Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Radiolysis”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Generation and Study of Am(IV) by Temperature-Controlled Electron Pulse Radiolysis

Used nuclear fuel (UNF) separation techniques that strive to separate radiotoxic americium (Am) from trivalent lanthanide fission products through oxidation state control have increased research efforts surrounding Am(V) and Am(VI). However, equivalent knowledge of the tetravalent state, Am(IV), has remained elusive, particularly in conditions more representative of UNF reprocessing, i.e., in concentrated nitric acid (HNO3). With this in mind, we have used electron pulse radiolysis to study the radiation-induced redox reaction of Am(III) with the oxidizing nitrate radical (NO3?) in 6 M HNO3: Am(III) + NO3? ? Am(IV) + NO3? . These experiments enabled us to observe the growth and decay of Am(IV) in a concentrated acidic solution for the first time. The transient Am(IV) species was found to have a lifetime of ~16 µs?sufficiently long-lived to play a critical mechanistic role in UNF reprocessing systems. Additionally, we performed the first-ever temperature-dependent kinetics study of an actinide element, elucidating unprecedented Arrhenius and Eyring activation parameters for the reaction of Am(III) with NO3?. This new knowledge provides much-needed molecular-level insights into the radiation-induced behavior of Am.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

A Critical Review of Radiolysis Issues in Water-Cooled Fission and Fusion Reactors: Part I, Assessment of Radiolysis Models

A critical review is presented on modeling of the radiolysis of the coolant water in nuclear power reactors with emphasis on ITER. The review is presented in two parts: In Part I, we assess previous work in terms of compliance with important chemical principles and conclude that no model proposed to date is completely satisfactory, in this regard. Thus, some reactions that have been proposed in various radiolysis models are not elementary in nature and can be decomposed into two or more elementary reactions, some of which are already included in the models. These reactions must be removed in formulating a viable model. Furthermore, elementary reactions between species of like charge are also commonly included, but they can be discounted upon the basis of Coulombic repulsion under the prevailing conditions (T < 350 °C) and must also be removed. Likewise, it is concluded that the current state of knowledge with respect to radiolytic yields (i.e., G-values) is also unsatisfactory. More work is required to ensure that the yields used in radiolysis models are truly “primary” yields corresponding to a time scale of nanoseconds or less. This is necessary to ensure that the impact of the reactions that occur outside of the spurs (ionizing particle tracks in the medium) are not counted twice. In Part II, the authors review the use of the radiolysis models coupled with electrochemical models to predict the water chemistry, corrosion potential, crack growth rate in Type 304 SS, and accumulated damage in the coolant circuits of boiling water reactors, pressurized water reactors, and the test fusion reactor, ITER. Based on experience with fission reactors, the emphasis should be placed on the control of the electrochemical corrosion potential because it is the parameter that best describes the state of corrosion in coolant circuits.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2024

Effect of Impurities on Radical Formation in Gibbsite Radiolysis

The generation and stabilization of gamma radiation-induced hydrogen atoms in gibbsite (Al(OH)3) nanoplates is directly related to the nature of residual ions from synthetic precursors used, whether nitrates or chlorides. The concentration of hydrogen atoms trapped in the interstitial layers of gibbsite is lower and decays faster in comparison to boehmite (AlOOH), which could affect the waste management of these materials.

Hlushko, Hannah↗
NASA NTRS1985

The radiolysis and radioracemization of amino acids on clays

The effects of the surfaces of kaolinite and bentonite clays on the radiolysis and radioracemization of L-leucine and its hydrochloride salt have been investigated experimentally. L-leucine and its hydrochloride salt were deposited on the clays and the amino acid/clay preparations were irradiated by a Co-60 gamma-ray source which induced 2-89 percent radiolysis. The efficiency of radiolysis and radioracemization were measured using gas chromatography. Results were obtained for leucine in 0.1 M aqueous solution for comparison with the clay-deposted leucine and leucine hydrochloride. It is found that radiolysis and radioracemization in the samples occurred according to a pseudo-first-order rate law. Comparison of the specific rate constants showed that leucine and its hydrochloride salt were the most resistant to both radiolysis and radioracemization, followed by leucine and its hydrochloride salt on kaolin. Leucine and its HCl salt on bentonite, and leucine in aqueous solution were found to be the least resistant to radiolysis and radioracemization. The experimental results are intepreted with respect to the Vester-Ulbricht mechanism for the origin of optical activity.

Bonner, W. A.↗
NASA NTRS2024

Organic Products of Fatty Acid and Magnesium Sulfate Mixtures after Gamma Radiolysis: Implications for Missions to Europa

If ocean-derived materials are present at Europa’s surface, they would represent accessible records of ocean chemistry and habitability, but such materials would be further processed by the moon’s harsh radiation environment. In this study, saturated fatty acids were precipitated onto a Europa-relevant hydrated magnesium sulfate and exposed to gamma radiation doses up to 2 MGy at -196° C. Alkane chains, with carbon numbers one less than those of the starting fatty acids, were the most abundant radiolysis products in solvent and thermal extracts analyzed by gas chromatography mass spectrometry. Detections of monounsaturated fatty acids and combined radiolysis products were attributed to the experiment’s Europa-like parameters. Additionally, elevated concentrations of shorter-chain saturated fatty acids suggest that gamma radiation induced charge remote fragmentation of the alkyl chains of some starting fatty acids under these experimental conditions. Quantitation of fatty acid concentrations in the irradiated samples enabled the calculation of a radiolysis constant that indicated exposure to a 5 MGy dose of gamma radiation would have resulted in a ~90% loss of the initial fatty acid population. The samples were further studied by Raman spectroscopy and laser desorption and ionization mass spectrometry, which characterized the distribution of fatty acids and their radiolysis products on sulfate surfaces. The substantial loss of starting fatty acids typically seen with increasing radiation dose, along with the remarkable diversity of radiolysis products identified, suggest that the detection of fatty acids in irradiated sulfate deposits on Europa will be challenged by rapid destruction of any initial fatty acid populations and scrambling of their residual signals by a myriad of organic radiolysis products. If missions to Europa encounter sulfate deposits, targeting minimally irradiated units may still enable the detection of surviving fatty acid signatures that could inform about Europa’s subsurface chemistry and habitability.

James M T Lewis↗
DOE OSTI2022

Coupling Pulse Radiolysis with Nanosecond Time-Resolved Step-Scan Fourier Transform Infrared Spectroscopy: Broadband Mid-Infrared Detection of Radiolytically Generated Transients

We describe the first implementation of broadband, nanosecond time-resolved step-scan Fourier transform infrared (S 2 -FT-IR) spectroscopy at a pulse radiolysis facility. This new technique allows the rapid acquisition of nano- to microsecond time-resolved infrared (TRIR) spectra of transient species generated by pulse radiolysis of liquid samples at a pulsed electron accelerator. Wide regions of the mid-infrared can be probed in a single experiment, which often takes < 20–30 min to complete. It is therefore a powerful method for rapidly locating the IR absorptions of short-lived, radiation-induced species in solution, and for directly monitoring their subsequent reactions. Time-resolved step-scan FT-IR detection for pulse radiolysis thus complements our existing narrowband quantum cascade laser-based pulse radiolysis-TRIR detection system, which is more suitable for acquiring single-shot kinetics and narrowband TRIR spectra on small-volume samples and in strongly absorbing solvents, such as water. We have demonstrated the application of time-resolved step-scan FT-IR spectroscopy to pulse radiolysis by probing the metal carbonyl and organic carbonyl vibrations of the one-electron-reduced forms of two Re-based CO 2 reduction catalysts in acetonitrile solution. Transient IR absorption bands with amplitudes on the order of 1 × 10 −3 are easily detected on the sub-microsecond timescale using electron pulses as short as 250 ns.

(S2-FT-IR)↗
DOE OSTI2025

Similarity Metric for Data Optimization and Efficient Training of Reactive Machine Learning Force Fields for Hydrocarbon Radiolysis

Radiolysis is a common approach to sterilize polymers, chemically modify them for upcycling, and accelerate their decomposition for recycling purposes. Reactive molecular dynamics (MD) simulations provide a powerful tool to generate atomic-level trajectories of the reactive processes and quantify radiolytic chemical degradation pathways. For this, machine learning (ML) surrogate models for reactive force fields with quantum mechanical accuracy are now widely used, which require ML training data sets that can provide information on atomic environments for target chemical systems. However, radiolysis chemistry can be highly complex and diverse, which poses significant challenges for generating training data to parametrize ML models. In this regard, we developed a method for optimizing the training data set using a cosine similarity metric to help guide training set selection for radiolysis of polyethylene, a model hydrocarbon polymer, as well as to enhance the transferability of our reactive ML force field (MLFF) to a variety of molecular and polymeric systems. Our approach performs atom-by-atom comparisons between local atomic environments to pinpoint important data points associated with rare and localized events, such as radiolysis damage within structures. We apply this approach to train the Chebyshev Interaction Model for Efficient Simulation (ChIMES) MLFF model, which expresses the atomic interaction potentials in terms of linear combinations of many-body Chebyshev polynomials. We first show that our method can reduce our training set size by ∼70% while improving overall accuracy compared to more standard MD model fitting approaches. We then validate our optimum model against diverse hydrocarbon simulation data, including simple alkanes and systems with unsaturated carbon bonds, over a wide range of thermodynamic conditions. Finally, we use our ChIMES model to perform MD simulations of radiolytic damage with large-scale systems that help avoid system size effects. Overall, our approach yields an MD force field that retains most of the accuracy of the underlying quantum method while yielding many orders of improvement in computational efficiency. In conclusion, our efforts will have impact on future hydrocarbon polymer radiolysis studies, where the chemical details of the polymer–radiation interactions can have a strong effect on the resulting products observed in experiments.

Hydrocarbons↗
NASA NTRS1971

Radiolysis of water in sealed aluminum capsules - Its prediction and inhibition.

This report presents the results of an investigation into methods of inhibiting the radiolysis of water in sealed aluminum capsules in the Plum Brook Reactor of NASA. Experimental design techniques are employed to identify the measured effects of eight variables and their interactions which control water decomposition and the resultant pressure buildup. Multiple regression analyses are used to develop predictive models for the pressure rise observed in an inpile capsule system. Predictive equations are derived for pressure rise due to the radiolysis of water with air as a cover gas or with helium cover gas containing air as an impurity or mixtures of hydrogen, oxygen, and nitrogen as impurities. Radiation induced reaction products of nitrogen and oxygen are identified as the key to radiolysis behavior. The prevention of radiolysis depends on the exclusion of air or mixtures of nitrogen and oxygen from the system. Pure inert gases, helium, neon, and argon prove to be satisfactory radiolysis inhibitors. This is demonstrated for helium by inpile tests lasting up to 14 days (one reactor cycle) in the Plum Brook Reactor.

Sheibley, D. W.↗
NASA NTRS1981

The radiolysis and radioracemization of amino acids on silica surfaces

Results are presented of experiments on the radioracemization of amino acids in the presence of silica surfaces such as may have been found on the prebiotic earth. L-leucine and a DL-leucine mixture deposited on samples of 1-quartz and an amorphous silica preparation (Syloid 63) was subjected to Co-60 gamma-ray irradiation, then analyzed by gas chromatography to determine the radiolysis and racemization rates. The quartz surface is found to have a marginal efficacy in enhancing radiolysis when compared with a crystalline L-leucine control, although enhancing radioracemization symmetrically by a factor of two. Both the radiolysis and radioracemization of L-leucine and DL-leucine on a Syloid-63 silica surface are observed to increase with increasing radiation dose, and to be substantially greater than in the crystalline controls. Additional experiments with the nonprotein amino acid isovaline deposited on Syloid 63 confirm the greater radiolysis susceptibility of amino acids deposited on silica with respect to the crystalline state, although racemization is not observed. The observations suggest that the presence of a silica surface would have a deleterious effect on any mechanism for the origin of molecular chirality relying on stereoselective beta-radiolysis.

Bonner, W. A.↗
DOE OSTI2023

Radiolysis of Thin Water Ice in Electron Microscopy

Little is known about the radiolysis of water ice, especially as compared to the radiolysis of liquid water. In this study, the radiolytic decomposition of thin water ice films is probed for an initial 80 keV electron beam using electron energy loss spectroscopy, EELS. Pre-peaks in the oxygen K-edge spectra give the relative intensities of most of the oxygen containing species produced by radiolytic water decomposition. Contrary to expectations from the extrapolation of liquid water radiolysis data to high dose rates where significant H 2 O 2 production is expected, the main molecular product observed in the oxygen K-edge EELS spectra of water ice is O 2 . Significant mass loss of water and decomposition of most of its radiolytic products are observed for higher exposures, and the O atom seems to have a major role in the subsequent chemistry. An inverse relationship between the formation of O 2 and of ·OH is observed. A new high-dose reaction scheme is proposed. Furthermore, the significance of our results with respect to the radiolysis of water ice and for electron microscopy studies is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A Model for Radiolysis in a Flowing-Water Target during High-Intensity Proton Irradiation

At the Facility for Rare Isotope Beams (FRIB), interactions between heavy-ion beams and beam-dump water will create a wide variety of radionuclides which can be accessed by a technique known as “isotope harvesting”. However, irradiation of water is always accompanied by the creation of numerous radical, ionic, and molecular radiolysis products. Some of the radiolysis products have sufficiently long lifetimes to accumulate in the irradiated water and affect the harvesting chemistry. Here we investigate the formation of hydrogen peroxide, molecular hydrogen, and molecular oxygen during a high-intensity proton irradiation of a flowing-water isotope-harvesting target and compare the experimental results to simulations. The simulations kinetically model the chemical reactions occurring in the homogeneous phase of radiolysis in flowing water and establish an “effective yield”. In both the experiment and simulations, the bulk quantities of H 2 , H 2 O 2 , and O 2 are considerably lower than predicted by primary radiolysis yields (escape yields), meaning that in the high beam intensity regime the homogeneous phase reactions have a considerable impact on the overall chemical composition of the water. Further, it could be shown that for radiation which is characterized by a limited linear energy transfer, such as the here applied protons, the bulk outcome of the microscopic kinetic modeling could be estimated by a simplified steady-state model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2006

Volume Ice Radiolysis in the Outer Solar System

The primary energy flux of charged particle components of the heliospheric and magnetospheric environments of the solar system is primarily carried by highly penetrating energetic particles. Although laboratory experiments on production of organics and oxidants typically only address effects on very thin surface layers, energy deposition occurs on surfaces of icy bodies of the outer solar system to meters in depth. Time scales for significant radiolytic deposition vary from thousands of years at millimeter depths on Europa to billions of years in the meters-deep regolith of Kuiper Belt Objects. Radioisotope decay (e.g., K-40) also contributes to volume radiolysis as the only energy source at much greater depths. Radiolytic oxygen is a potential resource for life within Europa and a partial source of oxygen for Saturn's magnetosphere and Titan's upper atmosphere. Interactions of very high energy cosmic rays with ices at Titan's surface may provide one of the few sources of oxidants in that highly reducing environment. The red colors of low-inclination classical Kuiper Belt Objects at 40-50 AU, and Centaur objects originating from this same population, may arise from volume radiolysis of deep ice layers below more refractory radiation crusts eroded away by surface sputtering and micrometeoroid impacts. A variety of techniques are potentially available to measure volume radiolysis products and have been proposed for study as part of the new Space Physics of Life initiative at NASA Goddard Space Flight Center. The technique of Electron Paramagnetic Resonance (EPR) has been used in medical studies to measure oxidant production in irradiated human tissue for cancer treatment. Other potential techniques include optical absorption spectroscopy and standard wet chemical analysis. These and other potential techniques are briefly reviewed for applicability to problems in solar system ice radiolysis and astrobiology.

Cooper, John F.↗
DOE OSTI2024

Dodecane Radiolysis Yields by Time-Resolved and Steady-State Methods

Liquid organic molecules are present as solvents, complexing ligands, and additives in both used nuclear fuel reprocessing solvent systems and in their subsequent nuclear waste streams. Under these extreme environments, these organic molecules are constantly exposed to ionizing radiation which promotes their radiolysis, forming a variety of short-lived, highly energetic, excited state and radical species.1-4 Here, we demonstrate new experimental results for the steady-state and time-resolved irradiations of dodecane (C12H26), a long chain, liquid, aliphatic hydrocarbon that is the prototypical solvent used for benchtop studies of aqueous-organic solvent extraction systems. When ionizing radiation interacts with neat dodecane, the energy transfer can result in molecular ionization, to give the dodecane radical cation (C12H26+•) and the solvated electron (eS–), and molecular electronic excitation (C12H26*), which rapidly produces transient carbon-centered radical fragments (CxHy•) and hydrogen atoms (H•).1-4 Studies on the initial yields of the ionization and excitation products were performed using time-resolved picosecond electron pulse radiolysis with the use of molecular probes. Using steady-state cobalt-60 gamma irradiations, the suite of products formed by dodecane radiolysis in aerated and deaerated solutions was determined. Then, using iodine as an alkyl radical scavenger, the loss of molecular iodine with dose was quantified, and by correlating with the molecular hydrogen yields of the system, the initial yields of the various carbon-centered radicals were also determined. Finally, the rates of reactions of the C12H26+• and eS– with ligands proposed for use in spent nuclear fuel reprocessing were studied as a function of temperature from 10 – 40 °C.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗
DOE OSTI2025

Indium Tin-Doped Oxide Interactions with Solvent Radiolysis Products

Transparent conductive oxides (TCOs), such as indium tin-doped oxide (ITO), are ubiquitous as components of electronics and are ideal electrode substrates for catalysis, energy transformation reactions, and energy storage applications. Recently, researchers have recognized their effectiveness as electrode materials for manipulating actinide oxidation states in solution. Despite their popularity as electrode materials, prior studies focused extensively on the direct radiolysis of TCO materials in air and rarely examined these effects within a solution, limiting our fundamental understanding of the interactions between solvent radiolysis products and these substrates in high radiation environments. Here, in this study, we characterize the effects of solvent radiolysis products—arising from the gamma irradiation of water, aqueous nitric acid solutions, and n-dodecane—on the composition, surface speciation, and band structure of ITO thin films on a glass substrate as a function of absorbed dose using UV-visible spectroscopy, scanning electron microscopy, photoelectrochemistry, and X-ray photoelectron spectroscopy. Our work demonstrates that mesoporous thin film electrodes of ITO exposed to gamma radiation in each solvent accumulate defects and exhibit solvent and dose dependent changes to their surface and interfacial properties. These electrodes maintain their electrochemical function and improve their photoelectrochemical performance up to at least 100 kGy of accumulated gamma dose, confirming their utility in solvents exposed to ionizing radiation fields.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

On the Mechanism of the Steady-State Gamma Radiolysis-Induced Scissions of the Phenyl-Vinyl Polyester-Based Resins

The major societal problem of polymeric waste necessitates new approaches to break down especially challenging discarded waste streams. Gamma radiation was utilized in conjunction with varying solvent environments in an attempt to discern the efficacy of radiolysis as a tool for the deliberate degradation of model network polyesters. Our EPR results demonstrated that gamma radiolysis of neat resin and in the presence of four widely used solvents induces glycosidic scissions on the backbone of the polyester chains. EPR results clearly show the formation of alkoxy radicals and C-centered radicals as primary intermediate radiolytic products. Despite the protective role of the phenyl groups on the backbone of the radiation-induced polyester chains, the radiolytic-glycosidic scissions predominate. Among the following three solvents used in this study (water, isopropyl alcohol, and dichloromethane), the highest radiolytic yield of glycosidic scission was achieved using water. The •OH radicals produced in the radiolysis of phenyl unsaturated polyester aqueous suspensions very rapidly abstract H atoms from the methylene group, which is followed by a very rapid glycosidic scission. The lowest glycosidic yield was found in the dichloromethane solutions of these polyester resins due to scavenging by the fast electron capture reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Synthesis of Yttrium Oxide Particles for Interfacial Water Radiolysis Studies

Radiolysis of water produces hydrogen gas (H2), posing safety issues for nuclear reactors. Metal oxides can impact H2 formation when water is present on metal oxide surfaces. This presentation focuses on the development of a controllable synthesis of spherical yttrium oxide (Y2O3), that later will be tested for H2 production in water radiolysis. Y2O3 was synthesized via hydrothermal hydrolysis precipitation to form yttrium hydroxide (Y(OH)3), followed by high temperature decomposition to form Y2O3. Various synthesis conditions were tested to determine their impact on particle morphology including reaction time, cooling rate, reactant concentration, and inert atmospheres. Through short reaction times and rapid cooling rate, spherical, relatively uniform particles of 350 nm were obtained. Despite inert atmospheres, carbonate formation occurred in all particles. A calcination temperature of 800°C is necessary to remove impurities. Future work will aim to reduce carbonate formation and improve particle uniformity. The synthetic procedure will be translated to other metal ions to study their impact on interfacial radiolysis.

08 - HYDROGEN↗
NASA NTRS2008

A Review of Radiolysis Concerns for Water Shielding in Fission Surface Power Applications

This paper presents an overview of radiolysis concerns with regard to water shields for fission surface power. A review of the radiolysis process is presented and key parameters and trends are identified. From this understanding of the radiolytic decomposition of water, shield pressurization and corrosion are identified as the primary concerns. Existing experimental and modeling data addressing concerns are summarized. It was found that radiolysis of pure water in a closed volume results in minimal, if any net decomposition, and therefore reduces the potential for shield pressurization and corrosion. With the space program focus m emphasize more on permanent return to the Moon and eventually manned exploration of Mars, there has been a renewed look at fission power to meet the difficult technical & design challenges associated with this effort. This is due to the ability of fission power to provide a power rich environment that is insensitive to solar intensity and related aspects such as duration of night, dusty environments, and distance from the sun, etc. One critical aspect in the utilization of fission power for these applications of manned exploration is shielding. Although not typically considered for space applications, water shields have been identified as one potential option due to benefits in mass savings and reduced development cost and technical risk (Poston, 2006). However, the water shield option requires demonstration of its ability to meet key technical challenges including such things as adequate natural circulation for thermal management and capability for operational periods up to 8 years. Thermal management concerns have begun to be addressed and are not expected to be a problem (Pearson, 2007). One significant concern remaining is the ability to maintain the shield integrity through its operational lifetime. Shield integrity could be compromised through shield pressurization and corrosion resulting from the radiolytic decomposition of water.

Schoenfeld, Michael P.↗
NASA NTRS2010

Radiolysis and Photolysis of Icy Satellite Surfaces: Experiments and Theory

The transport and exchange of material between bodies in the outer solar system is often facilitated by their exposure to ionizing radiation. With this in mind we review the effects of energetic ions, electrons and UV photons on materials present in the outer solar system. We consider radiolysis, photolysis, and sputtering of low temperature solids. Radiolysis and photolysis are the chemistry that follows the bond breaking and ionization produced by incident radiation, producing, e.g., O2 and H2 from irradiated H2O ice. Sputtering is the ejection of molecules by incident radiation. Both processes are particularly effective on ices in the outer solar system. Materials reviewed include H2O ice, sulfur-containing compounds (such as S02 and S8), carbon~contajning compounds (such as CH4), nitrogen-containing compounds (such as NH3 and N2), and mixtures of those compounds. We also review the effects of ionizing radiation on a mixture of N2 and CH4 gases, as appropriate to Titan's upper atmosphere, where radiolysis and photolysis produce complex organic compounds (tholins).

Cassidy, T.↗