Study of Raman spectrum of uranium using a surface‐enhanced Raman scattering technique

Raman spectroscopic investigation on weak scatterers such as metals is a challenging scientific problem. Technologically important actinide metals such as uranium and plutonium have not been investigated using Raman spectroscopy possibly due to poor signal intensities. We report the first Raman spectrum of uranium metal using a surface‐enhanced Raman scattering‐like geometry where a thin gold overlayer is deposited on uranium. Raman spectra are detected from the pits and scratches on the sample and not from the smooth polished surface. The 514.5‐ and 785‐nm laser excitations resulted in the Raman spectra of uranium metal whereas 325‐nm excitation did not give rise to such spectra. Temperature dependence of the B_3g mode at 126 cm⁻¹ is also investigated. Copyright © 2011 John Wiley & Sons, Ltd.     

Damage and molecular changes under a laser beam in SEM‐EDX/MRS interface: a case study on iron‐rich particles

The control of damage to individual environmental particles by a laser beam during Raman spectroscopy carried out in ambient air is generally well understood. The nature and control of damage under vacuum conditions (e.g. in the scanning electron microscopy with energy X‐ray detection combined with micro‐Raman spectroscopy—interfaced SEM‐EDX/MRS) are more complex and less well comprehended. The physical and chemical processes that affect the damage caused to small particles by lasers still remain somewhat unclear, but certainly the atmosphere (vacuum/air) and the beam intensity have very significant influences. Furthermore, it has been determined that some particles (e.g. haematite), although stable under an electron beam, are damaged by the laser beam, hampering their analysis. Additionally, when simultaneous analyses by SEM/EDX and MRS are considered, the correct choice of the collection surface plays a crucial role. As a result, the following collection substrates were tested to determine their influence on the laser beam damage process to the particle: silver and aluminium foils and silicon wafers. A test study was performed using artificial examples of haematite (Fe₂O₃) particles. Exposure of Fe₂O₃ particles in vacuum to 514‐ and 785‐nm laser radiation often leads to their melting, transformation and evaporation. The dependence of the damage caused by the laser beam on the particle structure is reported here. Molecular and crystallographic changes have also been revealed. Formation of magnetite (as an effect of re‐crystallisation) and Raman inactive structures was detected. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectrum of U4O9: a new interpretation of damage lines in UO2

Characterisation of uranium oxides in different conditions is a challenge both in nuclear and environment sciences. We focus here on U₄O₉, which is a superstructure of UO₂. Homogeneous U₄O₉ powder was fabricated and characterised by Raman spectroscopy. The Raman spectrum of a pure‐phase U₄O₉ is, for the first time, completely described and interpreted. U₄O₉ Raman spectrum derives from the well characterised one of UO₂. Besides reminiscent modes of UO₂, a band at 630 cm^‐1, which has a specific response to polarised light, was interpreted as characteristic of clusters of interstitial oxygen atoms. These experimental data will help to rationalise the interpretation of UO₂ damaged samples. Copyright © 2011 John Wiley & Sons, Ltd.     

Complexation between variable-valency uranium and organic ligands in solutions,their photostability and spectral identification

We discuss possible directions for searching for prospective materials based on low-valency uranium (III–V) as detection media for hard electromagnetic radiation. We have studied the processes of formation of tetravalent and pentavalent uranium complexes from UO₂(NO₃)₃·6H₂O and UO₂Cl₂·H₂O in DMF and with addition of CCl₄, including when the systems are exposed to radiation in the visible range (400–450 nm). In the first case (UO₂(NO₃)₃·6H₂O solutions in DMF), upon irradiation we observe stable complexes of pentavalent uranium, and when CCl₄ is added to the solution we observe complexes of tetravalent uranium. In the system UO₂Cl₂·3H₂O in DMF, we do not observe the appearance of new forms of uranium; but when CCl₄ is added, then complexes of tetravalent uranium are formed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 184–187, March–April, 2007.     

Characterisation of carbonaceous materials using Raman spectroscopy: a comparison of carbon nanotube filters,single‐ and multi‐walled nanotubes,graphitised porous carbon and graphite

Multi‐walled carbon nanotube (MWCNT) filters have been recently synthesised which have specific molecular filtering capabilities and good mechanical strength. Optical and scanning electron microscopy (SEM) reveals the formation of highly aligned arrays of bundles of carbon nanotubes having lengths up to 500 µm. The Raman spectra of this material along with four other carbonaceous materials, commercially available single‐walled carbon nanotubes (SWCNTs) and MWCNTs, graphitised porous carbon (Carbotrap) and graphite have been recorded using two‐excitation wavelengths, 532 and 785 nm, and analysed for band positions and shape with special emphasis paid to the D‐, G‐ and G′‐bands. A major difference between the different MWCNT varieties analysed is that G‐bands in the MWCNT filters exhibit almost no dispersion, whereas the other MWCNTs show a noticeable dispersive behaviour with a change in the excitation wavelength. Spectral features similar to those of the MWCNT filter varieties were observed for the Carbotrap material. From the line shape analysis, the intensity ratio, I_D/I_G, of the more ordered MWCNT filter material using the integral G‐band turns out to be two times lower than that of the less ordered MWCNT filter product at both excitation wavelengths. This parameter can, therefore, be used as a measure of the degree of MWCNT alignment in filter varieties, which is well supported also by our SEM study. Copyright © 2008 John Wiley & Sons, Ltd.     

Behavior of Uranium oxides and oxyfluorides exposed to moisture and 244Cm alpha radiation

Alpha radiolysis studies have been performed on uranium oxides and oxyfluorides (UO₃, U₃O₈, and UO₂F₂) to evaluate the long-term storage characteristics of ²³³U. These uranium compounds (using ²³⁸U as the surrogate for ²³³U) were subjected to relatively high alpha radiation doses (235–634 MGy) by doping with ²⁴⁴Cm. The typical irradiation time for these samples was about 1.5 years, which would be equivalent to more than 50 years irradiation by a ²³³U sample. Both dry and wet (up to 10 wt% water) samples were examined in an effort to identify the gas pressure and composition changes that occurred as a result of radiolysis. This study shows that several competing reactions occur during radiolysis with the net effect of generating only very low pressures of hydrogen, nitrogen, and carbon dioxide from water, nitrate, and carbon impurities, respectively. In the absence of nitrate impurities, no pressures greater than 1000 Torr are generated. Usually, however, the oxygen in the air atmosphere over the oxides is consumed with the corresponding oxidation of the uranium oxide. In the presence of up to 10 wt% water, the oxides first show a small pressure rise followed by a net decrease due to the oxygen consumption and the attainment of a steady-state pressure at which the rate of generation of gaseous components is balanced by their recombination and/or consumption in the oxide phase.     

Observation of carbon‐facilitated phase transformation of titanium dioxide forming mixed‐phase titania by confocal Raman microscopy

Confocal Raman microscopy, a relatively new and advanced technique, is found to be suitable for imaging the chemical morphology below the submicrometer scale. It has been employed to probe the phase transformation of carbon‐containing titania (TiO₂) nanopowder and titania thin film subjected to laser annealing. The observation of phase transformation from the anatase phase to the rutile phase at high laser power annealing is attributed to carbon inclusion inside or on the surface of titania. Upon annealing, carbon could react with the oxygen of titania and create oxygen vacancies favoring the transformation from the anatase to the rutile phase. This study provides evidence for the carbon‐assisted phase transformation for creating carbon‐containing mixed‐phase titanium dioxide by laser annealing. We explicitly focus on the presence of carbon in the phase transformation of TiO₂ using confocal Raman microscopy. In all of the investigated samples, mixed anatase/rutile phases with carbon specifically was found at the rutile site. X‐ray diffraction (XRD), scanning electron microscopy (SEM) and energy‐dispersive spectroscopy (EDS) studies have been performed in addition to Raman mapping to verify the mixed‐phase titania formation. Copyright © 2010 John Wiley & Sons, Ltd.     

Physico-Chemical Characteristics of Uranium Oxide Microspheres Produced by Internal Gelation

The developed Sol-Gel Hydrolysis Process was applied to produce uranium oxide microspheres suitable for use as nuclear fuel. Different preparation conditions of washing, feed solution aging and microsphere soaking were tried to produce dense UO₃- and UO₂-micospheres. The effect of reduction time and temperature on the density and porosity of the microspheres was carried out to optimize the preparation parameters. The total surface area, total pore volume and pore radius of UO₃- and UO₂-microspheres were measured through N₂ gas adsorption and application of the BET-equation at 77 K. The effect of the preparation conditions on crystallite size of the samples was made through ray diffraction analysis. Examination of the prepared uranium oxides by differential thermal analysis and thermal gravimetric analysis was carried out.     

High temperature Raman study of UO2: A possible tool for in situ estimation of irradiation‐induced heating

Recently, in situ Raman setups under irradiation become available, and uranium dioxide is one of the most studied compounds. This paper reports the temperature dependence of the only Raman‐active mode in fluorine UO₂. Besides the interest in terms of phonon anharmonicity knowledge, this can be used to estimate the heating induced by irradiation: The frequency shift and width of the T_2g peak can be used as an internal indirect probe of the local temperature in the 20–590 °C range. Copyright © 2015 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering investigations on silver nanoparticles deposited on alumina and titania nanotubes: influence of the substrate material on surface‐enhanced Raman scattering activity of Ag nanoparticles

Silver nanoparticles deposited on various ‘inert’ porous materials (mainly Al₂O₃ and TiO₂) are often used as substrates for surface‐enhanced Raman scattering (SERS) measurements. In this study, we used the sputter deposition technique to cover tubular arrays of Al₂O₃ and TiO₂ with Ag nanoparticles. Raman spectra of pyridine (as a probe molecule) and of two selected dyes (5‐(4‐dimethylaminobenzylidene)rhodanine and 5‐(4‐(dimethylamino)benzylidene)‐3‐(3‐methoxypropyl)rhodanine) adsorbed on fabricated Ag/TiO₂‐n/Ti and Ag/Al₂O₃‐n/Al substrates were measured. We found that the SERS spectra of pyridine adsorbed on Ag nanoparticles deposited on an Al₂O₃‐n/Al substrate are distinctly different from those measured for an Ag/TiO₂‐n/Ti composite. Similar effects were observed for dyes adsorbed on the surface of both composites. The spectral differences between two kinds of composites (Ag/TiO₂‐n/Ti and Ag/Al₂O₃‐n/Al) are discussed in terms of (1) the modified electronic structure of the Ag nanoparticles due to their interaction with different substrate materials and (2) the different atomic topology of the metal particles thus deposited on the surfaces of the substrates. Composite samples were also studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Copyright © 2012 John Wiley & Sons, Ltd.     

Identification of Mn‐related Raman modes in Mn‐doped ZnO thin films

This article aims to investigate the Raman modes present in Mn‐doped ZnO thin films that are deposited using the magnetron co‐sputtering method. A broad band ranging from 500 to 590 cm⁻¹ is present in the Raman spectra of heavily Mn‐doped ZnO films. The multi‐peak‐fitting results show that this broad band may be composed of six peaks, and the peak at 528 cm⁻¹ could be a characteristic mode of Mn₂O₃. The results of this study suggest that the origin of the Raman peaks in Mn‐doped ZnO films may be due to three major types: structural disorder and morphological changes caused by the Mn dopant, Mn‐related oxides and intrinsic host‐lattice defects. Copyright © 2010 John Wiley & Sons, Ltd.     

X-ray photoelectron spectra of uranium and uranium oxides. Correlation with the half-life of 235Um.

Uranium metal and the uranium oxides UO₂, U₃O₈, UO₃ are studied by photoelectron spectroscopy. Chemical shifts of the 4f electronic cor     

Raman spectroscopic study of the multi‐anion uranyl mineral schroeckingerite

Raman spectroscopy complemented with infrared (IR) spectroscopy has been used to study the mineral schroeckingerite. The mineral is a multi‐anion mineral and has (UO₂)²⁺, (SO₄)²⁻ and (CO₃)²⁻ units in its structure, and bands attributed to these vibrating units are readily identified in the Raman spectra. Symmetric stretching modes at 815, 983 and 1092 cm⁻¹ are assigned to (UO₂)²⁺, (SO₄)²⁻ and (CO₃)²⁻ units, respectively. The antisymmetric stretching modes of (UO₂)²⁺, (SO₄)²⁻ are not observed in the Raman spectra but may be readily observed in the IR spectrum at 898 and 1180 cm⁻¹. The antisymmetric stretching mode of (CO₃)²⁻ is observed in the Raman spectrum at 1374 cm⁻¹, as is also the ν₄ (CO₃)²⁻ bending modes at 742 and 707 cm⁻¹. No ν₂ (CO₃)²⁻ bending modes are observed in the Raman spectrum of schroeckingerite. All the spectroscopic evidence points to a highly ordered structure of this mineral. Copyright © 2007 John Wiley & Sons, Ltd.     

Raman and infrared spectroscopic study of the molybdate‐containing uranyl mineral calcurmolite

Raman and infrared spectra of calcurmolite were recorded and interpreted from the uranium and molybdenum polyhedra, water molecules and hydroxyls point of view. U O bond lengths in uranyl and Mo O bond lengths in MoO₆ octahedra were calculated and O H…O bond lengths were inferred from the spectra. The mineral calcurmolite is characterised by bands assigned to the vibrations of the UO₂ units. These units provide intense Raman bands at 930, 900 and 868 and 823 cm⁻¹. These bands are attributed to the anti‐symmetric and symmetric stretching modes of the UO₂ units, respectively. Raman bands at 794, 700, 644, 378 and 354 cm⁻¹ are attributed to vibrations of the MoO₄ units. The bands at 693 and 668 cm⁻¹ are assigned to the anti‐symmetric and symmetric A_g modes of the terminal MO₂ units. Similar bands are observed at 797 and 773 cm⁻¹ for koechlinite and 798 and 775 cm⁻¹ for lindgrenite. It is probable that some of the bands in the low wavenumber region are attributable to the bending modes of MO₂ units. Copyright © 2008 John Wiley & Sons, Ltd.     

Characterization of uranium tetrafluoride (UF4) with Raman spectroscopy

The Raman spectrum of uranium tetrafluoride (UF₄) is unambiguously characterized with multiple Raman excitation laser sources for the first time. Across different laser excitation wavelengths, UF₄ demonstrates 16 distinct Raman bands within the 50–400 cm⁻¹ region. The observed Raman bands are representative of various F–F vibrational modes. UF₄ also shows intense fluorescent bands in the 325–750 nm spectral region. Comparison of the UF₄ spectrum with the ZrF₄ spectrum, its crystalline analog, demonstrates a similar Raman band structure consistent with group theory predictions for expected Raman bands. Additionally, a demonstration of combined scanning electron microscopy and in situ Raman spectroscopy microanalytical measurements of UF₄ particulates shows that despite the inherent weak intensity of Raman bands, identification and characterization are possible for micron‐sized particulates with modern instrumentation. The published well‐characterized UF₄ spectrum is extremely relevant to nuclear materials and nuclear safeguard applications. Published 2016. This article is a U.S. Government work and is in the public domain in the USA. Journal of Raman Spectroscopy published by John Wiley & Sons Ltd.     

Probing high‐energy ion‐implanted silicon by micro‐Raman spectroscopy

The effect of ion implantation (4 MeV¹²C²⁺, 5 MeV¹⁶O²⁺, and 8 MeV²⁸Si²⁺) on [110] silicon wafers in channeling and random orientation is investigated by micro‐Raman spectroscopy. The profiles were measured using Scanning Electron Microscope (SEM) showing that the ions were penetrating deeper inside the wafer in the channeling case creating a 1–2 µm wide strongly modified region and agreeing with the d‐nuclear reaction analysis measurements. Micro‐Raman spectroscopy was employed for the assessment of the lattice damage, probing the side surface of the cleaved wafers at submicron step. The phonon modifications show strong lattice distortions in zones parallel to the front surface of the wafers and at depths, which agree with the results of the characterization techniques. In these strongly damaged zones, there is a substantial reduction in the phonon intensity, a small shift in wavenumber position, and a large increase in the phonon width. On the basis of a modification of the phonon confinement model that takes under consideration the laser beam profile, the reduction in intensity of scattered light, and the nanocrystallite size distribution from the simulation of the lattice displacements, the main characteristics of the Raman spectra could be reproduced for the random C and O implantations. The results indicate that at a critical doping level, the induced defects and lattice distortions relax by breaking the silicon single crystal into nanocrystallites, thus creating the observed zones of strongly distorted lattice. Copyright © 2014 John Wiley & Sons, Ltd.     

Electrochemical functionalisation of SWNTs with poly(3,4‐ethylenedioxythiophene) evidenced by anti‐Stokes/Stokes Raman spectroscopy

The capability of anti‐Stokes/Stokes Raman spectroscopy to evaluate chemical interactions at the interface of a conducting polymer/carbon nanotubes is demonstrated. Electrochemical polymerisation of the monomer 3,4‐ethylenedioxythiophene (EDOT) on a Au support covered with a single‐walled carbon nanotube (SWNT) film immersed in a LiClO₄/CH₃CN solution was carried out. At the resonant optical excitation, which occurs when the energy of the exciting light coincides with the energy of an electronic transition, poly(3,4‐ethylenedioxythiophene) (PEDOT) deposited electrochemically as a thin film of nanometric thickness on a rough Au support presents an abnormally intense anti‐Stokes Raman spectrum. The additional increase in Raman intensity in the anti‐Stokes branch observed when PEDOT is deposited on SWNTs is interpreted as resulting from the excitation of plasmons in the metallic nanotubes. A covalent functionalisation of SWNTs with PEDOT both in un‐doped and doped states takes place when the electropolymerisation of EDOT, with stopping at +1.6 V versus Ag/Ag⁺, is performed on a SWNT film deposited on a Au plate. The presence of PEDOT covalently functionalised SWNTs is rationalised by (1) a downshift by a few wavenumbers of the polymer Raman line associated with the symmetric C C stretching mode and (2) an upshift of the radial breathing modes of SWNTs, both variations revealing an interaction between SWNTs and the conjugated polymer. Raman studies performed at different excitation wavelengths indicate that the resonant optical excitation is the key condition to observe the abnormal anti‐Stokes Raman effect. Copyright © 2010 John Wiley & Sons, Ltd.     

Micro‐Raman spectroscopy and VP‐SEM/EDS applied to the identification of mineral particles and fibres in histological sections

Histological sections of a patient affected by an important respiratory disease were analysed firstly by optical microscope(OM)—crossed polarisers—to identify the presence of incorporated inorganic particles, with particular attention to the fibrous ones. Then, the particles/fibres that were found were studied both with micro‐Raman spectroscopy and variable‐pressure scanning electron microscopy with energy‐dispersive spectroscopy (VP‐SEM/EDS). The two techniques allowed the in situ characterisation of the inorganic phases without disintegration of the organic matter. Micro‐Raman spectroscopy was able to identify the vibrating chemical groups of the mineral phase associated with the inorganic grain while the crystalline structure was preserved by the biological system. The VP‐SEM/EDS characterisation, defining the elemental chemical composition of the analysed particle/fibre, allowed confirmation of the mineral phase deducible from spectroscopic data or its identification with certainty when the spectroscopic data were not exhaustive. Copyright © 2009 John Wiley & Sons, Ltd.     

Origin of the forbidden phonons in Raman scattering spectra of uranium‐doped Ca2CuO3, a spin 1/2 chain system

The Raman scattering spectra of uranium‐doped Ca₂CuO₃ were investigated. The small doping of uranium (≤5%) in this one‐dimensional spin 1/2 chain system induced three new first‐order scattering bands and two new multiphonon bands in the structure of forbidden phonons. The first‐order bands were found to agree well with the existing theoretical results from the ab initio and tight‐binding calculation. Among them, the 470 and 665 cm⁻¹ bands appeared as the basic wavenumbers of which the multiphonon overtones were composed. The grain size effect in this strongly anisotropic system was proposed not to originate from the classical phonon confinement but rather as a result of the segmentation of one‐dimensional spin chains due to doping, which in turn allowed the new vibrational modes and implied the appearance of higher overtones in the scattering spectra. Copyright © 2008 John Wiley & Sons, Ltd.     

Uranium oxides investigated by X-ray absorption and emission spectroscopies

X-ray absorption and resonant X-ray emission measurements at the O 1s edge of the uranium oxides UO₂, U₃O₈ and UO₃ are presented. The spectral shapes of the O Kα X-ray emission spectra of UO₃ exhibit significant excitation energy dependence, from an asymmetric to a symmetric form, which differs from those of UO₂ and U₃O₈. This energy dependence is attributed to a significant difference in the oxygen-uranium hybridization between two different sites in the crystal structure of UO₃. The spectral shapes of UO₂ and U₃O₈ are also found to be different but without significant energy dependence. The experimental spectra of the valence and conduction bands of the uranium oxides are compared to the results of electronic structure calculations available in the literature.