Engineering topics

Modolo, Giuseppe

Publications and source records attributed to Modolo, Giuseppe.

4 records

DOE OSTI2023

Gamma Radiolysis of Phenyl-Substituted TODGAs: Part I

The radiolytic stabilities of three phenylated analogs of N,N,N’,N’-tetraoctyl diglycolamide (TODGA) were investigated: 2-(2-(di-n-octylamino)-2-oxoethoxy)-N,N-di-n-octyl-2-phenylacetamide (PhTODGA), which has a phenyl substituent bound to a central methylene, 2-(2-(di-n-octylamino)-2-oxo-1-phenylethoxy)-N,N-di-n-octylpropanamide (PhMeTODGA), which also contains a methyl substituent bound to the methylene on the other side of the ether moiety, and, 2-(2-N-n-hexyl-N-phenylamino)-2-oxoethoxy)-N-n-hexyl-N-phenylacetamide (DHDPDGA), which has phenyl substituents located on the amide groups instead of the central methylenes. The objective of Part I of this series of papers covers was to evaluate the contribution of the phenyl group to the radiolytic stability of these diglycolamides when irradiated in a) n-dodecane, and b) n-dodecane in the presence of a nitric acid-containing aqueous phase. The results indicate that the presence of the phenyl group decreases the overall radiolytic stability compared to unsubstituted TODGA. However, the results also indicate that the phenyl groups interact with nitric acid in a cooperative fashion that enhances the radiation stability of the phenylated diglycolamide (DGA) derivatives in the presence of a nitric acid-containing aqueous phase compared to irradiation in only n-dodecane. So, the results are consistent with the hypothesized formation of nitric acid-phenylated DGA complexes in the n-dodecane phase that are significantly more stable with respect to gamma irradiation, compared to the phenylated DGA molecules alone.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

Gamma Radiolysis of Phenyl-Substituted TODGAs: Part II

The radiolytic degradation chemistry of three phenylated analogs of $N,N,N’,N’$-tetraoctyl diglycolamide (TODGA) was investigated: 2-(2-(di-$n$-octylamino)-2-oxoethoxy)-$N,N$-di-$n$-octyl-2-phenylacetamide (PhTODGA), which has a phenyl substituent bound to a central methylene, 2-(2-(di-$n$-octylamino)-2-oxo-1-phenylethoxy)-$N,N$-di-$n$-octylpropanamide (PhMeTODGA), which also contains a methyl substituent bound to the methylene on the other side of the ether moiety, and, 2-(2-$N$-$n$-hexyl-$N$-phenylamino)-2-oxoethoxy)-$N$-$n$-hexyl-$N$-phenylacetamide (DHDPDGA), which has phenyl substituents located on the amide groups instead of the central methylenes. In Part II of this series of papers radiolytic degradation products were identified after separation with liquid chromatography by High Resolution, Accurate-Mass mass spectrometry and collision-induced dissociation. At least twenty-two radiolytic degradation products were identified for PhTODGA, twenty-nine for PhMeTODGA, and over three dozen for DHDPDGA. The suite of radiolytic degradation products of these three investigated ligands was significantly larger than has been reported for previously studied diglycolamides, owing to their asymmetric nature, and to the identification of several new degradation mechanisms, including addition of methyl, hydroxyl, and nitrogen oxide radicals, that have not been previously reported for diglycolamides. Degradation products that contained addition of a NO 2 or NO 3 group were particularly prevalent for DHDPDGA, likely due to the phenyl side-groups. In conclusion, several of these newly observed mechanisms do not appear to depend on the presence of the phenyl groups, suggesting these novel mechanisms may apply to other diglycolamides.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2021

Gamma and pulsed electron radiolysis studies of CyMe 4 BTBP and CyMe 4 BTPhen: Identification of radiolysis products and effects on the hydrometallurgical separation of trivalent actinides and lanthanides

The radiolytic stability of the highly selective ligands CyMe 4 BTBP and CyMe 4 BTPhen against ionizing gamma radiation was studied in 1-octanol solution. CyMe 4 BTBP and CyMe 4 BTPhen are important extractants for a potential treatment of used nuclear fuel. They were studied under identical experimental conditions to directly compare the effects of gamma and pulsed electron radiolysis on the ligands and systematically study the influence of structural changes in the ligand backbone. Distribution ratios of Am 3+ , Cm 3+ and Eu 3+ , the residual concentration of CyMe 4 BTBP and CyMe 4 BTPhen in solution, and the formation of radiolysis products were studied as a function of absorbed gamma dose and presence of an acidic aqueous phase during irradiation. Quantitative and semi-quantitative analyses were used to elucidate the radiolysis mechanism for both ligands. Addition products of alpha-hydroxyoctyl radicals formed through radiolysis of the 1-octanol diluent to the ligand molecules were identified as the predominant radiolysis products. These addition products also extract trivalent metal ions, as distribution ratios remained high although the parent molecule concentrations decreased. Therefore, the utilization time of a solvent using these extractants under the harsh conditions of used nuclear fuel treatment could be considerably longer than expected. Understanding the radiolysis mechanism is crucial for designing more radiation resistant extractants.

99 GENERAL AND MISCELLANEOUS↗

DOE OSTI2020

Countercurrent Actinide Lanthanide Separation Process (ALSEP) Demonstration Test with a Simulated PUREX Raffinate in Centrifugal Contactors on the Laboratory Scale

An Actinide Lanthanide Separation Process (ALSEP) for the separation of trivalent actinides (An(III)) from simulated raffinate solution was successfully demonstrated using a 32-stage 1 cm annular centrifugal contactor setup. The ALSEP solvent was composed of a mixture of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) and N,N,N',N'-tetra-(2-ethylhexyl)-diglycolamide (T2EHDGA) in n-dodecane. Flowsheet calculations and evaluation of the results were done using the Argonne’s Model for Universal Solvent Extraction (AMUSE) code using single-stage distribution data. The co-extraction of Zr(IV) and Pd(II) was prevented using CDTA (trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid) as a masking agent in the feed. For the scrubbing of co-extracted Mo; citrate-buffered acetohydroxamic acid was used. The separation of An(III) from the trivalent lanthanides (Ln(III)) was achieved using citrate-buffered diethylene-triamine-N,N,N',N",N"-pentaacetic acid (DTPA), and Ln(III) were efficiently back extracted using N,N,N',N'-tetraethyl-diglycolamide (TEDGA). A clean An(III) product was obtained with a recovery of 95% americium and curium. The Ln(III) were efficiently stripped; but the Ln(III) product contained 5% of the co-stripped An(III). The carryover of Am and Cm into the Ln(III) product is attributed to too few actinide stripping stages, which was constrained by the number of centrifugal contactors available. Improved separation would be achieved by increasing the number of An strip stages. The heavier lanthanides (Pr, Nd, Sm, Eu, and Gd) and yttrium were mainly routed to the Ln product, whereas the lighter lanthanides (La and Ce) were mostly routed to the raffinate.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗