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Peterman, Dean R

Publications and source records attributed to Peterman, Dean R.

Benchmarking MCNP models to support gamma irradiation experiments

Seismic isolators and damping devices have been used for 30+ years to reduce seismic forces and deployed in 10,000+ structures, including bridges, buildings, and mission-critical infrastructure. Studies have shown that seismic isolation of nuclear power plants can reduce the seismic risk by several orders of magnitude and substantially reduce the overnight capital cost. Advanced reactor developers are considering seismic isolation as an integral design feature in their reactor design. It can either be deployed at the building level, isolating the entire reactor building, or at the component level, isolating individual pieces of safety-class equipment, such as a reactor vessel or a steam generator. For equipment isolation, located close to the reactor vessel, the seismic isolators and/or damping devices may be exposed to gamma and neutron radiation, with a possible effect on their mechanical properties which would affect the response of the isolated equipment under earthquake shaking. The Department of Energy, as part of its Nuclear Energy University Program (NEUP), in collaboration with the Idaho National Laboratory (INL), is funding a project at the University at Buffalo (UB) to investigate the effect of gamma radiation on the mechanical properties of various seismic protective devices. (When isolating equipment, the seismic protective devices will be located outside the reactor vessel where the neutron exposure will be insignificant.

22 - GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE-GENIORS Dynamic Irradiation Testing

As part of the homogeneous actinides recycling strategy, the EURO-GANEX process is one of the most promising options to achieve the goal of minor actinides recovery. Improvements made to EURO-GANEX system have resulted in the emergence of the so-called New EURO-GANEX process, where the composition of the solvent has been modified by replacing TODGA and DMDOHEMA with cis-mTDDGA in the organic phase and SO3-Ph-BTP with PyTri-Diol in the aqueous phase in order to resolve important issues. The objective of this work is twofold: evaluate the gamma radiolytic resistance of the new EURO-GANEX process by dynamic irradiation conditions simulating the three main steps of the process, and validate the design of CIEMAT Náyade, CEA Marcel and INL irradiation loop devices since each of them mimics different aspects of the real process. Náyade and the INL loops could irradiate the organic and aqueous phases together, whereas in the CEA loop, the irradiated solvent is recycled continuously inside a platform with several stages of mixer-settlers containing aqueous flows simulating the three main steps of the process. The extraction performances and changes in the composition of the solvent have been analyzed during the irradiation experiment by different techniques: gamma spectrometry and ICP-MS/OES for cations or radioactive tracer extraction, and HPLC-MS to identify and quantify the degradation compounds. Despite some differences between the three-irradiation facilities, this inter-institutional study shows that these three comparative tools provide similar trends in the radiolytic stability of a liquid-liquid extraction system. Favourable extraction results for the different steps are obtained according to the static irradiation studies found in literature. However, the degradation of cis-mTDDGA is appreciable leading to degradation compounds, some of which form precipitates and produce important changes in viscosity, important aspects that must be addressed prior to the successful industrial application of the new EURO-GANEX process.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗

Radiation Chemistry Research and Capabilities at Idaho National Laboratory

Radiation chemistry research and development to support the nuclear fuel cycle is a key role of the Fuel cycle Science and Technology Division at Idaho National Laboratory. Radiation chemistry research has primarily focused on solvent extraction processed being developed to support advanced aqueous recycle of spent nuclear fuel. This research is supported through a Co-60 Gamma irradiator and a radiolysis/hydrolysis test loop developed to support evaluation of the radiation chemistry of aqueous and organic phases while intimately mixed. Recently, research has expanded, through the Center for Radiation Chemistry Research, to include other area of radiation chemistry such as in solid phase adsorption, spent nuclear fuel, radiation kinetics modeling and formic acid degradation. Research advances will be detailed along with capabilities at INL as well as other institutions with which INL collaborates.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Degradation of CYANEX 301 in Contact with Nitric Acid Media

The nature of the degradation product obtained upon contacting CYANEX 301 (bis(2,4,4-trimethylpentyl)dithiophosphinic acid) with nitric acid has been elucidated and found to be a disulfide derivative. The first step to the degradation of CYANEX 301 in toluene has been studied using 31P{1H} NMR after being contacted with nitric acid media. The spectrum of the degradation product exhibits a complex multiplet around dP = 80 ppm. A succession of purifications of CYANEX 301 has resulted in single crystals of the acidic form and the corresponding ammonium salt. Unlike the original CYANEX 301, which consists of a complex diastereomeric mixture displaying all possible combinations of chiral orientations at the 2-methyl positions, the purified crystals were shown by single-crystal X-ray diffraction to be racemates, containing 50:50 mixtures of the [R;R] and [S;S] diastereomers. The comparison between the 31P {1H} NMR spectra of the degradation products resulting from the diastereomerically pure CYANEX 301 and the original diastereomeric mixture has elucidated the influence of the isomeric composition on the multiplicity of the 31P {1H} NMR peak. These NMR data indicate the initial degradation leads to a disulfide-bridged condensation product displaying multiple resonances due to phosphorus–phosphorus coupling, which is caused by the inequivalence of the two P atoms as a result of their different chirality. A total of nine different NMR resonances, six of which display phosphorus–phosphorus coupling, could be assigned, and the identity of the peaks corresponding to phosphorus atoms coupled to each other was confirmed by 31P {1H} homodecoupled NMR analysis.

99 GENERAL AND MISCELLANEOUS↗

Extractant compositions for co-extracting cesium and strontium, a method of separating cesium and strontium from an aqueous feed, and calixarene compounds

A mixed extractant solvent that includes at least one dialkyloxycalix[4]arenebenzocrown-6 compound, 4',4',(5')-di-(t-butyldicyclohexano)-18-crown-6, at least one modifier, and, optionally, a diluent. The dialkyloxycalix[4]arenebenzocrown-6 compound is 1,3-alternate-25,27-di(octyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(decyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(dodecyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(2-ethylhexyl-1-oxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(3,7-dimethyloctyl-1-oxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(4-butyloctyl-1-oxy)calix[4]arenebenzocrown-6, or combinations thereof. The modifier is a primary alcohol. A method of separating cesium and strontium from an aqueous feed is also disclosed, as are dialkyloxycalix[4]arenebenzocrown-6 compounds and an alcohol modifier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NMR Spectroscopy and Structural Characterization of Dithiophosphinates Relevant to Minor Actinide Extraction Processes

Synthetic routes to alkyl and aryl substituted dithiophosphinate salts that contain non-coordinating PPh{sub 4}{sup 1+} counter cations are reported. In general, these compounds can be prepared via a multi-step procedure that starts with reacting secondary phosphines, i.e. HPR{sub 2}, with two equivalents elemental S. This transformation proceeds in two steps - first oxidation of the phosphine and second insertion of S into the H-P bond - and has been used to synthesize a series of dithiophoshinic acids, which were fully characterized, namely HS{sub 2}P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 2}, HS{sub 2}P(m-CF{sub 3}C{sub 6}H{sub 4}){sub 2}, HS{sub 2}P(o-MeC{sub 6}H{sub 4}){sub 2}, and HS{sub 2}P(o-MeOC{sub 6}H{sub 4}){sub 2}. Although the insertion step was found to be much slower than the oxidation reaction, the formation of (NH{sub 4})S{sub 2}PR{sub 2} from HPSR{sub 2} occurs almost instantaneous upon addition of NH{sub 4}OH. Subsequent cation exchange reactions proceed readily with PPh{sub 4}Cl in water, under air, and at ambient conditions to provide analytically pure samples of [PPh{sub 4}][S{sub 2}PR{sub 2}] (R = p-CF{sub 3}C{sub 6}H{sub 4}, m-CF{sub 3}C{sub 6}H{sub 4}, o-CF{sub 3}C{sub 6}H{sub 4}, o-MeC{sub 6}H{sub 4}, o-MeOC{sub 6}H{sub 4}, Ph, and Me, 1b-7b, respectively), which were characterized by elemental analysis, multinuclear NMR, and IR spectroscopy. In addition the S{sub 2}PMe{sub 2}{sup 1-}, S{sub 2}PPh{sub 2}{sup 1-}, and dithiophosphinates with ortho-substituted arene rings were characterized by X-ray crystallography. Structural analysis show that, as opposed to the acids which have short P=S double bonds and long P-SH single bonds, the metric parameters for the S atoms in S{sub 2}PR{sub 2}{sup 1-} are equivalent. In addition, the presence of large non-coordinating PPh{sub 4}{sup 1+} cations guard against intermolecular P-S {hor_ellipsis} X interactions and insure that the P-S bond is isolated. Overall, this synthetic procedure provides high-purity S{sub 2}PR{sub 2}{sup 1-} compounds necessary for subsequent spectroscopic and theoretical studies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Bis(o-trifluoromethylphenyl)dithiophosphinic Methyl Ester

When bis(o-trifluoromethylphenyl)dithiophosphinic acid (1) was dissolved in methanol, crystals of bis(o-trifluoromethylphenyl)dithiophosphinic methyl ester (2) were isolated. The structure of dithiophosphinic methyl ester (2) has been identified via single-crystal X-ray diffraction and multinuclear NMR studies. Compound 2 is remarkable in that the dithiophosphinic (PS2) core is preserved during this transformation. Many dithiophosphinic acids degrade to other compounds over time which results in formation of dithiophosphinic dimers, like the bis(dithiophosphinic) anhydride. The transformation to 2 suggests that the o-trifluoromethylphenyl groups on phosphorus assist in retaining the PS2 core, possibly by steric hindrance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Long lasting decontamination foam

Compositions and methods for decontaminating surfaces are disclosed. More specifically, compositions and methods for decontamination using a composition capable of generating a long lasting foam are disclosed. Compositions may include a surfactant and gelatin and have a pH of less than about 6. Such compositions may further include affinity-shifting chemicals. Methods may include decontaminating a contaminated surface with a composition or a foam that may include a surfactant and gelatin and have a pH of less than about 6.

Demmer, Ricky L↗

Actinide extraction methods

Methods of separating actinides from lanthanides are disclosed. A regio-specific/stereo-specific dithiophosphinic acid having organic moieties is provided in an organic solvent that is then contacted with an acidic medium containing an actinide and a lanthanide. The method can extend to separating actinides from one another. Actinides are extracted as a complex with the dithiophosphinic acid. Separation compositions include an aqueous phase, an organic phase, dithiophosphinic acid, and at least one actinide. The compositions may include additional actinides and/or lanthanides. A method of producing a dithiophosphinic acid comprising at least two organic moieties selected from aromatics and alkyls, each moiety having at least one functional group is also disclosed. A source of sulfur is reacted with a halophosphine. An ammonium salt of the dithiophosphinic acid product is precipitated out of the reaction mixture. The precipitated salt is dissolved in ether. The ether is removed to yield the dithiophosphinic acid.

Peterman, Dean R↗

THERMODYNAMICS OF CESIUM EXTRACTION FROM ACIDIC MEDIA BY HCCD and PEG

This is a companion study to previous publications which expands the understanding of cesium extraction from nitrate media using chlorinated cobalt dicarbollide (HCCD) dissolved in the polar phenyl trifluoromethyl sulfone (FS-13) diluent. First, it is verified that the system is based solely on cation exchange between H+ and Cs+ and that NO3- does not intervene, i.e., that the apparent nitrate dependency is merely an artifact of solution non-idealities. Next, the enthalpy and entropy of the system were determined using appropriate corrections in the van’t Hoff analysis and are in excellent agreement with independently published calorimetry results. Finally, the extraction of Cs by the system containing both HCCD and polyethylene glycol (PEG) in FS-13 was characterized by the determination the species produced in the organic and aqueous phases and it is further demonstrated that synergistic extraction of Cs by HCCD and PEG does not occur. Although there is a definite interaction between HCCD and PEG, and it is well established that this interaction is responsible for the extraction of Sr, this association is actually antagonist with respect to the extraction of Cs.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Summary Report on Gamma Radiolysis of TBP/n-dodecane in the Presence of Nitric Acid Using the Radiolysis/Hydrolysis Test Loop

Design and installation has been completed for a state-of-the-art radiolysis/hydrolysis test loop system. The system is used to evaluate the effects of gamma radiolysis and acid hydrolysis on the stability and performance of solvent extraction process solvents. The test loop is comprised of two main sections; the solvent irradiation and hydrolysis loop and the solvent reconditioning loop. In the solvent irradiation and hydrolysis loop, aqueous and organic phases are mixed and circulated through a gamma irradiator until the desired absorbed dose is achieved. Irradiation of the mixed phases is more representative of actual conditions in a solvent extraction process. Additionally, the contact of the organic phase with the aqueous phase will subject the solvent components to hydrolysis. This hydrolysis can be accelerated by controlling the system at an elevated temperature. At defined intervals, the organic from the irradiation/hydrolysis loop will be transferred to the solvent reconditioning loop where the solvent is contacted with scrub, strip, and solvent wash solutions which simulate process flowsheet conditions. These two processes are repeated until the total desired dose is achieved. Since all viable solvent extraction components in an advanced fuel cycle must exhibit high radiolytic and hydrolytic stability, this test loop is not limited to any one solvent system but is applicable to all systems of interest. Also, the test loop is not limited to testing of process flowsheets. It is also a valuable tool in support of fundamental research on newly identified extractants/modifiers and the impact of gamma radiation on their stability in a dynamic environment. The investigation of the radiolysis of a TBP/n-dodecane process solvent in contact with aqueous nitric acid has been performed. These studies were intended to confirm/optimize the operability of the test loop system. Additionally, these data are directly applicable to numerous other solvent extraction processes containing TBP that are being developed to support advanced aqueous separations processes. Initial experimental results are consistent with existing literature reports regarding TBP/n-dodecane radiolysis. Additionally, the gamma dose rate has been characterized within the test loop and analytical methods have been developed for the characterization and quantification of radiolytic degradation products.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗