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McCloy, John S.

Publications and source records attributed to McCloy, John S..

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Photoluminescence spectroscopy of Cr 3+ in β-Ga 2 O 3 and (Al 0.1 Ga 0.9 ) 2 O 3

Alloying β-Ga 2 O 3 with Al 2 O 3 to create (Al x Ga 1–x ) 2 O 3 enables ultra-wide bandgap materials suitable for applications deep into ultraviolet. In this work, photoluminescence (PL) spectra of Cr 3+ were investigated in monoclinic single crystal β-Ga 2 O 3 , and 10 = mol. % Al 2 O 3 alloyed with β-Ga 2 O 3 , denoted β-(Al 0.1 Ga 0.9 ) 2 O 3 or AGO. Temperature-dependent PL properties were studied for Cr 3+ in AGO and β-Ga 2 O 3 from 295 to 16 K. For both materials at room temperature, the red-line emission doublet R 1 and R 2 occurs at 696 nm (1.78 eV) and 690 nm (1.80 eV), respectively, along with a broad emission band at 709 nm (1.75 eV). Here, the linewidths for AGO are larger for all temperatures due to alloy broadening. For both materials, the R-lines blue-shift with decreasing temperature. The (lowest energy) R 1 line is dominant at low temperatures due to the thermal population of the levels. For temperatures above ~50 K, however, the ratio of R 2 to R 1 peak areas is dominated by nonradiative combination.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Micro- and Nanoscale Surface Analysis of Late Iron Age Glass from Broborg, a Vitrified Swedish Hillfort

Abstract Archaeological glasses with prolonged exposure to biogeochemical processes in the environment can be used to understand glass alteration, which is important for the safe disposal of vitrified nuclear waste. Samples of mafic and felsic glasses with different chemistries, formed from melting amphibolitic and granitoid rocks, were obtained from Broborg, a Swedish Iron Age hillfort. Glasses were excavated from the top of the hillfort wall and from the wall interior. A detailed microscopic, spectroscopic, and diffraction study of surficial textures and chemistries were conducted on these glasses. Felsic glass chemistry was uniform, with a smooth surface showing limited chemical alteration (<150 nm), irrespective of the position in the wall. Mafic glass was heterogeneous, with pyroxene, spinel, feldspar, and quartz crystals in the glassy matrix. Mafic glass surfaces in contact with topsoil were rougher than those within the wall and had carbon-rich material consistent with microbial colonization. Limited evidence for chemical or physical alteration of mafic glass was found; the thin melt film that coated all exposed surfaces remained intact, despite exposure to hydraulically unsaturated conditions, topsoil, and associated microbiome for over 1,500 years. This supports the assumption that aluminosilicate nuclear waste glasses will have a high chemical durability in near-surface disposal facilities.

Matthews, Bethany E. (ORCID:0000000171932583)↗
DOE OSTI2022

Electro-Optical Characterization of Arsenic-Doped CdSeTe and CdTe Solar Cell Absorbers Doped in-situ During Close Space Sublimation

Most contemporary device models predict that an acceptor concentration of at least 10^16 cm^-3 is required to reach an open circuit voltage of 1 V in polycrystalline CdTe-based solar cells. While copper has traditionally been used as the de facto p-type dopant in polycrystalline cadmium telluride (CdTe) and cadmium selenide telluride (CdSeTe), reaching high acceptor concentrations has proved to be challenging in such devices due to significant dopant compensation. The acceptor concentration in copper-doped CdTe and CdSeTe typically ranges from 10^13 to 10^15 cm^-3 and routinely exhibit low external radiative efficiencies below 0.01%, limiting their implied voltage (i.e., quasi-Fermi level splitting) to approximately 900 mV. As an alternative to copper, this work explores the use of arsenic as a p-type dopant for CdTe and CdSeTe. Using a novel technique in which a thin layer of arsenic-containing material is deposited and used as a reservoir for arsenic to diffuse into a front layer of previously undoped material, this contribution demonstrates that high external radiative efficiencies are achievable, a direct result of combined high acceptor concentrations and long minority-carrier lifetimes in the absorber. This leads to improved implied voltages, and indicates that As-doping represents a promising pathway towards improving the external voltage of CdSeTe/CdTe solar cells.

cadmium telluride↗
DOE OSTI2022

Effect of network connectivity on behavior of synthetic Broborg hillfort glasses

There is wide industrial interest in developing robust models of long-term (>100 years) glass durability. Archeological glass analogs, glasses of similar composition, and alteration conditions to those being tested for durability can be used to evaluate and inform such models. Two such analog glasses from a 1500-year-old vitrified hillfort near Uppsala, Sweden have previously been identified as potential analogs for low concentration Fe-bearing aluminosilicate nuclear waste glasses. However, open questions remain regarding the melting environment from which these historic glasses were formed and the effect of these conditions on their chemical durability. A key factor to answering the previous melting and durability questions is the redox state of Fe in the starting and final materials. Past work has shown that the melting conditions of a glass-forming melt may influence the redox ratio value (Fe +3 /ΣFe), a measure of a glass's redox state, and both melting conditions and the redox ratio may influence the glass alteration behavior. Synthetic analogs of the hillfort glasses have been produced using either fully oxidized or reduced Fe precursors to address this question. In this study, the melting behavior, glass transition temperature, oxidation state, network structure, and chemical durability of these synthesized glass analogs is presented. Resulting data suggests that the degree of network connectivity as impacted by the oxidation state of iron impacted the behavior of the glass-forming melt but in this case does not affect the chemical durability of the final glass. Glasses with a lower degree of melt connectivity were found to have a lower viscosity, resulting in a lower glass transition temperature and softening temperature, as well as in a lower temperature of foam onset and temperature of foam maximum. This lower degree of network connectivity most likely played a more significant role in accelerating the conversion of batch chemicals into glass than the presence of water vapor in the furnace's atmosphere. Future work will focus on using the results from this work with outcomes from other aspects of this project to evaluate long-term glass alteration models.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Developing CdTe homojunctions applying high throughput deposition

In this project, we attempted to make CdTe homojunctions using single crystal p-type doped substrates and closed-space sublimation epitaxy (CSSE) n-type doped films. The project included modeling which determined the ideal thickness for the n-type layer as being <200 nm. Boules of high concentration indium-doped CdTe and CdSe 0.4 Te 0.6 (CST) were grown using modified vertical Bridgman (MVB) methods. Similarly, iodine-doped CdTe crystals were grown for the first time. Washington State University (WSU) stock phosphorus-doped CdTe was used as the p-type substrate layer. The crystals were characterized by Hall effect and time-resolved photoluminescence (TRPL, for electrical properties), photoluminescence microscopy (for uniformity), X-ray diffraction (for crystal structure), and glow discharge mass spectrometry (GDMS, for dopant and impurity concentration). CdTe:I crystals were also characterized by visible and infrared transmission measurements, and various Cd or Te heat treatments were performed to assess changes in optical and electrical properties. The grown n-type materials – CdTe:In, CdSe0.4Te0.6:In, and CdTe:I – were provided to the National Renewable Energy Laboratory (NREL) for growth of CSSE thick films for characterization by two photon TRPL (for carrier lifetime), electron back-scatter diffraction (EBSD, to assess epitaxy), and Hall effect. Several measurements of secondary ion mass spectroscopy (SIMS) were performed. Nearly 100% of the indium from the crystal was incorporated into the measured thick films, while only ~2-22% of the iodine from the crystal was incorporated. The net result of the diffusion issue is that homojunction devices created using CSSE have a buried homojunction, as indicated by the near infrared peak in the external quantum efficiency (EQE). Various parameterization of front and back contacts suggested that the poor device performance was primarily a result of this buried junction and not due to other effects. There may also be an issue with the CSSE film lifetime in addition to the dopant profile.

14 SOLAR ENERGY↗
DOE OSTI2022

Stirred-Reactor Coupon Analysis: An International Round Robin Study

The objective of this task was to determine the precision of the SRCA technique when used to determine the dilute condition corrosion rate. To this end, an interlaboratory round robin study was conducted per the instructions in ASTM Practice E691 to measure the precision with which the SRCA test method can be conducted. Twelve independent labs from eleven different institutions each evaluated four glass compositions in three different conditions. The ASTM procedures recommend at least 6 labs participate in a round robin testing the same 3 materials in the same conditions to determine precision. In this case, 12 labs each performed 12 independent tests. This was only possible thanks to the multi-glass testing capability of the SRCA test. A total of 108 duplicate pairs were used to calculate the repeatability of the tests, with the same glass tested in the same vessel, producing as identical conditions as possible for the replicates. These test results were quite tightly clustered, with a median difference from the average value of the pair of only 2.9%. Based on the calculations outlined in ASTM E177-20 and a measured standard deviation of 4.74%, the intralaboratory repeatability limit (r) was calculated to be within 13.3% of the expected value with 95% confidence level. The reproducibility limit (R) of the test was examined using all 277 data points from the round robin. Because of the differences in dissolution rates due to pH variability and intrinsically for the 12 conditions tested, the reproducibility limits for each condition and overall were calculated from the percent relative residual value for each test. The SRCA test is expected to be reproducible within 64% of the expected value with a 95% confidence level.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Microstructural examination of interactions between chromia-based refractory and nuclear glass in a melter

This study shows the effects of nuclear waste glass production on Monofrax K-3 refractory corrosion. A continuously fed research-scale melter containing an Fe- and Ni-rich simulated nuclear waste feed with borosilicate glass-forming chemicals was cyclically melted at 1150°C and idled at 1050°C for a total of 11 weeks. Chemical maps using scanning electron microscopy show the interactions between the quenched melt and the refractory. Nanoscale X-ray-computed tomography was used for a three-dimensional visualization of certain parts of the interface. Unreacted K-3 consists of primarily corundum (Al,Cr) 2 O 3 and spinel (Fe 2+ ,Mg)(Al,Cr) 2 O 4 interlocking crystalline phases. Some of the Cr from the refractory interacts with the Ni and Fe from the melt to form a reaction layer comprising (Ni,Fe 2+ )(Cr,Fe 3+ ) 2 O 4 spinel crystals. Simultaneously, melt components (Na,Si) infiltrate into the refractory. This interaction proceeds at the expense of the integrity of the refractory structure. Intact refractory grains (e.g., (Al,Cr) 2 O 3 ) as well as the reaction layer itself can lose mechanical integrity and spall off into the melt, especially near the top of the melter. As the reaction layer can be a protective boundary for the refractory against further melt infiltration, a reduction in the reaction layer thickness allows an increase in refractory corrosion.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Multivariate analysis: An essential for studying complex glasses

Understanding the impact of individual compositional components on the devitrification of complex multicomponent glasses, for example, 10–50+ oxides, typically requires numerous studies to examine each component's impact. Here we apply exploratory data analysis (EDA) to a heterogeneous data set of silicate glasses to determine the cations’ individual and interacting effects on the crystallization of nepheline (nominally NaAlSiO 4 ). Our data consisted of 795 simulated high-level nuclear waste glasses composed of, on average, 50 oxide components. We determine the interactions in the heterogeneous data that cause deviations from the behavior found in simplified composition studies. Using both univariate and bivariate EDA techniques, we demonstrate the importance of including calculated structural glass parameters on nepheline's devitrification, including field strength, cation-to-anion radius ratio, and single-bond strength. Here, we also show that studies with simplified glass compositions may fall short in generating knowledge directly transferrable to complex glass compositions. The method used in this study has the potential to inform experimental design for simplified compositions (~6+ oxides) that can generate knowledge directly transferrable to complex, multivariable compositions. The observations reported here have broad implications for any study attempting to map the physical properties of a complex glass containing numerous cations.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Major to trace element imaging and analysis of iron age glasses using stage scanning in the analytical dual beam microscope (tandem)

Dark and clear silicate glasses formed during an iron age vitrification event ≈ 1500 years ago at the Broborg hillfort near Uppsala, Sweden have been analyzed using a scanning electron microscope equipped with a micro-X-ray fluorescence (μXRF) spectrometer. Correlated µXRF and electron beam-induced energy dispersive spectrometry (EDS) X-ray maps were collected via stage-scanning at constant velocity. This coupled procedure represents a new approach for the cultural heritage community to conduct analytical studies of archaeometric specimens composed of metal, ceramic, or mixed inorganic/organic materials, where major and trace element compositions are registered in space for areas up to the centimeter-length scale at micrometer-scale resolution. Overview images were used to select areas for EDS beam scan maps correlated with multispectral cathodoluminescence (CL) imaging and co-located quantitative EDS and μXRF point analysis. Fe, Ca, Mg, Ti, P, Mn, Zr, Zn, and Y are enriched in the dark glass, while Si, Al, K, Na, Ba, Sr, Rb, and Ga are enriched in the clear glass. Unmelted material is comprised predominately of quartz (SiO 2 ) along with trace apatite (Ca 5 (PO 4 ) 3 [Cl,OH]) and zircon (ZrSiO 4 ). Multivariate statistical analysis was used to measure the area fractions of high variance components while lower variance components represented phase mixtures. Differences between calculated melt viscosities for the glass compositions are consistent with field and laboratory observations. Coupled large area EDS and μXRF imaging shows significant promise for informed selection of higher spatial resolution and higher sensitivity follow-up studies, e.g., those performed using synchrotron analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Assessment of the reason for the vitrification of a wall at a hillfort. The example of Broborg in Sweden

It was discovered around 250 years ago that some of the rock material in the walls of some hillforts had been subjected to such high temperature that it had vitrified. This prompted a debate as to the reason for it that is still going on today: did the vitrification come about as a result of hostile action, by accident, or for the purpose of constructing the fort? The present paper is based on the prerequisite that hillforts are different, and therefore should be evaluated individually. All identifiable factors of interest should be included, and especially those that might disprove any alternative. Thus, incentives, competence and petrographic aspects were evaluated for the hillfort Broborg (dated Migration Period, in Sweden A.D. 400 - 550), and it is concluded that the vitrification came about for the purpose of constructing the fort. This capability was lost when mortar was introduced half a millennium later.

42 ENGINEERING↗
DOE OSTI2022

Structure and thermodynamics of calcium rare earth silicate oxyapatites, Ca 2 RE 8 (SiO 4 ) 6 O 2 (RE = Pr, Tb, Ho, Tm)

Calcium rare earth silicate oxyapatites, (Ca 2 RE 8 (SiO 4 ) 6 O 2 ), are of interest as components of glass-ceramic nuclear waste forms. To assess their long-term behavior in a geologic repository, it is essential to determine their structure and thermodynamic stability at relevant conditions. Here, in this work, we performed detailed structural and thermodynamic investigations on Ca 2 Pr 8 (SiO 4 ) 6 O 2 , Ca 2 Tb 8 (SiO 4 ) 6 O 2 , Ca 2 Ho 8 (SiO 4 ) 6 O 2 , and Ca 2 Tm 8 (SiO 4 ) 6 O 2 by high energy synchrotron powder X-ray diffraction combined with Rietveld analysis and high temperature oxide melt drop solution calorimetry. Enthalpies of formation from constituent oxides (ΔH f,ox ) were determined to be -765.1 ± 22.8 kJ/mol for Ca 2 Pr 8 (SiO 4 ) 6 O 2 ; -638.9 ± 20.5 kJ/mol for Ca 2 Tb 8 (SiO 4 ) 6 O 2 ; -643.3 ± 10.3 kJ/mol for Ca 2 Ho 8 (SiO 4 ) 6 O 2 ; and -403.2 ± 5.1 kJ/mol for Ca 2 Tm 8 (SiO 4 ) 6 O 2 . These thermodynamic parameters were used in assessing the thermochemical stability of these phases in the presence of water vapor from room temperature to 600 K, as encountered in the subsurface environments of a geological repository.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Process optimization of caustic scrubber and iodine-129 immobilization in sodalite-based waste forms

Caustic scrubbers are proposed to remove vaporized iodine from nuclear fuel reprocessing plants. Resulting caustic slurries of radioactive iodine ( 129 I) and other anions can be captured and immobilized into the cage structures of sodalite-type minerals. Here, mixed anion sodalites were hydrothermally synthesized from a simulated caustic scrubber solution containing hydroxide/water, carbonate, chlorine, bromine, iodine, nitrate, and nitrite ions with added kaolinite. Experiments were conducted with twenty-five different sets of process conditions. Resulting powders were characterized by quantitative X-ray diffraction (XRD) and multi-functional thermal analysis, including gravimetry, calorimetry, and mass spectrometry. Using statistical analysis, process variables were tailored to maximize conversion of kaolinite into cage silicates, immobilize caustic scrubber anions, and minimize amorphous content. Further, chemical analysis showed the incorporation of all the targeted ions into the solids. Detailed investigation of a batch characterized after washing (creating secondary waste) and one without washing but subsequent calcination is given. This work contributes to defining the constraints required for subsequent consolidation process steps of the waste form to avoid volatilization.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Impact of non‐framework cation mixing on the structure and crystallization behavior of model high‐level waste glasses

Abstract Spinel crystallization is known to be detrimental to the operation of Joule heated ceramic melters during the vitrification of iron‐rich high‐level nuclear wastes (HLW) into borosilicate glasses. The literature on this subject focuses on tackling the problem by developing empirical constraints to design compositions, which limit the fraction of spinels formed in the melter or by developing empirical models to predict the settling behavior of spinels in the melter as a function of the glass composition. While these empirical models can predict the behavior of most of the compositions, they are not failsafe as there are always some compositions, whose behavior is beyond the predictive ability of these models. This can lead to undesirable situations during the vitrification of the nuclear waste, and therefore an in‐depth investigation of the chemo‐structural descriptors controlling the crystallization behavior in these glasses is warranted. Accordingly, the present study aims to understand the impact of non‐framework cation mixing (i.e., Li + /Na + and Ca 2+ /Na + ) on the structure (through Raman spectroscopy and Mössbauer spectroscopy) and crystallization behavior (through XRD, SEM‐EDS, and vibrating sample magnetometry) of iron‐rich model HLW glasses in the system: (mol.%) x M y O–(25− x ) Na 2 O–9.12 B 2 O 3 –6.4 Al 2 O 3 –51.25 SiO 2 –7.22 Fe 2 O 3 –0.38 MnO–0.08 Cr 2 O 3 –0.55NiO (M y O = Li 2 O or CaO).

Balasubramanya, Nikhila↗
DOE OSTI2022

Scoping studies for low-temperature melting ZnO–Bi 2 O 3 –(B 2 O 3 , SiO 2 ) binder glass

In this work, low melting point glass systems were explored as candidates for binders of solid oxide nuclear wastes which include volatile elements such as radioactive iodine. The base glass systems considered were ZnO-Bi 2 O 3 -B 2 O 3 and ZnO-Bi 2 O 3 -SiO 2 , with specific compositions selected for synthesis trials based on available phase diagrams and a desire to explore the whole glass-forming region. Ten compositions were synthesized by melt quenching. Promising candidate glass binders were selected based on absence of crystallization and favorable thermal properties, including low glass transition temperature (T g ) combined with a high crystallization onset temperature. These thermal properties indicate stable glass forming which would lead to sintering behavior needed for glass binding. Compositional effects include: higher Bi 2 O 3 content lead to lower Tg values, high ZnO content generally led to crystallization on quench, and high SiO 2 content resulted in requirements for excessively high melting temperature. 25ZnO-15Bi 2 O 3 -60B 2 O 3 was down-selected for some detailed crystallization versus time and temperature studies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Applying laboratory methods for durability assessment of vitrified material to archaeological samples

Abstract Laboratory testing used to assess the long-term chemical durability of nuclear waste forms may not be applicable to disposal because the accelerated conditions may not represent disposal conditions. To address this, we examine the corrosion of vitrified archeological materials excavated from the near surface of a ~1500-year old Iron Age Swedish hillfort, Broborg, as an analog for the disposal of vitrified nuclear waste. We compare characterized site samples with corrosion characteristics generated by standard laboratory durability test methods including the product consistency test (PCT), the vapor hydration test (VHT), and the EPA Method 1313 test. Results show that the surficial layer of the Broborg samples resulting from VHT displays some similarities to the morphology of the surficial layer formed over longer timescales in the environment. This work provides improved understanding of long-term glass corrosion behavior in terms of the thickness, morphology, and chemistry of the surficial features that are formed.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A Comparative Study on the Effect of Zr, Sn, and Ti on the Crystallization Behavior of Nepheline Glass

In alkali aluminosilicate glasses, additions of 4+ cations like Zr and Ti are often added to promote crystallization. In this study, Zr, Ti, or Sn are progressively substituted for Si in nepheline (NaAlSiO4) glass to determine their impact on the crystallization behavior. For glasses homogeneous on quenching, up to NaAlZr0.075Si0.925O4, NaAlSn0.100Si0.900O4, and NaAlTi0.300Si0.700O4, respectively, crystallization temperatures were investigated by thermal analysis. A subset of compositions was subjected to additional thermal analysis, varying heating rate and particle size, to investigate the subtleties of crystallization behavior. Subsequent heat treatment of glass powders was performed to maximize crystallization, and glass-ceramic microstructure was assessed by optical microscopy and electron microprobe, while crystalline phases were determined by X-ray diffraction. In all cases the major crystalline phase was orthorhombic carnegieite, which accommodated Ti in its structure but not Zr or Sn, and excess 4+ cations formed MO2, i.e., brookite, baddeleyite, and cassiterite, respectively.

Nienhuis-Marcial, Emily T.↗
DOE OSTI2021

Zinc–hydrogen and zinc–iridium pairs in β-Ga 2 O 3

Zinc-doped monoclinic gallium oxide (β-Ga 2 O 3 :Zn) has semi-insulating properties that could make it a preferred material as a substrate for power devices. In this work, infrared and UV/Visible spectroscopy were used to investigate the defect properties of bulk β-Ga 2 O 3 :Zn crystals. As-grown crystals contain a single O-H stretching mode at 3486.7 cm -1 due to a neutral ZnH complex. A deuterium-annealed sample displays the corresponding O-D stretching mode at 2582.9 cm -1 , confirming the O-H assignment. A strong Ir 4+ electronic transition at 5147.6 cm -1 is also observed, along with sidebands attributed to ZnIr pairs. These sidebands show distinct differences compared with Mg-doped samples; most importantly, several peaks are attributed to Ir 4+ paired with a Zn on the tetrahedral Ga(I) site. Annealing under an oxygen atmosphere produced insulating material with a resistance above 1 TΩ.

36 MATERIALS SCIENCE↗