Abstract
We have developed a methodology based on micro-Raman spectrometry performed inside a SEM/EDS for the chemical phase analysis of uranium particles sampled with sticky carbon tapes. We demonstrate that the electronic scanning increases the Raman background of the carbon tapes and decreases the Raman intensities of uranium oxides. Moreover, the most oxidized compounds are reduced into UO2 when the laser power is too intense. Therefore, uranium particles should be localized with the briefest possible electronic scanning, laser power must be limited, and high-resolution imaging and elemental analysis by EDS of uranium particles must be performed after the in-SEM Raman analysis.
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References
Donohue DL (1998) Strengthening IAEA safeguards through environmental sampling and analysis. J Alloys Compd 217–273:11–18
Donohue DL (2002) Strengthened nuclear safeguards. Anal Chem 74(1):28A–35A
Donohue DL, Ciurapinski A, Cliff J, Rüdenauer F, Kuno T, Poths J (2008) Microscopic studies of spherical particles for nuclear safeguards. Appl Surf Sci 255:2561–2568
Pidduck AJ, Houlton MR, Williams GM, Donohue DL (2006) Micro-analytical characterization of uranium particles in support of environmental sampling for safeguards. Proc Symp Int Safeguards, 16–20 October 2006, Vienna, pp 781–789
Sweet LE, Blake TA, Henager CH, Hu S, Johnson TJ, Meier DE, Peper SM, Schwantes JM (2013) Investigation of the polymorphs and hydrolysis of uranium trioxide. J Radioanal Nucl Chem 296:105–110
Ho DML, Manara D, Lindqvist-Reis P, Fanghänel T, Mayer K (2014) The use of different dispersive Raman spectrometers for the analysis of uranium compounds. Vib Spec 53:102–110
Stefaniak EA, Alsecz A, Sajo IE, Worobiec A, Mathé Z, Török S, Van Grieken R (2008) Recognition of uranium oxides in soil particulate matter by means of micro-raman spectrometry. J Nucl Mater 381:278–283
Stefaniak EA, Alsecz A, Frost R, Mathé Z, Sajo IE, Török S, Worobiec A, Van Grieken R (2009) Combined SEM/EDX and micro-raman spectroscopy analysis of uranium minerals from a former uranium mine. J Hazard Mater 168:416–423
Pointurier F, Marie O (2010) Identification of the chemical forms of uranium compounds in micrometer-size particles by means of micro-Raman spectrometry and scanning electron microscope. Spectrochim Acta Part B 65:797–804
Yomogida Y, Esaka F, Magara M (2017) Chemical state and isotope ratio analysis of individual uranium particles by a combination of micro-Raman spectroscopy and secondary ion mass spectrometry. Anal Methods 9:6261–6266
Holmgren-Rondhal S, Pointurier F, Ahlinder A, Ramebäck H, Marie O, Ravat B, Delaunay F, Young E, Blagojevitch N, Hester JR, Thorogood G, Nelwamondo A, Ntsoane TP, Roberts SK, Holliday KS (2018) Comparing results of X-ray diffraction, micro-Raman spectroscopy and neutron diffraction when identifying chemical phases in seized nuclear material, during a comparative nuclear forensics exercise. J Radioanal Nucl Chem 315:395–408
Kips R, Pidduck AJ, Houlton MR, Leenaers A, Mace JD, Marie O, Pointurier F, Stefaniak EA, Van den Taylor PDP, Van Espen P, Van Grieken R, Wellum R (2009) Determination of fluorine in uranium oxyfluoride particles as an indicator of particle age. Spectrochim Acta B 64:199–207
Stefaniak EA, Darchuk L, Sapundjiev D, Kips R, Aregbe Y, Van Grieken R (2013) New insights into UO2F2 particulate structure by micro-Raman spectroscopy. J Mol Struct 1040:206–212
Villa-Aleman E, Wellon MS (2016) Characterization of UF4 with Raman spectroscopy. J Raman Spectrosc 47:865–870
Pointurier F, Lelong C, Marie O (2020) Study of the chemical changes of µm-sized particles of uranium tetrafluoride (UF4) in environmental conditions by means of micro-Raman spectrometry. Vib Spec 110:103145
Shinonaga T, Donohue D, Aigner H, Bürger S, Klose D, Kärkelä T, Zilliacus R, Auvinen A, Marie O, Pointurier F (2012) Production and characterization of plutonium dioxide particles as a quality control material for safeguards purposes. Anal Chem 84:2638–2646
Pointurier F, Ho DML, Manara D, Marie O, Fanghänel T, Mayer K (2019) Capabilities of micro-raman spectrometry for the identification of uranium ore concentrates from analysis of single particles. Vib Spec 103:102925
Black L, Brooker A (2007) SEM–SCA: a combined SEM—Raman spectrometer for analysis of OPC clinker. Adv Appl Ceram 106:327–334
Pointurier F, Marie O (2013) Use of micro-Raman spectrometry coupled with scanning electron microscopy to determine the chemical form of uranium compounds in micrometer-size particles. J Raman Spectrosc 44:1753–1759
Stefaniak EA, Pointurier F, Marie O, Truyens J, Aregbe Y (2014) In-SEM Raman microspectroscopy coupled with EDX—a case study of uranium reference particles. Analyst 139:668–675
Middendorp R, Dürr M, Knott A, Pointurier F, Ferreira-Sanchez D, Samson V, Grolimund D (2017) Characterization of the aerosol-based synthesis of uranium particles as a potential reference material for microanalytical methods. Anal Chem 89:4721–4728
Neumeier S, Middendorp R, Knott A, Dürr M, Klinkenberg M, Pointurier F, Ferreira Sanchez D, Samson VA, Grolimund D, Niemeyer I, Bosbach D (2018) Microparticle production as reference materials for particle analysis methods in safeguards. MRS Adv 3:1005–1012. https://doi.org/10.1557/adv.2018.166
Kegler P, Pointurier F, Rothe J, Dardenne K, Vitova T, Beck A, Hammerich S, Potts S, Faure AL, Klinkenberg M, Kreft K, Niemeyer I, Bosbach D, Neumeier S (2021) Chemical and structural investigations on uranium oxide–based microparticles as reference materials for analytical measurements. MRS Adv. https://doi.org/10.1557/s43580-021-00024-1
Allen CG, Butler IS, Anh Tuan N (1987) Characterization of uranium oxides by micro-Raman spectroscopy. J Nucl Mater 144:17–19
Palacios ML, Taylor SH (2000) Characterization of uranium oxides using in situ micro-Raman spectroscopy. Appl Spectrosc 54(9):1372–1377
Jégou C, Carbello R, Peuget S, Roudil D, Desgranges L, Magnin M (2010) Raman spectroscopy characterization of actinide oxides (U1−yPuY)O23: resistance to oxidation by the laser beam and examination of defects. J Nucl Mater 405:235–243
Tiwari P, Srivastava AK, Khattak BQ, Verma S, Upadhyay A, Sinha AK, Ganguli T, Lodha GS, Deb SK (2012) Effect of electron beam irradiation on PMMA films. Solid state physics. AIP Conf Proc 1447:587–588
Wilhelm HA, McClusky JK (1969) Uranium metal by carbon reduction of oxide. J Metal 21:51–56
Guisard Restivo TA, Capocchi JDT (2004) Carbothermic reaction of uranium oxides into solvent metallic baths. J Nucl Mater 334:189–194
Fridman A (2008) In: plasma chemistry, Chap. 7.2.2: 429–430. Cambridge University Press, UK. ISBN-13 978-0-521-84735-3
Suzuki Y, Arai Y, Sasayama T, Watanabe H (1982) Kinetics on carbothermic reduction of UO2 + C powders and compacts to UC2. J Nucl Sci Technol 19:222–230
Suzuki Y, Arai Y, Sasayama T, Handa M (1983) Mechanism of carbothermic reduction of (U,Pu)O2 to (U,Pu)C. J Nucl Sci Technol 20:874–876
Mukerjee SK, Dehadraya JV, Vaidya VN, Sood DD (1990) Kinetic study of the carbothermic synthesis of uranium monocarbide microspheres. J Nucl Mater 172:37–46
Mukerjee SK, Dehadraya JV, Vaidya VN, Sood DD (1994) Kinetics and mechanism of UO2 + C reaction for UC/UC2 preparation. J Nucl Mater 210:107–104
Vidhya R, Antony MP, Vasudeva Rao PR (1997) Thermodynamic studies of uranium–gadolinium–carbon system through the carbothermic reduction of the oxides. J Nucl Mater 247:158–168
Stewart RL (1934) Insulating films formed under electron and ion bombardment. Phys Rev 45:488–490
Ennos AE (1953) The origin of specimen contamination in the electron microscope. Br J Appl Phys 4:101–108
Acknowledgements
To the memory of Maxim Penkin from the International Atomic Energy Agency (IAEA), who constantly gave warm support for this work and passed away too soon.
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FP: conceptualization, methodology, formal analysis, investigation, writing. OM: methodology.
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Pointurier, F., Marie, O. An optimized methodology for the determination of the uranium chemical phases in micro-particles by Raman spectrometry within a scanning electron microscope. J Radioanal Nucl Chem 332, 2841–2850 (2023). https://doi.org/10.1007/s10967-022-08712-4
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DOI: https://doi.org/10.1007/s10967-022-08712-4