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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Recreating Fuel Cell Catalyst Degradation in Aqueous Environments for Identical-Location Scanning Transmission Electron Microscopy Studies

The recent surge in interest of proton exchange membrane fuel cells (PEMFCs) for heavy-duty vehicles increases the demand on the durability of oxygen reduction reaction electrocatalysts used in the fuel cell cathode. This prioritizes efforts aimed at understanding and subsequently controlling catalyst degradation. Identical-location scanning transmission electron microscopy (IL-STEM) is a powerful method that enables precise characterization of degradation processes in individual catalyst nanoparticles across various stages of cycling. Recreating the degradation processes that occur in PEMFC membrane electrode assemblies (MEAs) within the aqueous cell used for IL-STEM experiments is vital for generating an accurate understanding of these processes. In this work, we investigate the type and degree of catalyst degradation achieved by cycling in an aqueous cell compared to a PEMFC MEA. While significant degradation is observed in IL-STEM experiments performed on a traditional Pt catalyst using the standard accelerated stress test potential window (0.6-0.95 VRHE), degradation of a PtCo catalyst designed for heavy-duty vehicle use is very limited compared to that observed in MEAs. We therefore explore various experimental parameters such as temperature, acid type, acid concentration, ionomer content, and potential window to identify conditions that reproduce the degradation observed in MEAs. We find that by extending the cycling potential window to 0.4-1.0 V RHE in an electrolyte containing Pt ions, the degraded particle size distribution and alloy composition better match that observed in MEAs. In particular, these conditions increase the relative contribution of Ostwald ripening, which appears to play a more significant role in the degradation of larger alloy particles supported on high-surface-area carbons than coalescence. Results from this work highlight the potential for discrepancies between ex situ aqueous experiments and MEA tests. While different catalysts may require a unique modification to the AST protocol, strategies provided in this work enable future in situ and identical-location experiments that will play an important role in the development of robust catalysts for heavy-duty vehicle applications.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2025

Summertime Carbonaceous Aerosol in Interior Versus Coastal Northern Alaska

Abstract Rapid warming is likely increasing primary production and wildfire occurrence in the Arctic. Projected changes in carbonaceous aerosols during the summer will impact atmospheric chemistry and climate, but our understanding of these processes is limited by sparse observations. Here, we characterize carbonaceous aerosol in Alaska, USA: Toolik Field Station in the Interior and the Atmospheric Radiation Measurement facility at Utqiaġvik on the Arctic coast, during the summers of 2022 and 2023. We estimated PM 2.5 and PM 10 concentrations using laser light scattering (PurpleAir sensors) and examined total carbon (TC) and its organic carbon (OC) and elemental carbon (EC) fractions in total suspended particles (TSP). We investigated the dominant sources of carbonaceous aerosol using air mass backward‐trajectories from the NOAA HYSPLIT model and radiocarbon source apportionment of TC. TC concentrations were about twice as high in the Interior compared to the coast, with contemporary sources dominating at both Toolik (95%–99%) and Utqiaġvik (86%–89%) over minor contributions from fossil sources. Elevated PM, TC, OC, and EC concentrations coincided with major boreal forest fire activity in North America that brought smoke to the region. The radiocarbon signature of EC measured at Toolik during these wildfire events indicated that over 90% of the EC came from contemporary sources. Our measurements demonstrate the potential for Arctic aerosol concentrations to respond significantly to climate warming‐induced changes to the landscape and emphasize the need for continuous atmospheric monitoring to advance our understanding of this rapidly changing environment.

Welch, Allison M. [Department of Earth System Scie↗
DOE OSTI2025

Zeta potential measurements of SiO 2 and TiO 2 particles in anionic and cationic surfactant solutions

Zeta potential measurements can provide valuable insights into colloidal stability and may reflect changes in the electrochemical double layer that influence electrocatalysis. In this study, we used zeta potential measurements to monitor and investigate the adsorption behavior of anionic sodium dodecyl sulfate (SDS), cationic dodecyl trimethyl ammonium bromide (DTAB), and cationic cetyl trimethyl ammonium bromide (CTAB) surfactants on SiO 2 and TiO 2 particles in DI water. The zeta potentials of SiO 2 and TiO 2 particles were measured as a function of particle concentration in 1.0 mM, 5.0 mM, and 10.0 mM surfactant solutions. Results indicate that there is no significant adsorption of DS - ions on SiO 2 particles across all SDS concentrations investigated in this study. The zeta potential of TiO 2 particles shifts from negative to positive as particle concentration increases at 1.0 mM SDS, indicating a decrease in DS - ions adsorption per TiO 2 particle. Adsorption plateaus at 5.0 mM SDS for all TiO 2 concentrations studied. In contrast, DTA + and CTA + ions showed clear adsorption on SiO 2 particles, but DTA + exhibited no apparent adsorption on TiO 2 particles. Interestingly, CTA + adsorption on TiO 2 was only evident at higher surfactant concentrations. This study presents a systematic investigation of zeta potential behavior as a function of particle and surfactant concentration, highlighting adsorption saturation and electrostatic reversal. Unlike prior work that was limited to single particle concentration measurements, our approach reveals how surfactant adsorption per particle decreases with increasing surface area. Despite the structural similarity between DTAB and CTAB, this study captured the different adsorption behaviors of both surfactants on SiO 2 and TiO 2 , emphasizing the role of the overall structure of the surfactant on surfactant adsorption behavior. These insights refine the interpretation of zeta potential data and advance understanding of surfactant adsorption on oxide particles. The insight provided in this study about surfactant adsorption on SiO 2 and TiO 2 particles could have important implications for the design of more effective colloidal and catalytic systems.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

A large nitrogen supply from the stable mineral-associated soil organic matter fraction

Soil organic matter (SOM) mineralization and nitrogen (N) release are key biogeochemical processes for which the relative contribution of particulate (POM) and mineral-associated organic matter (MAOM) fractions is poorly understood. MAOM is generally considered to be a more stable fraction that contains most of the soil organic N, whereas POM is more readily decomposable and contains less N. We measured variations in the potentially mineralizable N from each SOM fraction across three contrasting land uses (forest, pasture, and croplands) and two different grazing managements (rotational and continuous grazing). Contrary to expectations, we found that the MAOM fraction consistently supplied more N than the POM fraction during SOM mineralization in all land-uses evaluated. Across our environmental gradient, potentially mineralizable N from POM increased with the carbon (C) concentration and C/N ratio of POM, while potentially mineralizable N from MAOM increased with the C concentration of MAOM but decreased with clay content. Our work suggests that MAOM contributions to short-term N mineralization and N supply to plants have been undervalued.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Annual simulation of photovoltaic retrofits within existing parabolic trough concentrating solar powerplants

Solar power for electricity production comes from either photovoltaics or concentrating solar power plants. The former has seen rapid growth and expansion due to the rapid fall in global prices, while the latter has seen moderate growth due to ability to cheaply store thermal energy for later use. Hybridization, or combining photovoltaics with concentrating solar power represents a potential way for lowering cost while enabling long term storage. Over 5 GW of capacity exist worldwide using parabolic trough style technology for concentrating solar power which presents a unique option for optimization in the form of a photovoltaic retrofit. While it is possible to analyze the performance with detailed physics models, it is necessary to create a model that can handle simulating the plant level performance to fully understand the potential performance. Here, the first utility scale plant level model of a hybrid photovoltaic-concentrating solar power plant is developed. The model is applied to existing concentrating solar power plants around the world utilizing RP-3 mirrors without thermal energy storage to understand the impact on electricity production. Model results indicate that the photovoltaic retrofit can increase yearly electricity production by up to 30% for plants with solar multiples exceeding 1.5, and that increasing the fraction of solar energy reflected further increases the yield. The increased electrical production declines as the plant solar multiple is decreased. The minimum LCOE observed was $0.07/kWh for plants with larger solar multiple and fraction of solar energy reflected to the PV is 50% of the total aperture.

14 SOLAR ENERGY↗
DOE OSTI2020

Effect of Water Concentration in LiPF 6 -Based Electrolytes on the Formation, Evolution, and Properties of the Solid Electrolyte Interphase on Si Anodes

A trace amount of water in an electrolyte is one of the factors detrimental to the electrochemical performance of silicon (Si)-based lithium-ion batteries that adversely affect the formation and evolution of the solid electrolyte interphase (SEI) on Si-based anodes and change its properties. Thus far, a lack of fundamental and mechanistic understanding of SEI formation, evolution, and properties in the presence of water has inhibited efforts to stabilize the SEI for improved electrochemical performance. As such, we investigated the SEI formed in a Gen2 electrolyte (1.2 M LiPF6 in ethylene carbonate/ethyl methyl carbonate, 3:7 wt %, water content: <10 ppm) with and without additional water (50 ppm) at varying potentials (1.0, 0.5, 0.2, and 0.01 V vs Li/Li + ). The impact of additional water on the morphological, (electro)chemical, and structural properties of SEI was studied using microscopic (atomic force microscopy and scanning spreading resistance microscopy) and spectroscopic (X-ray photoelectron spectroscopy, attenuated total reflection Fourier-transform infrared spectroscopy, and time-of-flight secondary ion mass spectrometry) techniques. The SEI exhibits both potential- and water concentration-dependent trends in its morphology and chemical composition. The presence of additional water in the electrolyte causes parasitic reactions, which onset at ~1.0 V, resulting in a reduction of electrolyte components and result in the formation of an insulating, fluorophosphate-rich SEI. In addition, hydrolysis of LiPF 6 creates hydrofluoric acid, which reacts with the surface oxide layer on the Si electrode, leading to a pitted and inhomogeneous SEI structure.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Probe the Localized Electrochemical Environment Effects and Electrode Reaction Dynamics for Metal Batteries using In Situ 3D Microscopy

Uncontrollable dendrite growth is closely related to non-uniform reaction environments. However, there is a lack of understanding and analysis methods to probe the localized electrochemical environment (LEE). Here the effects of the LEE are investigated, including localized ion concentrations, current density, and electric potential, on metal plating/stripping dynamics and dendrite minimization. A novel in situ 3D microscopy technique is developed to image the morphology dynamics and deposition rate of Zn plating/stripping processes on 3D Zn–Mn anodes. Using the in situ 3D microscope, the electrode morphology changes during the reactions are directly imaged and Zn deposition rate maps at different time points are obtained. It is found that reaction kinetics are highly correlated to LEE and electrode morphology. To further quantify the LEE effects, the digital twin technique is employed that allows the accurate calculation of the electrochemical environments, such as localized ion concentrations, current density, and electric potential, which cannot be directly measured from experiments. We found that the curvature of the 3D electrode surface determines the LEE and significantly influences reaction kinetics. This provides a new strategy to minimize the dendrite formation by designing and optimizing the 3D geometry of the electrode to control the LEE.

36 MATERIALS SCIENCE↗
DOE OSTI2021

High Temperature Acclimation of Leaf Gas Exchange, Photochemistry, and Metabolomic Profiles in Populus trichocarpa

High temperatures alter the thermal sensitivities of numerous physiological and biochemical processes that impact tree growth and productivity. Foliar and root applications of methanol have been implicated in plant acclimation to high temperature via the C 1 pathway. Here, we characterized temperature acclimation at 35°C of leaf gas exchange, chlorophyll fluorescence and extractable metabolites of potted Populus trichocarpa saplings and examined potential influences of mM concentrations of methanol added during soil watering over a two-month period. Relative to plants grown under the low growth temperature (LGT), high growth temperature (HGT) plants showed a suppression of leaf water use and carbon cycling including transpiration (E), net photosynthesis (P n ), an estimate of photorespiration (R p ), and dark respiration (R d ), attributed to reductions in stomatal conductance and direct negative effects on gas exchange and photosynthetic machinery. In contrast, HGT plants showed an upregulation of non-photochemical quenching (NPQ t ), the optimum temperature for ETR, and leaf isoprene emissions at 40°C. A large number of metabolites (867) were induced under HGT, many implicated in flavonoid biosynthesis highlighting a potentially protective role for these compounds. Methanol application did not significantly alter leaf gas exchange but slightly reduced the suppression of R d and R p by the high growth temperature while slightly impairing ETR, Fv’/Fm’, and q p . However, we were unable to determine if soil methanol was sufficiently taken up by the plant to have a direct effect on foliar processes. A small number of extracted leaf tissue metabolites (55 out of 10,015) showed significantly altered abundances under LGT and methanol treatments relative to water controls, and this increased in compound number (222) at the HGT. The results demonstrate the large physiological and biochemical impacts of high growth temperature on poplar seedlings and highlights the enhancement of the optimum temperature of ETR as a rapid thermal acclimation mechanism. Finally, although no large effect on leaf physiology was observed, the results are consistent with methanol both impairing photochemistry of the light reactions via formaldehyde toxicity, and stimulating photosynthesis and dark respiration through formate oxidation to CO 2 .

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Fully‐Printed Ion Sensor Arrays for Measuring Agricultural Nitrogen and Potassium Concentrations Using Nernstian and AI Models

Abstract The chemical composition of growing media is a key factor for plant growth, impacting agricultural yield and sustainability. However, there is a lack of affordable chemical sensors for ubiquitous nutrient ion monitoring in agricultural applications. This work investigates using fully printed ion‐sensor arrays to measure the concentrations of nitrate, ammonium, and potassium in mixed‐electrolyte media. Ion sensor arrays composed of nitrate, ammonium, and potassium ion‐selective electrodes and a printed silver‐silver chloride (Ag/AgCl) reference electrode are fabricated and characterized in aqueous solutions in a range of concentrations that encompass what is typical for agricultural growing media (0.01 m m –1 m ). The sensors are also tested in mixed‐electrolyte solutions of NaNO 3 , NH 4 Cl, and KCl of varying concentrations, and the recorded potentials are input into Nernstian and artificial neural network models to compare the prediction accuracy of the models against ground truth. The artificial neural network models demonstrated higher accuracy over the Nernstian model, and the model using only ion‐sensor inputs is 7.5% more accurate than the Nernstian model under the same conditions. By enabling more precise and efficient fertilizer application, these sensor arrays coupled to computational models can help increase crop yields, optimize resource use, and reduce environmental impact.

Goodrich, Payton [University of California Berkele↗
DOE OSTI2024

A survey study on arsenic speciation in coal fly ash and insights into the role of coal combustion conditions

Coal fly ashes (CFAs) are the low-density byproducts of the coal combustion process. Improper or uncontrolled CFA disposal poses significant environmental and health concerns due to the potential leaching of toxic heavy metals such as arsenic (As). Previous studies have investigated the content and speciation of As in different CFA samples, yet systematic information on As speciation in CFA with representative coal source and combustion conditions is still missing. Based on a recent survey study on the typical coal sources and combustion conditions across the U.S., this study selected 19 representative CFA samples to systematically investigate As speciation and potential correlations with these parameters. The composition, morphology, mineralogy, and As speciation of these CFA samples were characterized by complementary analytical, microscopic, and spectroscopic techniques. Synchrotron X-ray spectroscopy and microscopy analyses revealed the dominant As oxidation state to be As(V) and with strong associations to Ca, with the exception of 3 samples that had 19–51% As(III), likely due to the use of selective catalytic reduction (SCR) process. Principal component analysis was conducted to identify potential correlations of As concentration and oxidation state with parameters such as major element content, loss on ignition (LOI), average particle size, coal source, and combustion condition. Al 2 O 3 and FeO content were found to capture a majority of the variability. Further, results from this study provide fundamental basis for understanding the correlations between coal source, combustion conditions, CFA characteristics, and As speciation, and providing insights for downstream beneficial utilization or disposal management.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2024

An integrated approach to optimizing concentration shock wave electrodialysis using 2D multicell simulation and response surface models

Shock wave electrodialysis (SWED) is a highly promising technique for energy-efficient ion separation in the context of a circular economy. This paper presents a approach way of modeling and improving SWED using a two-dimensional multicell model combined with the COMSOL program and response surface methodology. The model integrates the Nernst-Planck equation, Darcy's law, and first-order electroosmosis to examine the local concentration, flux of ionic species, distribution of current, and velocity of flow in SWED cells under various operating conditions. We first illustrate the clear depiction of concentration, velocity, and electric potential distribution through contours which aids in identifying optimal operating conditions and designing scalable SWED systems. The results emphasize the significance of surface charge density and voltage in influencing the features of shock waves for obtaining effective ion separation while optimizing energy consumption and improving current efficiency by controlling the retention time of feed flow. Here, this study defines two crucial characteristics of shock waves, namely the length of the flat depletion zone of a fully developed shock wave (shock wave height) and the distance of shock wave propagation (shock wave length). These properties significantly impact separation performance, as determined by the simulation results. Additionally, the response surface methodology is incorporated with the COMSOL models to develop predictive models and graph responses, enabling a more comprehensive understanding of the interactions between parameters and performance indicators, such as removal ratio, energy consumption, and water recovery. Finally, this work suggests design tactics for expanding SWED processes and outlines potential areas for further research. This research provides valuable insights into the prospective applications, design optimization, and scalability of SWED in the field of electrokinetic separation technologies for green chemistry and a circular economy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Adapting confocal Raman microscopy for in situ studies of redox transformations at electrode-electrolyte interfaces

Confocal Raman microscopy was applied to quantify redox species present within the diffusion layer adjacent to an electrode surface under potentiostatic control. A glass microscope coverslip with a thin indium tin oxide (ITO) coating served as both the working electrode and optical window for a microscope-stage mountable spectroelectrochemical cell. A high numerical aperture objective mounted in an inverted microscope frame just below the stage brought excitation radiation through the coverslip window and to a tight focus a few micrometers above the ITO film surface. Species diffusing into the confocal probe volume defined by the excitation beam focus and the collected light region were detected, identified and quantified based on their Raman scattering frequencies and intensities. Here, in measurements that interrogated the interconversion of ferrocyanide and ferricyanide ions as a function of applied voltage, least-squares regression analysis of spectral datasets predicted the formal potential and relative surface concentrations of the ions in good agreement with the expected Nernstian response. Preliminary studies of methyl viologen reduction at an ITO film/Nafion membrane interface were conducted and show the possibility for estimation of mass transport coefficients of redox species within ionic polymer materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Characterization of 3D printing filaments containing metal additives and their particulate emissions

Polylactic acid (PLA) filaments are widely used in fused filament fabrication (FFF) processes (3D printing). Filament additives such as metallic particles incorporated into PLA to modify functional and aesthetic features of print objects are becoming increasingly popular. However, the identities and concentrations of low percentage and trace metals in these filaments have not been well described in either the literature or product safety information included with the product. Here, we report the structures and concentrations of metals in selected Copperfill, Bronzefill and Steelfill filaments. We also report size-weighted number concentrations and size-weighted mass concentrations of particulate emissions as a function of print temperature for each filament. Particulate emissions were heterogenous in shape and size with airborne particles below 50 nm diameter dominating the size-weighted particle concentrations and larger particles (approximately 300 nm) dominating the mass weighted particle concentration. Results indicate that potential exposure to particles in the nano-size range increase when using print temperatures above 200o C. Because inhalation exposure to nanoparticles has been linked to adverse health outcomes, we suggest that using lower print temperatures for specific metal-fill filaments may reduce their operational hazard.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Role of Intermolecular Interactions in Deep Eutectic Solvents for CO 2 Capture: Vibrational Spectroscopy and Quantum Chemical Studies

Recent research and reviews on CO 2 capture methods, along with advancements in industry, have highlighted high costs and energy-intensive nature as the primary limitations of conventional direct air capture and storage (DACS) methods. In response to these challenges, deep eutectic solvents (DESs) have emerged as promising absorbents due to their scalability, selectivity, and lower environmental impact compared to other absorbents. However, the molecular origins of their enhanced thermal stability and selectivity for DAC applications have not been explored before. Therefore, the current study focuses on a comprehensive investigation into the molecular interactions within an alkaline DES composed of potassium hydroxide (KOH) and ethylene glycol (EG). Combining Fourier transform infrared (FT-IR) and quantum chemical calculations, the study reports structural changes and intermolecular interactions induced in EG upon addition of KOH and its implications on CO 2 capture. Experimental and computational spectroscopic studies confirm the presence of noncovalent interactions (hydrogen bonds) within both EG and the KOH-EG system and point to the aggregation of ions at higher KOH concentrations. Additionally, molecular electrostatic potential (MESP) surface analysis, natural bond orbital (NBO) analysis, quantum theory of atoms-in-molecules (QTAIM) analysis, and reduced density gradient-noncovalent interaction (RDG-NCI) plot analysis elucidate changes in polarizability, charge distribution, hydrogen bond types, noncovalent interactions, and interaction strengths, respectively. Evaluation of explicit and hybrid models assesses their effectiveness in representing intermolecular interactions. This research enhances our understanding of molecular interactions in the KOH-EG system, which are essential for both the absorption and desorption of CO 2 . The study also aids in predicting and selecting DES components, optimizing their ratios with salts, and fine-tuning the properties of similar solvents and salts for enhanced CO 2 capture efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Diploid genomic architecture of Nitzschia inconspicua, an elite biomass production diatom

Abstract A near-complete diploid nuclear genome and accompanying circular mitochondrial and chloroplast genomes have been assembled from the elite commercial diatom species Nitzschia inconspicua . The 50 Mbp haploid size of the nuclear genome is nearly double that of model diatom Phaeodactylum tricornutum , but 30% smaller than closer relative Fragilariopsis cylindrus . Diploid assembly, which was facilitated by low levels of allelic heterozygosity (2.7%), included 14 candidate chromosome pairs composed of long, syntenic contigs, covering 93% of the total assembly. Telomeric ends were capped with an unusual 12-mer, G-rich, degenerate repeat sequence. Predicted proteins were highly enriched in strain-specific marker domains associated with cell-surface adhesion, biofilm formation, and raphe system gliding motility. Expanded species-specific families of carbonic anhydrases suggest potential enhancement of carbon concentration efficiency, and duplicated glycolysis and fatty acid synthesis pathways across cytosolic and organellar compartments may enhance peak metabolic output, contributing to competitive success over other organisms in mixed cultures. The N. inconspicua genome delivers a robust new reference for future functional and transcriptomic studies to illuminate the physiology of benthic pennate diatoms and harness their unique adaptations to support commercial algae biomass and bioproduct production.

09 BIOMASS FUELS↗
DOE OSTI2021

Kinetics of furfural electrochemical hydrogenation and hydrogenolysis in acidic media on copper

Electrochemical processes can be implemented for the valorization of biomass-derived species such as furfural to generate fine chemicals and fuels. The electrochemical hydrogenation and hydrogenolysis (ECH) of furfural (FF) can produce furfuryl alcohol (FA) and 2-methylfuran (MF) as the major products over Cu catalysts in acidic conditions. The production of these species are in competition and the kinetics of these reactions should be studied so that the product distribution can be better controlled. In this work, the competing kinetics of furfural ECH to furfuryl alcohol and 2-methylfuran were studied on Cu in acidic media by using the applied cathodic potential, temperature, and initial concentration of furfural as probes. Furthermore, an increased temperature of the system was shown to promote the MF production in the range tested (15 °C and 45 °C), however the production of FA was decreased when the temperature was increased from 35 °C to 45 °C, due to significant promotion of side reactions. By varying the concentration of FF used in bulk electrolysis, we saw that the rates of reaction to FA and MF shift from positive order to zero order, suggesting a Langmuir–Hinshelwood or Eley–Rideal mechanism at –0.56 V vs. RHE and 25 °C. An analysis of the reaction mechanisms showed that a non-competitive Langmuir–Hinshelwood mechanism is likely occurring. In addition, we suggest the likely rate limiting steps based on the mechanisms are the first hydrogenation step of FF to C 4 H 3 O–CH 2 O to form FA, and the C–O cleavage of the C 4 H 3 O–CHOH intermediate to form MF.

09 BIOMASS FUELS↗
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↗