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Photothermal Atomic Force Microscopy Coupled with Infrared Spectroscopy (AFM-IR) Analysis of High Extinction Coefficient Materials: A Case Study with Silica and Silicate Glasses

Photothermal atomic force microscopy coupled with infrared spectroscopy (AFM-IR) brings significant value as a spatially resolved surface analysis technique for disordered oxide materials such as glasses, but additional development and fundamental understanding of governing principles is needed to interpret AFM-IR spectra, since the existing theory described for organic materials does not work for materials with high extinction coefficients for infrared (IR) absorption. This paper describes theoretical calculation of a transient temperature profile inside the IR-absorbing material considering IR refraction at the interface as well as IR adsorption and heat transfer inside the sample. Furthermore, this calculation explains the differences in peak positions and amplitudes of AFM-IR spectra from those of specular reflectance and extinction coefficient spectra. It also addresses the information depth of the AFM-IR characterization of bulk materials. AFM-IR applied to silica and silicate glass surfaces has demonstrated novel capability of characterizing subsurface structural changes and surface heterogeneity due to mechanical stresses from physical contacts, as well as chemical alterations manifested in surface layers through aqueous corrosion.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

National nuclear forensics libraries: a case study on benefits and possibilities for identification of sealed radioactive sources

A National Nuclear Forensic Library (NNFL) is a useful nuclear forensics tool which consists of information and subject matter expertise on radioactive and nuclear (RN) materials produced, used or stored within a State. If RN material is found out of regulatory control the NNFL can be used as part of a nuclear forensics investigation to help identify whether or not the material is consistent with a country’s national holdings. In previous work, a number of signatures which can be useful to identify sealed sources of 241 Am were investigated. To validate the measurement results, an official query concerning information about two of the previously investigated 241 Am sources was sent to the United States Department of State, the international point-of-contact (POC) for the U.S. NNFL. The aim of this work is to show how data obtained in a characterization of a radioactive source can be used in conjunction with an NNFL to investigate the history of a source out of regulatory control.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Toward Rapid Actinium-225 Purification via Membrane Adsorbers with Covalently Tethered Diglycolamide Ligands

Extractive diglycolamide (DGA) resins are used in several state-of-the-art techniques for purifying 225 Ac, a promising radiometal for targeted alpha therapy. Unfortunately, separation processes that rely on resins are often limited to slow flow rates, high elution volumes, and long processing times. Membrane adsorbers functionalized with DGA ligands are an alternative separation material that may overcome these challenges. This work presents (1) the synthesis of an aminated tetrahexyldiglycolamide ligand, (2) the covalent tethering of the ligand to electrospun poly(vinylbenzyl chloride) fiber mats, and (3) the adsorption and desorption of La(III) and 225 Ac. Chemical and physical characterization supports the covalent tethering of the ligand to the fiber mat, as well as the preservation of the fiber surface area and porosity after functionalization. Equilibrium adsorption experiments were performed with stable La(III) and radioactive 225 Ac. Trends in affinity are consistent between commercial resins and the synthesized membrane adsorbers; however, the Langmuir constants and the maximum binding capacity of the membrane adsorbers were generally lower than the resins. Despite these differences, the modeled selectivity for an equimolar solution of La(III)/ 225 Ac in 10 M nitric acid is 57. Furthermore, 225 Ac is rapidly desorbed from the fibers in 10 M nitric acid (<20 min). The La(III)/ 225 Ac selectivity and rapid 225 Ac desorption indicate this class of materials is promising for rapid radioanalytical separations.

07 ISOTOPE AND RADIATION SOURCES↗

Composition Measurements of the LAW ALG Glasses

This report provides the results from the chemical analyses of glass compositions for the Low-Activity Waste Algorithm study glasses, a series of simulated nuclear waste glasses designed and fabricated at Pacific Northwest National Laboratory. These data will be used in the development, validation, and implementation of enhanced property/composition models for waste glass vitrification at Hanford. Chemical analyses were performed on a representative sample of each of the quenched glasses to allow for comparisons with targeted compositions. The relative differences between the targeted and measured concentrations of SO 3 for most of the glasses were greater than 10%. The relative differences between the targeted and measured concentration of F- was greater than 10% for one glass. The relative differences between the targeted and measured concentration of SnO 2 was greater than 10% for one glass. These results can be used in further characterization of this series of glasses, including the normalization of Product Consistency Test results.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of cathode keeper wear by surface layer activation

In this study, the erosion rates of the discharge cathode keeper in a 30 cm NSTAR configuration ion thruster were measured using a technique known as Surface Layer Activation (SLA). This diagnostic technique involves producing a radioactive tracer in a given surface by bombardment with high energy ions. The decrease in activity of the tracer material may be monitored as the surface is subjected to wear processes and correlated to a depth calibration curve, yielding the eroded depth. Analysis of the activities was achieved through a gamma spectroscopy system. The primary objectives of this investigation were to reproduce erosion data observed in previous wear studies in order to validate the technique, and to determine the effect of different engine operating parameters on erosion rate. The erosion profile at the TH 15 (23 kw) setting observed during the 8200 hour Life Demonstration Test (LDT) was reproduced. The maximum keeper erosion rate at this setting was determined to be 0.085 pm/hr. Testing at the TH 8 (1.4 kw) setting demonstrated lower erosion rates than TH 15, along with a different wear profile. Varying the keeper voltage was shown to have a significant effect on the erosion, with a positive bias with respect to cathode potential decreasing the erosion rate significantly. Accurate measurements were achieved after operating times of only 40 to 70 hours, a significant improvement over other erosion diagnostic methods.

surface layer activation↗

Risks of nuclear waste disposal in space. III - Long-term orbital evolution of small particle distribution

A study of long term risks is presented that treats an additional pathway that could result in earth reentry, namely, small radioactive particles released in solar orbit due to payload fragmentation by accidental explosion or meteoroid impact. A characterization of such an event and of the initial mass size distribution of particles is given for two extremes of waste form strength. Attention is given to numerical results showing the mass-time distribution of material and the fraction of initial mass intercepted by earth. It is concluded that it appears that program planners need not be to concerned about the risks of this particular failure mechanism and return pathway.

Friedlander, A. L.↗

A laserball calibration device for the SNO+ scintillator phase

Located 2 km underground in SNOLAB, Sudbury, Canada, SNO+ is a large scale liquid scintillator experiment that primarily aims to search for neutrinoless double beta decay. Whilst SNO+ has light and radioactive calibration sources external to the inner volume, an internally deployed optical source is necessary for the full characterization of the detector model. A laser diffuser ball developed for SNO has previously demonstrated to be an effective optical calibration device for both SNO and SNO+ water phase. Since the introduction of liquid scintillator for SNO+, the material compatibility, cleanliness, and radiopurity requirements of any materials in contact with the internal medium have increased. Improving on the original SNO laserball design, a new laserball calibration device has been developed for the SNO+ scintillator phase with the goal of measuring the optical properties of the detector and performing routine PMT gain and timing calibrations. Simulations have been written to model the diffusion properties to optimise optical and temporal performance for calibration. Prototype laserballs have been built and characterised, demonstrating sub-ns timing resolution and a quasi-isotropic light distribution.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

TRIPWIRE – Deployment and Field-Testing Report

TRIPWIRE is a multi-modal system for containment verification in inaccessible radiological and nuclear waste repositories. The sensing modes are focused on radiation, electromagnetic and vibration. The radiation detection component has been developed over the last three years at Idaho National Laboratory (INL). This development has focused on the fabrication, characterization, and testing of long-length (greater than 10-m) plastic scintillating fibers. This fiscal year, the focus of TRIPWIRE has been on field testing and demonstration of the radiation sensing component in a relevant environment. After reviewing the static storage facilities at INL, the Radioactive Scrap Waste Facility (RSWF) south storage area outside the Materials and Fuels Complex (MFC) was selected due to its periodic changes in configuration and inventory. This report summarizes the research outcomes for the work performed in fiscal year (FY) 2023.

98 - NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL↗

Development of ultralow-background cryogenic calorimeters for the measurement of surface α contamination

Next-generation experiments searching for rare events must satisfy increasingly stringent requirements on the bulk and surface radioactive contamination of their active and structural materials. The measurement of surface contamination is particularly challenging, as no existing technology is capable of separately measuring parts of the 232 Th and 238 U decay chains that are commonly found to be out of secular equilibrium. We will present the results obtained with a detector prototype consisting of 8 silicon wafers of 150mm diameter instrumented as bolometers and operated in a low-background dilution refrigerator at the Gran Sasso Underground Laboratory of INFN, Italy. Furthermore, the prototype was characterized by a baseline energy resolution of few keV and a background <100nBq/cm 2 in the full range of α energies, obtained with simple procedures for cleaning of all employed materials and no specific measures to prevent recontamination. Such performance, together with the modularity of the detector design, demonstrate the possibility to realize an alpha detector capable of separately measuring all alpha emitters of the 232 Th and 238 U chains, possibly reaching a sensitivity of few nBq/cm 2 .

07 ISOTOPE AND RADIATION SOURCES↗

Characterizing The Mechanical Properties of Polyurethane Foams

The Department of Energy has many radioactive facilities that are on the path of deactivation and decommissioning (D and D). These facilities can sit cold and dark for many years before final disposition, and must be maintained to ensure no radiological release occurs in the interim. Improvements and additions to D and D tool sets can greatly: Save time and money, Reduce worker risk. Conventional fixatives widely used often take the form of paints or films that are not readily applicable to 3-dimensional void spaces. Foams are one promising platform that may offer solutions to a number of contaminated problem sets such as: Gloveboxes, Pipes, Tanks. SRNL is working to characterize various commercial foams that would encapsulate the interior volume of a given space and are capable of immobilizing any remaining contamination. One key performance metric of these foams is how well they will perform in an accident scenario. To this end, SRNL is researching the mechanical properties of these foams to ensure that the material can withstand the environment of application while maintaining structural integrity. ASTM standard E3191-18 served as a guiding document for this project, outlining the requirements that foaming fixatives used for the mitigation of radioactive contamination need to meet before being implemented. Objective: Quantification of the mechanical properties of 6 commercial polyurethane foams was performed using multiple ASTM standards to record measurements for: Compression testing: Flexible Foams, Force required to produce 50% compression, Rigid Foams, Compressive and apparent modulus, Point of 10% core deformation, The 'Zero Deformation' point, Compressive strength, Yield point. Tensile testing: Tensile strength, Tensile stress, Percent elongation. Experiment 1: An electromechanical compressive tester (MTS Criterion Series 43) was used to evaluate 6 foams (4 flexible, 2 rigid). Per ASTM D1621, each rigid foam was compressed at 10% of the measured thickness per minute until the sample was 13% of it's original thickness. Per ASTM D35/4, each flexible foam was pre-flexed twice to 80% original thickness at a rate of 250 mm/min, then compressed to 80% original thickness at a rate of 50 mm/min. Experiment 2: An electromechanical tensile tester (MTS Criterion Series 43) was used to evaluate 6 foams (4 flexible, 2 rigid). Per ASTM D1623, rigid foams were pulled apart at a rate of 1.27 mm/min until the sample broke. Per ASTM D35/4, flexible foams were pulled apart at a rate of 500 mm/min until the sample broke. The strongest material in both compression and tensile testing scenarios was found to be the rigid intumescent polyurethane Hilti foam. The experiments revealed that the Hilti foam in a tensile scenario had a peak stress value that was larger than the closest competitor by a factor of 2.3 and a compressive yield point that was larger than the closest competitor by a factor of 1.4, indicating that the Hilti foam is the best choice for implementation in mechanically harsh environments. The performance metrics measured can serve as a basis for future mechanical tests that would help set relevant ASTM standards (E3191) for intumescent polyurethane foams in fixating applications. Tests like surface adhesion, impact, and flame tests would serve as a better indicator as to how this material would perform in environmentally harsh scenarios often found in decommissioned nuclear facilities. Further tests of the foams' intumescent properties would also be important should these foams be implemented in environmentally harsh scenarios.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of a pulsed, variable-energy positron beam for atomic scale defect studies

Positron annihilation spectroscopy provides a sensitive means of non-destructive characterization of materials, capable of probing single atom vacancies in solids with 10 –7 sensitivity. Here, in this work, we detail the development of a magnetically guided, variable energy, pulsed positron beam designed to conduct depth-dependent defect studies in metals, semiconductors, and dielectrics, which will be the first of its kind in the United States. The design of the target stage provides capabilities for measurements during in situ annealing up to 800 °C and incorporates a new approach to minimize the background due to energetic backscattered positrons. The developed beam at Bowling Green State University provides a powerful tool for characterization of thin films, devices, and ion irradiated materials.

47 OTHER INSTRUMENTATION↗

Certifying the Performance of Fixative Technologies under Open Air Demolition Activities for D and D - 20096

Department of Energy (DOE) facilities undergoing deactivation and decommissioning (D and D) activities struggle with safety concerns of residual radioactive contamination leftover after gross decontamination efforts have concluded. The positive effects of implementing fixative technologies for decommissioning and maintenance is known across the DOE complex. However, there is no standardized metric in place that quantifies the performance of these technologies such as incombustible fixative platforms that immobilize the contamination in a solid polymer material under normal operating conditions or when exposed to stressors. The primary focus of this research is to provide the empirical data necessary to properly characterize the effects of implementing fixative technologies on mitigating the release of contamination. In addition, this effort has been used to identify and establish uniform testing protocols to quantify operational parameters of fixating platforms and properly credit such systems under a variety of operational conditions and stressors that can arise during open air demolition efforts (e.g. impact, water, thermal, etc.). The established protocols will be provided to the ASTM International E10.03 Subcommittee on Radiological Protection for Decontamination and Decommissioning of Nuclear Facilities and Components for the potential of formal standardization. Attributes to be addressed during testing are material compromise from impact stress, thermal stress for incombustible fixative materials, and immobilization factors (how well an immobilizing platform is capable of retaining fixated material during thermal and impact stressors). In developing these test methods, a greater understanding of the material's behavior under anticipated and unanticipated events, such as decommissioning activities and contingency events as outlined in the Basis of Interim Operations (BIO), can be successfully characterized. There are several key components of the experimental methodology that is essential in empirically certifying fixative technologies. A surrogate contaminant with a unique signature has been utilized with the implementation of a uniform contamination process of test coupons that is quantifiable and replicable for direct fixative comparisons. A modular test chamber has also been used to apply the various stressors of interest. Collection of released contamination that includes airborne and resettled contaminant particles and analyzed using mass spectrometry. This research directly supports DOE complex-wide concerns in terms of final disposition of nuclear facilities and the considerations made during their time between ceasing facility operation and final disposition. The results of this effort aims to provide a standardized road map and logical decision flow to better facilitate fixative technologies into D and D activities required to achieve the desired facility end state. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Dirty bomb source term characterization and downwind dispersion: Review of experimental evidence

Dirty bombs are considered one of the easiest forms of radiological terrorism, a form of terrorism based on the deliberate use of radiological material to cause adverse effects in a target population. One U.S. Government official has even described a dirty bomb attack as “all but inevitable”. While people in the vicinity of the blast may experience acute radiation effects, people downwind may unknowingly be contaminated by the radioactive airborne particulate and face increased long-term cancer risk. The likelihood of increased cancer risk depends on the radionuclide used and its specific activity, its aerosolization potential, the particle sizes generated in the blast, and where a person is with respect to the detonation. Different studies have reported that plausible radionuclides for dirty bomb include 60 Co, 90 Sr, 137 Cs, 192 Ir, 241 Am based on their availability in commercial sources as well as safeguards, the amount needed for adverse health effects, previous mishandling of radionuclides and malicious uses. In order to have increased long-term cancer risk, the radionuclide would have to deposit inside the body by entering the respiratory tract and then possibly migrate to other organs or bones (ground shine is not considered in this paper because areas affected by the event will likely become inaccessible). This implies that the particles will have to be smaller than 10 μm to be inhaled. Experiments involving the detonation of dirty bombs have shown that particles or droplets smaller than 10 μm are generated, independently from the initial radionuclide or its state (e.g., powder, solution). Atmospheric tests have shown that in unobstructed terrain, the radionuclide laden cloud can travel kilometers downwind even for relatively small amounts of explosives. Furthermore, buildings in the path of the cloud can change the dose rate. For instance, in one experiment with a single building, the dose rate was 1–2 orders of magnitude lower behind the obstacle compared to its front face. For people walking around, the amount of particulate deposited on them and inhaled will depend on their path relative to the cloud, resulting in the counterintuitive result that the closer people may actually not be the ones more at risk because they could simply miss the bulk of the cloud in their wandering. In summary, the long-term cancer risk for people caught in a dirty bomb cloud away from the detonation requires considering where and when the people are, which radionuclide was used, and the layout of the obstacles (e.g., buildings, vegetation) in the path of the cloud.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Cs absorption capacity and selectivity of crystalline and amorphous Hf and Zr phosphates

Removal of radioactive Cs from sodium-rich solutions is a technical challenge that goes back to post World War II nuclear waste storage and treatment; and interest in this topic was reinvigorated by the Fukushima-Daiichi nuclear power plant disaster, 10 years ago. Since the 1960's there has been considerable focus on layered Zr phosphates as robust inorganic sorbents for separation of radionuclides such as Cs. Here we present synthesis and characterization, and direct comparison of Cs sorption capacity and selectivity of four related materials: 1) crystalline α-Zr phosphate and α-Hf phosphate, and 2) amorphous analogues of these. Powder X-ray diffraction, thermogravimetry, solid-state 31P magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy, and compositional analysis (inductively coupled plasma optical emission spectroscopy and mass spectroscopy, ICP OES and ICP MS) provided formulae; respectively M(HPO4)2∙1H2O and M(HPO4)2∙4H2O (M = Hf, Zr) for crystalline and amorphous analogues. Maximum Cs loading, competitive Cs-Na selectivity and maximum Cs-Na loading followed by the above characterizations plus 133Cs MAS-NMR spectroscopy revealed that amorphous analogues are considerably better Cs-sorbents (based on maximum Cs-loading and selectivity over Na) than the well-studied crystalline Zr-analogue. Additionally, crystalline α-Hf phosphate is better Cs-sorbent than crystalline α-Zr phosphate. All these studies consistently show that Hf phosphate is less crystallize than Zr phosphate, when obtained under similar or identical synthesis conditions. We attribute this to lower solubility of Hf phosphate compared to Zr phosphate, preventing ‘defect healing’ during the synthesis process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

316L Stainless Steel Wire Arc Additive Manufacturing and Characterization for Potential SNF Canister Production

In this paper, 316L stainless steel (316L SS) straight walls, curved walls, and vessels were printed by wire arc additive manufacturing (WAAM) using the 316L SS welding wire, to demonstrate the feasibility of spent nuclear fuel (SNF) canisters using this advanced manufacturing technique. Helium leak test with leak tight criteria of 1 × 10-7 ref-cc/s were performed on printed vessels with various wall thickness, and testing pressures were from 0.345 MPa (50 psi) to 1.724 MPa (250 psi). Printed wall microstructures were characterized using optical microscopy (OM) and scanning electron microscopy (SEM). Tensile specimens were machined out from printed walls along the length, height, and thickness directions, respectively, and tested at different temperature conditions, room temperature, 80 °C, 150 °C and 250 °C, respectively. Results showed t hat, all five WAAM-printed canisters with different thickness passed the helium leaktight criteria of radioactive materials containers by the ANSI N14.5; Dispersed micrometer-level size inclusions/voids were observed at printed wall cross sections, dendritic microstructures were found with grain size variation through the welding torch shifting direction, and very small amount of δ-ferrite and σ-phase were also observed in those cross sections; The printed walls were ductile, all tensile specimens broke with large plastic deformation/elongation and without brittle failure, and printed specimens yield strengths and tensile strengths under room temperature and 80 °C conditions are higher than minimum values of 316L SS for pressure vessels and for general applications at room temperature required by the ASTM standard, respectively.

Tang, Wei↗

Charpy Impact Characterization of Surveillance Specimens Harvested from Palisades High Fluence A-60 Capsule

Located on the shores of Lake Michigan, the Palisades Nuclear Generating Station (PNGS) was a nuclear power plant that operated in Covert Township, Michigan. The plant had a single pressurized water reactor that produced electricity for the region. The PNGS was shut down in 2022 after more than four decades of service. The PNGS included in its surveillance program a surveillance capsule, designated A-60, containing specimens of a weld metal with nickel content of about 1.36 wt% and copper content of about 0.25 wt%. The capsule was removed from its surveillance position in early 1995 and has been resident in the spent fuel pool since that time. This capsule was irradiated to a fluence of 1.96×10 20 n/cm 2 (E>1MeV) that is equivalent for more than 150 effective full power years (EFPYs) for the US reactor pressure vessel (RPV) fleet. The material is also of special interest because of its very high nickel content and potential for development of NiMnSi (nickel-manganese-silicon) precipitates. Combination of very high fluence and very high Ni and Cu content makes the material in this capsule of great interest as benchmark for currently developing embrittlement trend curves (ETC) aiming to predict embrittlement at high fluences. Multi-year efforts by the Light Water Reactor Sustainability (LWRS) Program personnel from the Materials Research Pathway (MRP) to harvest this capsule finally succeeded in 2023. As a result, the Westinghouse Electric Company (WEC) through contract with Oak Ridge National Laboratory (ORNL) came to PNGS site, retrieved the A-60 capsule, brought it to WEC Churchill hot cell facility, opened the capsule and sent all surveillance specimens in the capsule to ORNL for future characterization by July 2023. Total of 9 tensile and 48 Charpy specimens were inventoried in the ORNL hot cells. Testing plan has been developed based on available specimens. It includes hardness, tensile, Charpy impact, Mini-CT fracture toughness testing, in-situ thermal annealing, and microstructural characterization, including Atom Probe Tomography (APT). Charpy impact testing has been completed and results are presented in this report. Moreover, negotiations with Pressurized Water Reactors Owners Group (PWROG) and Westinghouse resulted in Westinghouse donating to ORNL a piece of archive weld and base metal such that unirradiated characterization of these materials can be performed as part of this project. Comparison of measured hardening and embrittlement has been performed and data are compared to available large database.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Modeling Explosive Dispersal of Radiological Material: A Nonparametric Analysis

The National Atmospheric Release Advisory Center (NARAC) is a Department of Energy (DOE) asset that provides guidance on the potential effects of atmospherically released hazards based on dispersion simulation results. Numerical simulation results are compared to well-characterized experimental measurements whenever possible to validate and refine the model predictions. In 2012, such measurements were obtained by Defence Research and Development Canada (DRDC) and collaborating organizations for the case of explosively released 140 La – a radioactive isotope with a half-life of 1.6781 days.

42 ENGINEERING↗

Thermal Dehydration of Aluminum (Oxy)hydroxides on Fuel Cladding Material - 20200

The aluminum cladding of research-reactor fuel undergoes general corrosion with resulting formation of adherent aluminum (oxy)hydroxide films during in-reactor and post-discharge exposure to water under various conditions and temperatures. These (oxy)hydroxides contain chemically-bound water that poses challenges for extended dry storage due to the risk of thermal or radiolytic decomposition releasing free water and/or hydrogen and oxygen gases. This study comprised laboratory experiments of thermal drying behavior of aluminum (oxy)hydroxides to identify approaches for reducing bound water on fuel cladding prior to sealed dry storage. Effective drying strategies for adherent (oxy)hydroxides on fuel cladding will improve the safety of dry storage by mitigating potential avenues for additional corrosion and/or generation of flammable gases inside the storage canister. This work is part of a broader investigation to address knowledge gaps and technical data needs for dry storage of aluminum-clad spent nuclear fuel (ASNF), which included investigation of (oxy)hydroxide formation on aluminum alloy substrates immersed in water, characterization of service-grown films from ASNF, and radiolytic yield of hydrogen from (oxy)hydroxide powders and films. The current work comprises experimental thermal dehydration of aluminum trihydroxides (bayerite and gibbsite) characteristic of low-temperature (<80 deg. C) corrosion in water and aluminum oxyhydroxide (boehmite) characteristic of high temperature (>80 deg. C) corrosion in water. First, commercially produced (oxy)hydroxide powders (boehmite and gibbsite) were tested via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The effort aimed to identify or confirm key temperature ranges/thresholds for the thermal decomposition reactions, as well as impacts of ramp rate and hold times, for drying of isolated, high-surface-area (oxy)hydroxides. The information gleaned from powder tests was used to guide subsequent drying tests on adherent (oxy)hydroxide films grown on aluminum alloy substrates. TGA was used to analyze small samples of the aluminum coupons with adherent (oxy)hydroxide films. Specimens were characterized both pre- and post-drying using X-ray diffraction (XRD) to determine the film composition and scanning electron microscopy (SEM) to determine its morphology. Drying of adherent (oxy)hydroxide films was anticipated to pose additional complications relative to drying of (oxy)hydroxide powders. Anticipated challenges include achieving sufficient drying of the (oxy)hydroxide at low-enough temperature to avoid melting or other undesirable phase changes in the aluminum substrate and overcoming transport limitations of water through the thickness of a dense film or through a tortuous pore structure to reach the outer surface of the film. Inn addition, dehydration of (oxy)hydroxides significantly changes the film density, which may lead to substantial alterations in the morphology, including potential cracking and spalling of the film. TGA/DSC tests of gibbsite powders resulted in successful conversion to boehmite or alumina, depending on the maximum temperature reached. At low ramp rates (≤5 deg. C/min), the conversion to boehmite occurred around 300 deg. C (210-340 deg. C). XRD confirmed that boehmite was the only phase detected after tests reaching 450 deg. C. The transition to alumina occurred around 510 deg. C (470-550 deg. C), with XRD detecting only alumina after tests reaching at least 600 deg. C. Boehmite powders dehydrated to alumina at about 400 deg. C (330-460 deg. C) for coarse (77-μm particle diameter) powder and about 490 deg. C (420-520 deg. C) for fine (0.7-μm particle diameter) powder. For all powders tested, the maximum percent mass loss after drying to high temperature slightly exceeded the theoretical mass loss for complete dehydration of the stoichiometric (oxy)hydroxide to alumina, which is likely attributable to physisorbed water in the powder. Drying of a thick (∼8.6 μm), predominantly bayerite adherent film displayed a dramatic change in film morphology, with the initially continuous trihydroxide film cracking into sections on the order of 50 μm square and partially delaminating. The outermost layer of the film completely faked of in some regions. The layer exposed under the spalled oxide also displayed prominent cracking, with spacing on the order of 10 μm, but this surface layer appeared to remain completely adhered to the aluminum substrate. TGA showed mass losses per unit surface area up to ∼1.0 mg/cm{sup 2}. XRD characterization of the remaining oxide was inconclusive, with no crystalline phases detected. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗