Danilo Bersani

Micro-Raman investigation of iron oxide films and powders produced by sol–gel syntheses

Films and powders of iron oxide (Fe2O3) prepared by two different sol–gel syntheses, starting from Fe(NO3)3·9H2O or FeCl3·6H2O, were investigated by Raman microscopy. Different phases with different morphology were produced according to the preparation. The spectra obtained in the micro-Raman configuration were compared with the ambiguous data in the literature given by conventional Raman techniques. The principal difficulty in the correct interpretation of the Raman spectrum of the iron oxides is the co-existence of different phases. Contradictory results are also explained by laser–induced thermal effects which easily change the wavenumbers and lineshapes of the phonons. A Stokes–Anti-Stokes procedure was utilized to control the local temperature during the measurement and also for calibration of the wavenumbers. The micro-Raman spectra of hematite, magnetite and other iron oxides are presented and compared with literature data. Copyright

Thermal stability of 12-tungstophosphoric acid supported on zirconia

A freshly precipitated zirconia was impregnated with an ethanol solution of H3[W12PO40]6H2O (TPA) in order to obtain 0‐25 wt.% TPA/ZrO2. The solids, heat-treated from 373 to 1073 K, were examined by means of differential thermal analysis, X-ray diffraction, surface area, infrared, Raman, 31 P nuclear magnetic resonance analyses, and used as catalysts in the decomposition of isopropanol. Below 673 K, TPA on ZrO2 exist as distorted intact Keggin species interacting with Zr‐OH or Zr C groups. However, at 773 K, bulk-like intact TPA species were detected. Above 773 K, the Keggin structure of TPA collapse and transforms into WO3 and phosphorous oxides. The characteristic diffraction peaks of TPA cannot be observed even with 20 wt.% TPA loading, indicating a high dispersion or a very small crystal size of TPA, while 20 wt.% TPA loaded on SiO2 clearly shows the presence of TPA particles.The heat-treatment temperature affects the catalytic activity of TPA on Zirconia. The reaction rate was 3.3 times higher in a TPA/ZrO2 calcined at 773 than that at 473 K. ©2000 Elsevier Science B.V. All rights reserved.

Raman scattering characterization of gel-derived titania glass

The preparation by the sol-gel method of bulk vitreous TiO2 is reported and its transformation both by controlled thermal treatment and by laser-induced heating in the anatase and rutile crystalline forms is studied by Raman spectroscopy. The results are compared with those existing for amorphous TiO2 thin films. The dependence of the Raman frequencies and linewidths on the incident laser power is presented and the Raman spectrum of the brookite (a third naturally occurring form of TiO2) is also reported as a comparison.

Study of Anatase to Rutile Phase Transition in Nanocrystalline Titania Films

Nanocrystalline titania films were prepared by a complexing agent-assisted sol-gel dip-coating process. The effect of acetylacetone, diethanolamine and polyethylene glycol on the structure of the heat-treated titania films was examined by Raman and FTIR spectroscopy and X-ray diffraction. The effect the complexing agents have on the anatase to rutile phase transition during the heat treatment process is studied. The understanding of this effect is expected to enhance our capacity to tailor the composition and morphology of films and thus their properties. The Raman and the infrared spectra of nanocrystalline titania films and the changes induced by the heat treatment were also investigated. We have also studied the size of the crystallites in TiO2 films and its dependence on the type of complexing agent used.

Raman study of nanosized titania prepared by sol–gel route

Abstract TiO 2 polycrystalline powders have been prepared by different sol–gel routes and have been investigated by Raman spectroscopy and transmission electron microscopy. The influence of different catalysts on the crystalline phases obtained by thermal annealing is studied. The mechanisms that determine the Raman line shapes are discussed, including phonon confinement and pressure effects. The analysis of the Raman spectra, after thermal treatments in air and N 2 , indicates the importance of the non-stoichiometry due to oxygen vacancies.

Low Temperature Sol-Gel Preparation of Nanocrystalline TiO2 Thin Films

TiO2 nanocrystalline thin films with varying degree of porosity have been prepared using a low temperature method. TiO2 films of the anatase form have been obtained by using a polyethylene glycol (PEG) modified sol-gel method. Densification and crystallization of the films was found to result from the thermal treatment of the dip coated films in boiling water. The films have been characterized by Raman, XRD, FTIR, AFM and optical methods. Highly transparent films with transmission in excess of 85% and porosity as high as 58% are formed predominantly of anatase crystallites of dimensions of the order of 5 nm. Initial results on lithium intercalation into these films resulting in an efficient optical modulation in the visible and near infrared regions demonstrate a good potential of these films for electrochromic applications.

Green pigments of the Pompeian artists’ palette

Green colored samples on wall paintings and green powder from a pigment pot found in Pompeii area are investigated by micro-Raman, FT-IR and, for one sample, SEM-EDX. To obtain the green color, green earths and malachite were used, together with mixture of Egyptian blue and yellow ochre. The mineralogical identification of the green earths has been attempted through the comparison of the vibrational features, discriminating between celadonite and glauconite spectra. Traces of a modern synthetic pigment containing copper phthalocyanine were found in a fresco fragment.

Hydroxy- and fluorapatite films on Ti alloy substrates: Sol-gel preparation and characterization

In this paper we describe the preparation of hydroxyfluorapatite (HFA) and fluorapatite (FA) films deposited on titanium alloys by means of the dip-coating method starting from a sol-gel prepared colloidal solution. These materials are compared with hydroxyapatite (HA) films prepared via sol gel and commercial films prepared by means of plasma spray. The film characterization from the point of view of the composition and crystallinity, performed by means of XRD, FTIR and Raman Spectroscopies, has shown a good purity degree, and compositional homogeneity for the sol-gel materials, though traces of carboxy-hydroxy apatite were found. Also, the samples exhibit a good crystallinity. SEM pictures, taken on HA coating deposited via sol-gel, revealed a homogeneous surface structure and optimum features to set up a good prosthesis-tissue interface.

Characterisation of a portable Raman spectrometer for in situ analysis of art objects.

During the last decades, Raman spectroscopy has grown to an established analytical technique in archaeometry, art analysis and conservation science. Mobile Raman instruments were designed to be used for in situ characterisation and identification of inorganic and organic materials in art and archaeometry. This research paper aims to point out several aspects that need to be considered when selecting a mobile Raman spectrometer for in situ archaeometrical studies. We describe an approach to evaluate these parameters and apply this to a dual laser portable Raman spectrometer. Twofold characterisation of mobile Raman instrumentation for art analysis: (i) investigation of spectroscopic characteristics such as (amongst others) spectral resolution, spectral window, signal to noise ratio and limit of detection; (ii) evaluation of specific properties that are useful for mobile studies in archaeometry. These include options for easy positioning and focussing, the ability to reduce laser power on the surface of the art object and the working distance between the probehead and the artefact. Finally, the research was completed with field tests by studying the pigments of a mediaeval wall painting.

Sol-Gel Preparation of α-Fe2O3 Thin Films: Structural Characterization by XAFS and Raman

Films of Fe2O3 have been prepared by two different sol-gel syntheses, starting from inorganic salts as precursors, Fe(NO3)3 · 9H2O or FeCl3 · 6H2O. Differences in the local order between the two preparations are investigated by XAFS (X-Ray Absorption Fine Structure) and Raman measurements.