Engineering topics

Kroll, Jared O.

Publications and source records attributed to Kroll, Jared O..

17 records

DOE OSTI2024

A Modular Oxygen-Selective System for Combustion Systems

Small-scale modular systems for oxygen generation offer clear benefits, including improved energy efficiency, reduced operating costs, and the flexibility to meet location-specific needs. We propose that a compact modular system could be developed using a solvent-based method for capturing and releasing oxygen, enabling “oxygen on demand” for various combustion technologies. In this project, we aim to develop and demonstrate a modular oxygen-selective approach based on Battelle IPID 31740. The use of designer solvents, which are reversible, single-component solvents capable of dissolving and separating oxygen from air, offers the advantage of unlimited chemical tunability to achieve desirable properties for efficient oxygen separation. We filed U.S. Patent (32845-E, iEdison No. 0685901-23-0184).

36 MATERIALS SCIENCE↗

DOE OSTI2024

Integrated Approach to CO 2 Capture and Conversion to Cyclic Carbonates under Solvent- and Additive-Free Conditions Utilizing the CO 2 Capture Solvent EEMPA

An integrated CO 2 capture and conversion to materials (IC 3 M) implementation utilizing a CO 2 capture solvent is an efficient approach to reduce the amount of CO 2 in the atmosphere while producing value-added chemicals. In this work, we demonstrate that the advanced water-lean CO 2 capture solvent, N-(2-Ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA), can catalyze the cycloaddition reaction between CO 2 and propylene oxide to produce the value-added chemical propylene carbonate in an IC 3 M fashion. When excess propylene oxide is used relative to EEMPA, yields as high as 75% with 85% selectivity toward propylene carbonate can be achieved under solvent-free conditions without the need of additives/cocatalysts. The reaction temperature (120 °C) is comparable to that used in the thermal regeneration of the capture solvent under industrial conditions. Formation of an undesired amino alcohol side product was observed, but it may be reversible or avoidable with continued research despite the unsuccessful initial attempts. Finally, we show that this can be applied to other epoxides for the production of various cyclic carbonates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Sol–gel synthesis of iodosodalite precursors and subsequent consolidation with a glass binder made from oxides and sol–gel routes

Radioiodine accumulates in aqueous solutions and off-gas streams during nuclear fuel reprocessing due to its solubility in aqueous solutions and volatility, respectively. Additionally, radioiodine is highly mobile in geological environments and iodine-129 has been found to be one of the largest long-term contributors to chronic dose to humans in scenarios of radionuclide migration from geological repositories. Most of the radioiodine can be captured during fuel reprocessing in off-gas streams using solid sorbents and scrubbing solutions. Once iodine is captured, it must be stored in a durable form for eventual disposal. Iodosodalite has been investigated as a waste form for radioiodine, however these synthesis processes typically result in mixed products and iodine volatilization during consolidation. Therefore, this paper proposes a novel approach to synthesizing iodosodalite utilizing a sol-gel method. This method was chosen to lower processing temperatures and improve product yield. Preliminary experiments conducted to determine the viability of this synthetic method are presented. Additionally, consolidation of sol-gel derived iodosodalite with a glass-binder was explored using three different methods: 1) incorporating the glass-binder during gel preparation using alkoxide precursors; 2) separately preparing the glass binder using a sol-gel method; and 3) separately preparing the glass-binder using a melt-quench technique. Glass-bonded iodosodalite was successfully synthesized using these novel sol-gel approaches.

36 MATERIALS SCIENCE↗

DOE OSTI2019

X-Ray Diffraction and Product Consistency Test Results for the Phase 6 Study of Nepheline Formation in High-Level Waste Glasses

Hanford high-level waste (HLW) contains relatively high concentrations of Al 2 O 3 . A major constraint limiting the waste loading of high-Al 2 O 3 glasses is nepheline (nominally NaAlSiO 4 ) formation upon slow cooling of HLW glasses after melts are poured into steel canisters. The model currently planned to be used at the Hanford Waste Treatment and Immobilization Plant (WTP) for avoiding nepheline formation is too conservative and drastically limits waste loading. To increase operational flexibility and effectively operate the WTP, the effects of glass composition on glass properties must be determined and glass property-composition models must be developed. Determining the impacts of glass composition on nepheline formation and the effects of nepheline on Product Consistency Test (PCT) response is an important part of this effort. As a part of this effort, data related to the Hanford high-Al 2 O 3 HLW composition region was generated to supplement existing data for model development. Twenty glasses were fabricated, heat treated, and analyzed for crystallinity and PCT response. The heat treatment was designed to mimic the canister centerline cooling (CCC) profile of Hanford HLW glass canisters. It was found that only 6 of the 20 prepared glasses (#4, #7, #8, #10, #19, and #20) formed nepheline upon heat treatment. All glasses except for one (#19) precipitated spinel upon quenching and no glasses contained nepheline upon quenching. Of the 20 glasses, the PCT-normalized boron release of the quenched glasses and all but five of the CCC glasses satisfied the environmental assessment glass benchmark value (16.695 g/L). The CCC glass samples that exceeded the limit were #8 (48.21 g/L), #10 (19.77 g/L), #13 (20.17 g/L), #19 (60.85 g/L), and #20 (61.08 g/L). Those glasses coincide with the highest amounts of nepheline found in the CCC glasses, except for #13, which did not form nepheline after CCC.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2019

Formulation of high-Al2O3 waste glasses from projected Hanford waste compositions

Not Available

Kroll, Jared O.↗

DOE OSTI2019

Developing a space-filling mixture experiment design when the components are subject to linear and nonlinear constraints

This article presents a case study of developing a space-filling design (SFD) for a constrained mixture experiment when the experimental region is specified by single-component constraints (SCCs), linear multiple-component constraints (LMCCs), and nonlinear multiple-component constraints (NMCCs). Traditional methods and software for designing constrained mixture experiments with SCCs and LMCCs (using either optimal design or SFD approaches) are not directly applicable because of the NMCCs. A SFD algorithm in the JMP software was modified to accommodate the nonlinear MCCs; the modification is described in this article. The case study involves high-level waste (HLW) glass that is subject to the formation of nepheline crystals as the glass cools. This can significantly reduce the durability of HLW glass (which is undesirable). The goal of the study was to develop a SFD for the HLW glass compositional region where nepheline may form, and generate data for modeling nepheline formation as a function of HLW glass composition. The HLW glass composition region was specified in terms of eight components with SCCs, two LMCCs, and two NMCCs. The NMCCs were based on a nonlinear logistic regression model for a binary-response nepheline response that was developed from previous data. This article discusses the HLW glass example, the constraints specifying the experimental composition region, and how an existing algorithm for generating SFDs was modified to accommodate the NMCCs. The methodology discussed in this article can be applied to any example in which the experimental region is specified by one or more nonlinear constraints in addition to linear constraints on mixture components and/or non-mixture variables.

Mixture experiment, space-filling experimental des↗

DOE OSTI2019

Synthesis of Nd3BSi2O10 using a LiCl-flux method

This paper details synthesis methods that were used to fabricate phase-pure Nd3BSi2O10 using a LiCl-flux method. In this study, a variety of conditions were evaluated to find the optimal processing parameters for maximizing the Nd3BSi2O10 yield including the mass ratio of LiCl to target mass of Nd3BSi2O10 including 1:3, 1:2, 1:1, 2:1, and 6:1 as well as the soak temperature (i.e., 700, 800, or 900°C) at the 1:1 ratio. It was found that the optimal ratio of LiCl:Nd3BSi2O10 was 1:1 and the optimal heat-treatment temperature was 900°C. Product made from the 1:1 material synthesized at 900°C was recovered and fired at temperatures of 925–1350°C. After 4-h firings at temperatures of 925–1100°C, the Nd3BSi2O10 phase purity was found to be 100% with powder X-ray diffraction, but started to decompose at the longer firing times at 1100°C and higher temperatures (1350°C) at the 4-h dwell time. The durability of the Nd3BSi2O10 product was examined in flow-through conditions at pH 5.6 and 7.7 and 90°C. The release rate of Nd from the material at pH 5.6 was calculated to be 1.6×10-3 g m-2 d-1 and was determined to have a maximum release rate of Nd at pH 7.7 of 5.6×10-3 g m-2 d-1. These release rates are roughly three orders of magnitude lower than what is typically measured from glass waste forms.

Kroll, Jared O.↗

DOE OSTI2018

Results from Phase 5 Study on Nepheline Formation in High-Level Waste Glasses Containing High Concentrations of Alumina

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2018

Immobilization of LiCl-Li2O pyroprocessing salt wastes in chlorosodalite using glass-bonded hydrothermal and salt-occlusion methods

Not Available

Riley, Brian J. (ORCID:0000000277456730)↗

DOE OSTI2017

Assessment of lead tellurite glass for immobilizing electrochemical salt wastes from used nuclear fuel reprocessing

This paper provides an overview of research evaluating the use of lead tellurite glass as a waste form for salt wastes from electrochemical reprocessing of used nuclear fuel. The efficacy of using lead tellurite glass to immobilize three different salt compositions was evaluated: a LiCl-Li2O oxide reduction salt containing fission products from oxide fuel, a LiCl-KCl eutectic salt containing fission products from metallic fuel, and SrCl2. Physical and chemical properties of glasses made with these salts were characterized with X-ray diffraction, bulk density measurements, differential thermal analysis, chemical durability tests, scanning and transmission electron microscopies, and energy-dispersive X-ray spectroscopy. These glasses were found to accommodate high salt concentrations and have high densities, but further development is needed to improve chemical durability. (C) 2017 Published by Elsevier B.V.

Riley, Brian J.↗

DOE OSTI2017

Silver-Loaded Aluminosilicate Aerogels As Iodine Sorbents

Here, in this paper, aluminosilicate aerogels were used as scaffolds for silver nanoparticles to capture I 2 (g). The starting materials for these scaffolds included Na–Al–Si-O and Al–Si–O aerogels, both synthesized from metal alkoxides. The Ag 0 particles were added by soaking the aerogels in aqueous AgNO 3 solutions followed by drying and Ag + reduction under H 2 /Ar to form Ag 0 crystallites within the aerogel matrix. In some cases, aerogels were thiolated with 3-(mercaptopropyl)trimethoxysilane as an alternative method for binding Ag + . During the Ag + -impregnation steps, for the Na–Al–Si-O aerogels, Na was replaced with Ag, and for the Al–Si–O aerogels, Si was replaced with Ag. The Ag-loading of thiolated versus nonthiolated Na–Al–Si–O aerogels was comparable at ~35 atomic %, whereas the Ag-loading in unthiolated Al–Si–O aerogels was significantly lower at ~7 atomic % after identical treatment. Iodine loadings in both thiolated and unthiolated Ag 0 -functionalized Na–Al–Si–O aerogels were >0.5 m I m s –1 (denoting the mass of iodine captured per starting mass of the sorbent) showing almost complete utilization of the Ag through chemisorption to form AgI. Iodine loading in the thiolated and Ag 0 -functionalized Al–Si–O aerogel was 0.31 m I m s –1 . The control of Ag uptake over solution residence time and [Ag] demonstrates the ability to customize the Ag-loading in the base sorbent to regulate the loading capacity of iodine.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Glass binder development for a glass-bonded sodalite ceramic waste form

This paper discusses work to develop Na2O-B2O3-SiO2 glass binders for immobilizing LiCl-KCl eutectic salt waste in a glass-bonded sodalite waste form following electrochemical reprocessing of used metallic nuclear fuel. Here, five new glasses with high Na2O contents were designed to generate waste forms having higher sodalite contents and fewer stress fractures. The structural, mechanical, and thermal properties of the new glasses were measured using variety of analytical techniques. The glasses were then used to produce ceramic waste forms with surrogate salt waste. The materials made using the glasses developed during this study were formulated to generate more sodalite than materials made with previous baseline glasses used. The coefficients of thermal expansion for the glass phase in the glass-bonded sodalite waste forms made with the new binder glasses were closer to the sodalite phase in the critical temperature region near and below the glass transition temperature. These improvements should result in lower probability of cracking in the full-scale monolithic ceramic waste form, leading to better long-term chemical durability. Additionally, a model generated during this study for predicting softening temperature of silicate binder glasses is presented.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2016

Results from Phase 1, 2, and 3 Studies on Nepheline Formation in High-Level Waste Glasses Containing High Concentrations of Alumina

The composition of Hanford high-level waste (HLW) is dominated by relatively high concentrations of Al 2 O 3 . A major constraint limiting the waste loading of high-Al 2 O 3 glasses is nepheline (nominally NaAlSiO 4 ) formation upon slow cooling of HLW glasses after melts are poured into canisters. The model currently planned to be used at the Hanford Tank Waste Treatment and Immobilization Plant (WTP) for avoiding nepheline formation is too conservative and drastically limits waste loading. To increase loadings of high-Al 2 O 3 waste at the WTP, the effects of glass composition on glass properties must be determined and glass property-composition models must be developed. An important task of this effort is determining the impacts of glass composition on nepheline formation and the effects of nepheline on Product Consistency Test (PCT) response.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2016

Effects of Al2O3, B2O3, Li2O, Na2O, and SiO2 on Nepheline Crystallization in Hanford High Level Waste Glasses

Nepheline (nominally NaAlSiO4) formation during slow cooling of high-alumina (25.4 - 34.5 mass% Al2O3) Hanford high level waste glasses may significantly reduce product durability. To investigate the effects of composition on nepheline crystallization, 29 compositions were formulated by adjusting Al2O3, B2O3, Li2O, Na2O, and SiO2 around a baseline glass that precipitated 12 mass% nepheline. Thirteen of these compositions were generated by adjusting one-component-at-a-time, while two or three components were adjusted to produce the other 16 (with all remaining components staying in the same relative proportions). Quantitative X-ray diffraction was used to determine nepheline concentration in each sample. Twenty two glasses precipitated nepheline, two of which also precipitated eucryptite (nominally LiAlSiO4), and one glass formed only eucryptite upon slow cooling. Increasing Na2O and Li2O had the strongest effect in promoting nepheline formation. Increasing B2O3 inhibited nepheline formation. SiO2 and Al2O3 showed non-linear behavior related to nepheline formation. The composition effects on nepheline formation in these glasses are reported.

Kroll, Jared O.↗

DOE OSTI2016

Submixture model to predict nepheline precipitation in waste glasses

Abstract High‐alumina high‐level waste ( HLW ) glasses are prone to nepheline precipitation during canister‐centerline cooling ( CCC ). If sufficient nepheline forms, the chemical durability of the glass will be significantly impacted. Overly conservative constraints have been developed and used to avoid the deleterious effects of nepheline formation in U.S. HLW glasses. The constraints used have been shown to significantly limit the loading of waste in glass at Hanford and therefore the cost and schedule of cleanup. A 90‐glass study was performed to develop an improved understanding of the impacts of glass composition on the formation of nepheline during CCC . The CCC crystallinity data from these glasses were combined with 657 glasses found in the literature. The trends showed significant effects of Na 2 O, Al 2 O 3 , SiO 2 , B 2 O 3 , CaO, Li 2 O, and potentially K 2 O on the propensity for nepheline formation. A pseudo‐ternary submixture model was proposed to identify the glass composition region prone to nepheline precipitation. This pseudo‐ternary with axes of SiO 2 + 1.98B 2 O 3 , Na 2 O + 0.653Li 2 O + 0.158CaO, and Al 2 O 3 was found to divide glasses that precipitate nepheline during CCC from those that do not. Application of this constraint is anticipated to increase the loading of Hanford high‐alumina HLW s in glass by roughly one‐third.

Vienna, John D.↗

DOE OSTI2015

Consolidation of Tin Sulfide Chalcogels and Xerogels with and without Adsorbed Iodine

Tin sulfide (Sn 2 S 3 ) chalcogels are one of the most effective non-oxide aerogels evaluated to date for iodine gas capture. Here, this is attributed to the fact that the Sn within the gel network has a strong affinity for chemisorption of iodine to form SnI 4 . This study demonstrates an approach for consolidating the raw and iodine-sorbed Sn 2 S 3 chalcogels into a chalcogenide glass using GeS 2 as a glass forming additive. The system with both iodine-sorbed and iodine-free Sn 2 S 3 chalcogels provides better glass-forming characteristics than Sn-S or Sn-S-I alone, and the quantity of iodine measured in the bulk glass of the consolidated iodine-sorbed Sn 2 S 3 chalcogel was at ~45 mass%. Additional experiments were also conducted using microwave sintering and hot isostatic pressing with Sn 2 S 3 xerogels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

SCOPING MELTING STUDIES OF HIGH ALUMINA WASTE GLASS COMPOSITIONS

Glass property models will be used at the Hanford Tank Waste Treatment and Immobilization Plant to formulate durable high-level waste glasses for disposal. A major effort is focused on expanding glass property models to cover a broader range of wastes and higher waste-loaded glasses. As a part of this effort, a statistically designed matrix of high-alumina glass compositions was developed. Forty five compositions were selected from the matrix to evaluate glass properties. Of these compositions, thirty three produced homogeneous glasses. The other twelve compositions contained segregated phases and high crystallinity; these were iteratively modified in an attempt to produce homogeneous glass samples while altering the original composition as little as possible. This paper focuses on the characterization of the twelve inhomogeneous compositions and their modifications using X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy.

Kroll, Jared O.↗