the proposed molecular-recognition approach.
Moyer, Bruce A↗
Effects of Chemical Complexity on the Autoxidation Mechanisms of Endocyclic Alkene Ozonolysis Products: From Methylcyclohexenes toward Understanding α-Pinene
Formation of highly oxidized, multifunctional products in the ozonolysis of three endocyclic alkenes, 1- methylcyclohexene, 4- methylcyclohexene, and α-pinene, was investigated using a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer with a nitrate ion (NO 3 - ) based ionization scheme. Also, the experiments were performed in borosilicate glass flow tube reactors at room temperature (T = 293 ± 3 K) and at ambient pressure. An ensemble of oxidized monomer and dimer products was detected, with elemental compositions obtained from the high-resolution mass spectra. The monomer product distributions have O/C ratios from 0.8 to 1.6 and can be explained with an autocatalytic oxidation mechanism (=autoxidation) where the oxygen-centered peroxy radical (RO 2 ) intermediates internally rearrange by intramolecular hydrogen shift reactions, enabling more oxygen molecules to attach to the carbon backbone. Dimer distributions are proposed to form by homogeneous peroxy radical recombination and cross combination reactions. Our conclusions were supported by experiments where H atoms were exchanged to D atoms by addition of D 2 O to the carrier gas flow. Methylcyclohexenes were observed to autoxidize in accordance with our previous work on cyclohexene, whereas in α-pinene ozonolysis different mechanistic steps are needed to explain the products observed.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Review of corrosion interactions between different materials relevant to disposal of high-level nuclear waste
Abstract This review covers the corrosion interactions between different materials that are relevant to the disposal of high-level nuclear waste, in particular the waste forms and containers. The materials of interest are borosilicate glass, crystalline ceramics, metal alloys, and any corrosion products that might form. The available data show that these interactions depend on the structure, chemistry, thermodynamic history, and proximity of the materials in contact, as well as the environmental attributes, such as temperature, solution chemistry, and radiation. Several key mechanisms that govern these interactions are highlighted. Scientific gaps and open questions are summarized and discussed.
Materials Science↗
Effects of molecular confinement and crowding on horseradish peroxidase kinetics using a nanofluidic gradient mixer
Here, we studied the effects of molecular confinement and crowding on enzyme kinetics at length scales and under conditions similar to those found in biological cells. These experiments were carried out using a nanofluidic network of channels constituting a nanofluidic gradient mixer, providing the basis for measuring multiple experimental conditions simultaneously. Furthermore, the 100 nm × 40 μm nanochannels were wet etched directly into borosilicate glass, then annealed and characterized with fluorescein emission prior to kinetic measurements. The nanofluidic gradient mixer was then used to measure the kinetics of the conversion of the horseradish peroxidase (HRP)-catalyzed conversion of non-fluorescent Amplex Red (AR) to the fluorescent product resorufin in the presence of hydrogen peroxide (H 2 O 2 ). The design of the gradient mixer allows reaction kinetics to be studied under multiple (five) unique solution compositions in a single experiment. In order to characterize the efficiency of the device the effects of confinement on HRP-catalyzed AR conversion kinetics were studied by varying the starting ratio of AR : H 2 O 2 . Equimolar concentrations of Amplex Red and H 2 O 2 yielded the highest reaction rates followed by 2 : 1, 1 : 2, 5 : 1, and finally 1 : 5 [AR] : [H 2 O 2 ]. Under all conditions, initial reaction velocities were decreased by excess H 2 O 2 . Crowding effects on kinetics were studied by increasing solution viscosity in the nanochannels in the range 1.0–1.6 cP with sucrose. Increasing the solution viscosities in these confined geometries decreases the initial reaction velocity at the highest concentration from 3.79 μM min -1 at 1.00 cP to 0.192 μM min -1 at 1.59 cP. Variations in reaction velocity are interpreted in the context of models for HRP catalysis and for molecular crowding.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Can Cr( iii ) substitute for Al( iii ) in the structure of boehmite?
The dissolution of boehmite is a technical issue for the Al industry because of its recalcitrant nature. In fact, a similar problem exists with boehmite in nuclear waste sludge at the Hanford site in eastern Washington State, USA. Dissolution of Al phases is required to reduce the waste loadings in the final borosilicate glass waste form. Although not the most common Al-bearing species in the sludge, boehmite may become a rate limiting step in the processing of the wastes. Hanford boehmite is an order of magnitude more resistant to dissolution in hot caustic solutions than expected from surface-normalized rates. We are exploring potential intrinsic and extrinsic effects that may limit boehmite reactivity; one clue comes from microstructural analyses that indicate an association of Cr with Al in the Hanford nuclear waste. Hence, in this first paper, we investigated the potential role of chromium on the reactivity of boehmite in caustic solution. An important finding was that irrespective of the synthesis pathway, amount of Cr(III), or the resultant morphology, there was no evidence for Cr incorporation in the bulk structure, in agreement with QM calculations. In fact, electron microscopic (EM) and spectroscopic analyses showed that Cr was enriched at the (101) edges of the boehmite. However, Cr had no measurable effect on the morphology during the synthesis step. In contrast, comparison of the morphologies of the synthetic Cr-doped and pure boehmite samples after exposure to caustic solutions provided evidence that Cr inhibited the corrosion. TEM showed that Cr was not homogeneously distributed at the surface. Consequently, Cr may have partially passivated the surface by blocking discrete energetic sites on the lateral surfaces of boehmite.
1-Cra and 1-Crb↗
The crystal chemistry of plutonium( iv ) borophosphate
Pu IV borophosphate crystallized from a complex solution in a borosilicate glass vial after one year. The suspected leaching of B from the glass vial could have important implications for the corrosion of vitrified nuclear waste.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Optical basicity and polarizability for copper-zinc doped sol-gel glasses
CaO-SiO{sub 2}-B{sub 2}O{sub 3}-P{sub 2}O{sub 5} glasses have been studied by varying ratios of Copper oxide and Zinc oxide. Glasses were prepared using Sol-Gel technique. Opitical Basicity and oxide ion Polarizability were calculated and discussed in relation with non bridging Oxygen ions (NBOs). Optical basicity is average electron donating capability of an oxide atom. All glasses had a little difference in optical basicity and polarizability values but CZ8 glass (20CaO-60SiO{sub 2}-5B{sub 2}O{sub 3}-5P{sub 2}O{sub 5}-2CuO-8ZnO) came out to show highest optical basicity and polarizability with value 0.5177 and 0.9798 respectively. This showed the highest electron donating tendency of CZ8 glass and highest number of NBOs. These were minimum for CZ2 glass with 8CuO and 2ZnO. In aspect of optical basicity and polarizability glasses follow the series CZ2 < CZ4 < CZ6 < CZ8. Increasing concentration of ZnO and decreasing concentration of CuO lead to higher optical basicity and oxide ion polarizability.
36 MATERIALS SCIENCE↗
Fast-timing microchannel plate photodetectors: design, fabrication and characterization
We report a detailed design, fabrication, and characterization of 6 x 6 cm(2) fast timing photodetectors based on next-generation microchannel plates (MCPs). The whole assembly is made of low-cost borosilicate glass materials and hermetically sealed with a bialkali photocathode in a vacuum. The flexible photodetector design provides the potential of modifying individual components as well as the entire configuration to fit for different applications. A series of prototype MCP-photodetectors were fabricated following a step-by-step process including functionalization of glass capillary array through atomic layer deposition, MCP baking and scrubbing, photocathode deposition, and hermetic thermo-compression sealing. The prototype MCP-photodetectors exhibit electron gains well beyond 107 level with good relative uniformity. An excellent rise time of 439 ps, timing distribution root-mean-square at a single photoelectron mode of 105 ps, a timing resolution of 20 ps, and magnetic field tolerance up to 1.3 T were achieved for a photodetector with 10 mu m pore size MCPs, comparing to that of 536 ps, 205 ps, 63 ps, and 0.7 T for the one with 20 mu m pore size MCPs. Published under license by AIP Publishing.
fast timing↗