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Photocatalytic properties of Au-deposited mesoporous SiO{sub 2}–TiO{sub 2} photocatalyst under simultaneous irradiation of UV and visible light

Mesoporous SiO{sub 2} templates deposited TiO{sub 2} nanocrystals are synthesized via a sol–gel route, and Au nanoparticles (NPs) are deposited in the tubular mesopores of the templates by a photodeposition method (Au/SiO{sub 2}–TiO{sub 2}). The photocatalytic characteristics of Au/SiO{sub 2}–TiO{sub 2} are discussed with the action spectra of photoreactions of 2-propanol and methylene blue. Photocatalytic activities of SiO{sub 2}–TiO{sub 2} under individual ultraviolet (UV) and visible (Vis) light illumination are enhanced by deposition of Au NPs. Furthermore, Au/SiO{sub 2}–TiO{sub 2} shows higher photocatalytic activities under simultaneous irradiation of UV and Vis light compared to the activity under individual UV and Vis light irradiation. Since the photocatalytic activity under simultaneous irradiation is almost the same as the total activities under individual UV and Vis light irradiation, it is concluded that the electrons and the holes generated by lights of different wavelengths are efficiently used for photocatalysis without carrier recombination. - Graphical abstract: This graphic shows the possible charge behavior in Au/SiO{sub 2}–TiO{sub 2} under independent light irradiation of ultraviolet and visible light irradiation. Both reactions under independent UV and Vis light irradiation occurred in parallel when Au/SiO{sub 2}–TiO{sub 2} photocatalyst was illuminated UV and Vis light simultaneously, and then photocatalytic activity is improved by simultaneous irradiation. - Highlights: • Au nanoparticles were deposited in mesoporous SiO{sub 2}–TiO{sub 2} by a photodeposition method. • Photocatalytic activity under UV and Vis light was enhanced by deposition of Au. • Photocatalytic activity of Au/SiO{sub 2}–TiO{sub 2} was improved by simultaneous irradiation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pulsed laser irradiation-assisted electrodeposition of germanium in ionic liquid: From amorphous film to polycrystalline branched structures

Highlights: • Ge branched structures was prepared by electrodeposition in ([EMIm]Tf2N) ionic liquid with laser irradiation. • The crystallinity of Ge with laser irradiation is obviously improved compared to the Ge film without laser irradiation. • By controlling the deposition time, the nanostructures with different morphology and size are obtained. - Abstract: The effect of a pulsed laser on the electrodeposition of germanium on indium tin oxide glass in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm]Tf{sub 2}N) was investigated. Cyclic voltammetric analysis of GeCl{sub 4} in [EMIm]Tf{sub 2}N showed that laser irradiation produced a positive shift of the reduction potential and an increase in the reduction current. Laser irradiation influenced the morphology and crystallinity of the Ge deposits. A deposition time of 1200 s gave rise to amorphous Ge deposits when laser irradiation was not applied, whereas laser irradiation led to a polycrystalline branched structure. The length and width of the branched structures were about 9.58 and 2.18 μm, respectively, and the average grain size of the sample was ∼76 nm. The morphology and size of the Ge deposits could be controlled by adjusting the deposition time under laser irradiation. The mechanism of growth of the Ge deposits under laser irradiation was discussed in detail.

36 MATERIALS SCIENCE↗

A comparative study of standard intensity-modulated radiotherapy and RapidArc planning techniques for ipsilateral and bilateral head and neck irradiation

The purpose of this study was to investigate class solutions using RapidArc volumetric-modulated arc therapy (VMAT) planning for ipsilateral and bilateral head and neck (H&N) irradiation, and to compare dosimetric results with intensity-modulated radiotherapy (IMRT) plans. A total of 14 patients who received ipsilateral and 10 patients who received bilateral head and neck irradiation were retrospectively replanned with several volumetric-modulated arc therapy techniques. For ipsilateral neck irradiation, the volumetric-modulated arc therapy techniques included two 360° arcs, two 360° arcs with avoidance sectors around the contralateral parotid, two 260° or 270° arcs, and two 210° arcs. For bilateral neck irradiation, the volumetric-modulated arc therapy techniques included two 360° arcs, two 360° arcs with avoidance sectors around the shoulders, and 3 arcs. All patients had a sliding-window-delivery intensity-modulated radiotherapy plan that was used as the benchmark for dosimetric comparison. For ipsilateral neck irradiation, a volumetric-modulated arc therapy technique using two 360° arcs with avoidance sectors around the contralateral parotid was dosimetrically comparable to intensity-modulated radiotherapy, with improved conformity (conformity index = 1.22 vs 1.36, p < 0.04) and lower contralateral parotid mean dose (5.6 vs 6.8 Gy, p < 0.03). For bilateral neck irradiation, 3-arc volumetric-modulated arc therapy techniques were dosimetrically comparable to intensity-modulated radiotherapy while also avoiding irradiation through the shoulders. All volumetric-modulated arc therapy techniques required fewer monitor units than sliding-window intensity-modulated radiotherapy to deliver treatment, with an average reduction of 35% for ipsilateral plans and 67% for bilateral plans. Thus, for ipsilateral head and neck irradiation a volumetric-modulated arc therapy technique using two 360° arcs with avoidance sectors around the contralateral parotid is recommended. For bilateral neck irradiation, 2- or 3-arc techniques are dosimetrically comparable to intensity-modulated radiotherapy, but more work is needed to determine the optimal approaches by disease site.

61 RADIATION PROTECTION AND DOSIMETRY↗

Annealing influence on the microstructure of irradiated U-Mo monolithic fuel foils

In this study we compared the microstructure evolution of U-Mo fuel foils produced with and without heat treatment at low burn-up via advanced post-irradiation examination. The aim of this study is to observe after irradiation the ways in which the fabrication processes have influenced fuel behavior at early-stage irradiation, as for very low burn up microstructural studies are lacking. In this work it was observed that the larger grain size detected in the heat-treated samples before irradiation led to decreased grain refinement after irradiation. Grain refinement was associated with the presence of small nano-size bubbles and precipitates. This phenomenon is hypothesized to influence early fuel swelling during reactor irradiation. Grain refinement was also observed to increase in regions where γ-U decomposition was present. Thus, it was enhanced in the samples fabricated without heat treatment. The heat treatment also increased the thickness of the U-Mo/Zr interface, namely of the UZr 2 layer. However, the influence of this layer on fuel performance needs further investigation. On one side, it may contribute to better mechanical bonding; on the other, it may influence swelling and blistering in the interaction layer as porosity increases when this layer is increased. This was observed especially in the presence of increased area containing low Mo concentration, and thus containing a higher fraction of the α-U phase, which is highly susceptible to irradiation induced swelling. Strong evidence of reverse transformation under irradiation (α-U + γ'-U2Mo → bcc γ-U) was observed in these samples. While the precipitates (carbides and oxide) seem to be unaffected by the irradiation at these low burnups. However, further analyses are necessary at higher burn-up to assess the exact impact different heat treatments have on fuel performance.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Design and testing of an enriched uranium fueled molten salt irradiation vehicle

Molten salt reactors (MSRs) have garnered increasing attention recently with several demonstration efforts on the way. A key challenge to the licensing basis for these reactors is the lack of experimental data on fueled salts. This is expected to be crucial to the safety evaluation and licensing basis of reactors of this type deployed in the future. While capability for irradiating molten salts has started being reestablished in the recent decade, no enriched fuel irradiation capability has been developed and tested as of yet. A new experiment vehicle under development at Idaho National Laboratory (INL) is presented here. The Molten-salt Research Temperature-controlled Irradiation (MRTI) experiment was developed to host enriched-uranium bearing salt samples to be irradiated at a test reactor within the lab complex. One of the key scientific objectives is to provide irradiated salt samples for post irradiation examination (PIE) to study the impact of fission product generation and neutron/gamma radioactivity on the salt solution and salt-facing wall material. This paper provides a detailed overview of the mechanical design of the experiment, followed by an overview of the fabrication and assembly of an initial prototype vehicle (with non-fuel bearing salt). A summary of the key analyses conducted as a part of the performance and safety evaluation is then provided. Lastly, an overview of the test conducted in prototypic out-of-pile (non-neutron) environment are shown. These evaluations provide the foundation for a planned irradiation of and enriched uranium-bearing chloride salt sample in the near term. The upcoming irradiation will contain 13cm 3 of UCl 3 -NaCl salt (93% enrichment) generating around 20 W/cm 3 of fission energy during irradiation and a temperature range that can be contained between bounds of 525-900°C.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Effect of initial γ -irradiation on infrared laser ablation of poly(vinyl alcohol) studied by infrared spectroscopy

We report the effect of initial γ-irradiation of poly(vinyl alcohol) (PVA) on the kinetics of polymer ablation under CO 2 laser irradiation was studied using infra-red spectroscopy. The rate of laser ablation rapidly decreases with increasing time of laser ablation up to 10 s. Initial γ-irradiation of a dose up to 100 kGy reduces the rate of the laser ablation, just like the effect of laser exposure. The number of OH and CH groups decrease in PVA both with laser irradiation and with γ-irradiation. The number of OH groups decreases more under laser irradiation. Unsaturated bonds are formed in γ–irradiated PVA on the surface of the crater formed by laser ablation of the polymer that has undergone radiolysis. Increasing the dose of initial γ-irradiation from 100 to 2300 kGy leads to an increase in the intensity of the IR bands of the unsaturated bonds. The number of IR bands in the spectra of the laser ablation crater of PVA does not change with the dose of initial γ-irradiation. A dose of radiolysis of 3500 kGy significantly changes the IR spectra of both the ablation crater and the coating formed from the ablation products. Many bands characteristic for PVA are no longer present and the intensities of bands corresponding to unsaturated bonds are increased. A computational model for loss of water and ketone formation was developed for PVA and PVA including a diol using G3(MP2). The highest activation energy barrier step in the decomposition reaction was formation of the enol species and water was shown to catalyze all decomposition steps.

36 MATERIALS SCIENCE↗

Emulation of reactor irradiation damage using ion beams

The continued operation of existing light water nuclear reactors and the development of advanced nuclear reactor depend heavily on understanding how damage by radiation to levels degrades materials that serve as the structural components in reactor cores. The first high dose ion irradiation experiments on a ferritic-martensitic steel showing that ion irradiation closely emulates the full radiation damage microstructure created in-reactor are described. Ferritic-martensitic alloy HT9 (heat 84425) in the form of a hexagonal fuel bundle duct (ACO-3) accumulated 155 dpa at an average temperature of 443°C in the Fast Flux Test Facility (FFTF). Using invariance theory as a guide, irradiation of the same heat was conducted using self-ions (Fe++) at 5 MeV at a temperature of 460°C and to a dose of 188 displacements per atom. The void swelling was nearly identical between the two irradiation and the size and density of precipitates and loops following ion irradiation are within a factor of two of those for neutron irradiation. The level of agreement across all of the principal microstructure changes between ion and reactor irradiation establishes the capability of tailoring ion irradiation to emulate the reactor-irradiated microstructure.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Low-energy D{sup +} and H{sup +} ion irradiation effects on highly oriented pyrolytic graphite

We have investigated the low-energy (100 eV) D{sup +} and H{sup +} ion irradiation effects on the structural and chemical properties of highly oriented pyrolytic graphite (HOPG). Structural disorder due to the ion irradiation was identified by the Raman spectroscopy, the D{sup +} irradiation giving rise to greater structural disorder than the H{sup +} irradiation. Only sp{sup 2} bonding was identified in the X-ray photoemission spectroscopy of the D{sup +}-irradiated HOPG, indicating no change in the surface chemical structure. The H{sup +} irradiation, on the other hand, gave rise to sp{sup 3} bonding and π−π{sup *} transition, the sp{sup 3} bonding increasing with increasing irradiation dose. It is thus shown that the chemical properties of the HOPG surface may be sensitively modified by the low-energy H{sup +} ion irradiation, but not by the low-energy D{sup +} ion irradiation.

36 MATERIALS SCIENCE↗

Effect of electron irradiation exposure on phase formation, microstructure and mechanical strength of Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} superconductor prepared via co-precipitation method

In this work the effect of electron irradiation on the mechanical properties of Bi2Sr2CaCu2O8 (Bi-2212) superconductor was studied by exposing the Bi-2212 superconductor with different doses of electron irradiation. Bi-2212 samples were prepared by using co-precipitation method. Irradiation was performed with irradiation dose of 100 kGray and 200 kGray, respectively. Characterization of the samples was performed by using X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Instron Universal Testing machine was used to measure the strength of the samples. The XRD patterns for the non-irradiated and irradiated samples show well-defined peaks of which could be indexed on the basis of a Bi-2212 phase structure. XRD patterns also indicate that electron irradiation did not affect the Bi-2212 superconducting phase. SEM micrographs show disorientation in the texture of the microstructure for irradiated samples. Sample exposed to 200 kGray electron irradiation dose shows enhancement of grain size. Their grain growth and texture improved slightly compared to other sample. The results also show that enlargement of grain size resulted in higher mechanical strength.

36 MATERIALS SCIENCE↗

The effect of gamma irradiation on chitosan and its application as a plant growth promoter in Chinese kale (Brassica alboglabra)

This research project was conducted to study the effects of irradiation on chitosan and its potential application as a plant growth promoter. Chitosan in the form of flakes was irradiated with gamma rays at irradiation dosage of 50 kGy, 100 kGy, 200 kGy and 400 kGy. The effect of irradiation on chitosan in terms of intrinsic viscosity and average molecular weight was measured using Ubbelohde capillary viscometry technique and the results obtained showed irradiation at doses of up to 50 kGy had caused an extremely significant reduction of both parameters and this trend continued at higher irradiation doses, although the decrease were not significant. The effect of various concentrations of chitosan and irradiated chitosan on growth promotion of Chinese kale (Brassica alboglabra) was hydroponically grown and cultivated for 50 days. Statistical analysis showed addition of 10 ppm of irradiated chitosan of 200 kGy and 400 kGy, respectively, resulted in an extremely significant increase in the percentage weight gain of Chinese kale (Brassica alboglabra). Results obtained in this study showed the potential use of irradiated chitosan as a plant growth promoter for plants grown hydroponically.

60 APPLIED LIFE SCIENCES↗

Proton irradiated graphite grades for a long baseline neutrino facility experiment

In search of a low-Z pion production target for the Long Baseline Neutrino Facility (LBNF) of the Deep Underground Neutrino Experiment (DUNE) four graphite grades were irradiated with protons in the energy range of 140–180 MeV, to peak fluence of ~6.1×10 20 p/cm 2 and irradiation temperatures between 120–200 °C. The test array included POCO ZXF-5Q, Toyo-Tanso IG 430, Carbone-Lorraine 2020 and SGL R7650 grades of graphite. Irradiation was performed at the Brookhaven Linear Isotope Producer. Postirradiation analyses were performed with the objective of (a) comparing their response under the postulated irradiation conditions to guide a graphite grade selection for use as a pion target and (b) understanding changes in physical and mechanical properties as well as microstructure that occurred as a result of the achieved fluence and in particular at this low-temperature regime where pion graphite targets are expected to operate. A further goal of the postirradiation evaluation was to establish a proton-neutron correlation damage on graphite that will allow for the use of a wealth of available neutron-based damage data in proton-based studies and applications. Macroscopic postirradiation analyses as well as energy dispersive x-ray diffraction of 200 KeV x rays at the NSLS synchrotron of Brookhaven National Laboratory were employed. The macroscopic analyses revealed differences in the physical and strength properties of the four grades with behavior however under proton irradiation that qualitatively agrees with that reported for graphite under neutrons for the same low temperature regime and in particular the increase of thermal expansion, strength and Young’s modulus. The proton fluence level of ~10 20 cm -2 where strength reaches a maximum before it begins to decrease at higher fluences has been identified and it agrees with neutron-induced changes. X-ray diffraction analyses of the proton irradiated graphite revealed for the first time the similarity in microstructural graphite behavior to that under neutron irradiation and the agreement between the fluence threshold of ~5×10 20 cm -2 where the graphite lattice undergoes a dramatic change. The confirmed similarity in behavior and agreement in threshold fluences for proton and neutron irradiation effects on graphite reported for the first time in this study will enable the safe utilization of the wealth of neutron irradiation data on graphite that extends to much higher fluences and different temperature regimes by the proton accelerator community searching for multi-MW graphite targets.

43 PARTICLE ACCELERATORS↗

SU-E-T-457: Design and Characterization of An Economical 192Ir Hemi-Brain Small Animal Irradiator

Purpose: To describe the design and dosimetric characterization of a simple and economical small animal irradiator. Methods: A high dose rate 192Ir brachytherapy source from a commercially available afterloader was used with a 1.3 centimeter thick tungsten collimator to provide sharp beam penumbra suitable for hemi-brain irradiation of mice. The unit is equipped with continuous gas anesthesia to allow robust animal immobilization. Dosimetric characterization of the device was performed with Gafchromic film. The penumbra from the small animal irradiator was compared under similar collimating conditions to the penumbra from 6 MV photons, 6 MeV electrons, and 20 MeV electrons from a linear accelerator as well as 300 kVp photons from an orthovoltage unit and Monte Carlo simulated 90 MeV protons. Results: The tungsten collimator provides a sharp penumbra suitable for hemi-brain irradiation, and dose rates on the order of 200 cGy/minute were achieved. The sharpness of the penumbra attainable with this device compares favorably to those measured experimentally for 6 MV photons, and 6 and 20 MeV electron beams from a linear accelerator. Additionally, the penumbra was comparable to those measured for a 300 kVp orthovoltage beam and a Monte Carlo simulated 90 MeV proton beam. Conclusions: The small animal irradiator described here can be built for under $1,000 and used in conjunction with any commercial brachytherapy afterloader to provide a convenient and cost-effective option for small animal irradiation experiments. The unit offers high dose rate delivery and sharp penumbra, which is ideal for hemi-brain irradiation of mice. With slight modifications to the design, irradiation of sites other than the brain could be accomplished easily. Due to its simplicity and low cost, the apparatus described is an attractive alternative for small animal irradiation experiments requiring a sharp penumbra.

07 ISOTOPE AND RADIATION SOURCES↗

SU-E-T-103: An Evaluation of Multiple Irradiations of the IROC Houston QA Center Anthropomorphic Liver Phantom

Purpose: Analyze the results from irradiations of an anthropomorphic liver phantom based on irradiation technique and number of isocenters used for the SBRT delivery. Methods: The phantom consists of a water-fillable plastic shell that has a polystyrene insert, representing the liver which includes two Solid WaterTM targets (PTV1 and PTV2) mimicking liver metastases. The two targets, PTV1 and PTV2 are non-coplanar and are an ovoid 2 cm in diameter and 2.5 cm long and a 3 cm diameter sphere, respectively. Each PTV houses one TLD and 2 planes of radiochromic film. The phantom and a motion table to simulate respiratory motion is sent to institutions sthat are instructed to design and deliver a stereotactic treatment plan that delivers 6 Gy to ≥ 95% of each PTV. The maximum motion of the phantom on the motion table was 1 cm in the superior-inferior direction. Results: Irradiations from 93 institutions have been analyzed. The acceptance criteria are ±7% for the TLD and 85% of the pixels in a region surrounding each PTV passing a ±7%/4 mm global gamma analysis. Sixty-seven (71%) irradiations meet this criteria. The majority, 74 (80%), of the irradiations were performed with IMRT. 73% of the IMRT deliveries were within criteria and 68% of the 3D CRT delivery were within criteria. 32 of the irradiations had a single isocenter plan, 50 were performed with two isocenters and 11 irradiations were performed with CyberKnife and TomoTherapy units where the concept of isocenter is not applicable. The pass rate for the single, dual and no isocenter irradiations were 69%, 74% and 73%, respectively and are not statistically different. Conclusion: The pass rate for the anthropomorphic liver phantom is approximately 70%. There does not seem to be any correlation with number of isocenters used or irradiation technique used for the delivery. This work was supported by PHS CA180803 awarded by NCI, DHHS.

60 APPLIED LIFE SCIENCES↗

Preliminary irradiation effect on corrosion resistance of zirconium alloys - 2016-0067

In order to improve the composition and structure of zirconium alloys, it is important to know how changes in their structure-phase state under irradiation affect various properties, including corrosion. In this work, autoclave corrosion tests were carried out on fuel cladding samples made of zirconium-niobium and zirconium-niobium-tin-iron alloy systems. All samples were preliminarily irradiated in a BOR-60 nuclear reactor at a fluence of 2 X10{sup 26} m{sup -2} (E>0.1 MeV). The autoclave tests of irradiated and unirradiated samples were performed at 350 deg. C for 240 days in distilled water containing 10 ppm lithium and 1,600 ppm boron. The irradiation of all alloys resulted in a significant change in their initial structure-phase state. The content of niobium in b-niobium-phase precipitates was reduced from 80 % to - 90 % to 50 % to - 60 %. Iron atoms from the Laves-phase particles were diffused into a matrix, and their lattice transformed from hexagonal close-packed to body-centered cubic. An average size of the transformed second-phase precipitates in the irradiated alloys increased relatively to an average size of the initial precipitates. Elongated radiation-induced precipitates (RIPs) with an average length up to 7 nm were formed in all alloys under irradiation. In comparison with the unirradiated state, irradiation reduced the corrosion of zirconium-niobium alloys, and this effect became more apparent with increased niobium content in the alloy. For zirconium-niobium-tin-iron alloys, irradiation led to more severe corrosion, mostly because of increasing tin content. Niobium content increased up to 2.37 %, and iron content decreased up to 0.18 % in the alloys, contributing to higher corrosion resistance. An interconnection between the niobium/(tin + iron) alloying parameter, quantity of nanometric precipitates formed therein under irradiation, and their corrosion performance has been suggested. (authors)

36 MATERIALS SCIENCE↗

Status Report for NEET In-Pile Sensor Irradiation Capabilities at TREAT

The recently-established in-pile sensor development project under the Nuclear Energy Enabling Technology (NEET) program is focused on the development of measurement technologies to enable acquisition of data focused on the performance, properties, and boundary conditions of nuclear fuels/materials under irradiation in nuclear reactors. These sensors can be used in steady state irradiation tests to measure parameters of interest under conditions representing normal nuclear plant operation, or in transient irradiation tests to determine specimen performance under postulated unplanned conditions. In either case, development of suitable sensor technologies must include instrument irradiations to help guide sensor material/design selection, verify instrument performance, and demonstrate deployment viability. The Transient Reactor Test facility (TREAT) while just a part of the overall capabilities portfolio needed to enable this sensor development mission, has unique capabilities and characteristics that make it well poised for a number of instrument irradiation data objectives including sensor survivability screening, response characterization, qualification tests, and in-situ properties measurements. TREAT’s brilliantly-basic design, when married with appropriate irradiation hardware and analytic capabilities, fills a crucial capability gap between out-of-pile testing and irradiation in steady state high power research reactors. Leveraging a recently developed approach to irradiation testing in TREAT, the present work demonstrates that cost-effective and scientifically-impactful instrument irradiation capabilities for TREAT are a well-placed capability in the NEET in-pile sensor development project.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Microstructural Characterization of Irradiated U0.7ZrH1.6 Using Ultrasonic Techniques

In recent years, there has been an increased level of effort to understand the changes in microstructure that occur due to irradiation of nuclear fuel. The primary driver for this increased effort is the potential for designing new fuels that are safer and more reliable, in turn enabling new and improved reactor technologies. Much of the data on microstructural change in irradiated fuels is generated through a host of post irradiation examination techniques such as optical microscopy (OM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) to determine grain structure, porosity, crack geometry, etc. in irradiated fuels. Such “traditional” examination techniques were recently used to characterize a novel new fuel consisting of U0.17ZrH1.6 pellets bonded to zircaloy-2 cladded with lead-bismuth eutectic before and after irradiation. However, alternative methods such as ultrasonic inspection can provide an opportunity for nondestructively assessing microstructure in both in-pile and post-irradiation examinations. In this paper, we briefly describe initial results of ultrasonic examination of the U0.17ZrH1.6 pellets (unirradiated and irradiated), in a post-irradiation examination study. Data indicate some correlation with microstructural changes due to irradiation; however, it is not clear what the specific microstructural changes are that are influencing the ultrasonic measurements. Interestingly, specimens with nominally identical burnup show differences in ultrasonic signatures, indicating apparent microstructural differences between these specimens. A summary of the experimental study, preliminary data and findings are presented in this short paper. Additional details of the analysis will be included in the presentation.

Microstructure evaluation↗

Chemical Characterization and Removal of Carbon-14 from Irradiated Graphite II - 13023

Approximately 250,000 tonnes of irradiated graphite waste exists worldwide and that quantity is expected to increase with decommissioning of Generation II reactors and deployment of Generation IV gas-cooled, graphite moderated reactors. This situation indicates the need for a graphite waste management strategy. Of greatest concern for long-term disposal of irradiated graphite is carbon-14 (C-14), with a half-life of 5730 years. Study of irradiated graphite from some nuclear reactors indicates C-14 is concentrated on the outer 5 mm of the graphite structure. The aim of the research presented last year and updated here is to identify the chemical form of C-14 in irradiated graphite and develop a practical method by which C-14 can be removed. A nuclear-grade graphite, NBG-18, and a high-surface-area graphite foam, POCOFoam{sup R}, were exposed to liquid nitrogen (to increase the quantity of C-14 precursor) and neutron-irradiated (10{sup 13} neutrons/cm{sup 2}/s). Finer grained NBG-25 was not exposed to liquid nitrogen prior to irradiation at a neutron flux on the order of 10{sup 14} /cm{sup 2}/s. Characterization of pre- and post-irradiation graphite was conducted to determine the chemical environment and quantity of C-14 and its precursors via the use of surface sensitive characterization techniques. Scanning Electron Microscopy (SEM) was used to evaluate the morphological features of graphite samples. The concentration, chemical composition, and bonding characteristics of C-14 and its precursors were determined through X-ray Photoelectron Spectroscopy (XPS), Time-of-Flight Secondary Ion Mass Spectrometry (SIMS), and Energy Dispersive X-ray Analysis Spectroscopy (EDX). Results of post-irradiation characterization of these materials indicate a variety of surface functional groups containing carbon, oxygen, nitrogen and hydrogen. During thermal treatment, irradiated graphite samples are heated in the presence of an inert carrier gas (with or without oxidant gas), which carries off gaseous products released during treatment. Graphite gasification occurs via interaction with adsorbed oxygen complexes. Experiments in argon were performed at 900 deg. C and 1400 deg. C to evaluate the selective removal of C-14. Thermal treatment also was performed with the addition of 3 and 5 volume % oxygen at temperatures 700 deg. C and 1400 deg. C. Thermal treatment experiments were evaluated for the effective selective removal of C-14. Lower temperatures and oxygen levels correlated to more efficient C-14 removal. (authors)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of He Ion Irradiation in Simple Borosilicate Glasses for HLW Immobilisation - 20324

High-level radioactive waste (HLW) consists of fission products and minor actinides. Borosilicate glass is the host material of choice in most countries to safely immobilize HLW, followed by eventual geological disposal. HLW glasses will experience both self-heating and self-irradiation effects due to the decay of fission products and minor actinides present therein. During the first 500 years of geological disposal, beta-gamma decay will be the main source of radiation due to short half-lives of fission products, as compared to very long-lived actinides which will be responsible for irradiation over much longer timescales. High-energy alpha particles and alpha recoil nuclei can potentially have significant impact (stored energy, volume change, accumulated dose, chemical durability) on the performance of the wasteform over longer timescales. Thus, to ensure safe and economic disposal over geological periods (10{sup 4} - 10{sup 6} years), the assessment of performance and properties in terms of radiation effects becomes indispensable. This work aims to simulate the effects of alpha decay in radioactive waste glasses. Two international glasses, namely UK 'MW' lithium-sodium borosilicate and Indian sodium-barium borosilicate, which are being used as HLW immobilization matrices by the UK and India respectively, were prepared by a melt-quench method and annealed below their glass transition temperatures. Both glasses were irradiated with 650 KeV He{sup 2+} ions with doses ranging from 10{sup 15} to 10{sup 17} ions/cm{sup 2}. Structural analysis was carried out using electron paramagnetic resonance (EPR) and Raman spectroscopies. First derivative continuous wave EPR spectra were recorded for all pristine and irradiated glass monoliths at room temperature using an X-band (frequency 9.6 GHz) EPR Bruker spectrometer. Results from EPR analyses showed the formation of irradiation induced paramagnetic centers at g ∼ 2.00 in all irradiated glasses. Raman spectra of pristine and irradiated samples were acquired, and showed notable changes in glass structure post-irradiation, with the emergence of a broad Raman band at 1560 cm{sup -1} upon irradiation with high fluences. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗