Gas-solid reactions of single crystals: a study of the reaction of bromine with single crystals of trans-cinnamic acid and a range of its derivatives by infrared and Raman microspectroscopy

Single crystals of trans-cinnamic acid and of a range of derivatives of this compound containing halogen substituents on the aromatic ring have been reacted with 165 Torr pressure of bromine vapour in a sealed desiccator at 20 degrees C for 1 week. Infrared and Raman microspectroscopic examination of the crystals shows that bromination of the aliphatic double bond, but not of the aromatic ring, has occurred. It is demonstrated also that the reaction is truly gas-solid in nature. A time-dependent study of these reactions shows that they do not follow a smooth diffusion-controlled pathway. Rather the reactions appear to be inhomogeneous and to occur at defects within the crystal. The reaction products are seen to flake from the surface of the crystal. It is shown, therefore, that these are not single crystal to single crystal transitions, as have been observed previously for the photodimerisation of trans-cinnamic acid and several of its derivatives. It is shown that there are no by-products of the reaction and that finely ground samples react to form the same products as single crystals.

Investigation in SrTiO3-CaTiO3-PbTiO3 ternary thin films by dielectric proprieties and Raman spectroscopy

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structural studies of NaPO3-WO3 glasses by solid state NMR and Raman spectroscopy

Vitreous samples were prepared in the (100 2 x) NaPO3-x WO3 (0 <= x <= 70) glass forming system using conventional melting-quenching methods. The structural evolution of the vitreous network was monitored as a function of composition by thermal analysis, Raman spectroscopy and high resolution one- and two-dimensional P-31 solid state NMR. Addition of WO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures, suggesting a significant increase in network connectivity. At the same time Raman spectra indicate that up to about 30 mol% WO3 the tungsten atoms are linked to some non-bridging oxygen atoms (W-O- or W=O bonded species), suggesting that the network modifier sodium oxide is shared to some extent between both network formers. W-O- W bond formation occurs only at WO3 contents exceeding 30 mol%. P-31 magic angle spinning (MAS)-NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. The possible formation of some anionic tungsten sites suggested from the Raman data implies an average increase in the degree of polymerization for the phosphorus species, which would result in diminished P-31/Na-23 interactions. This prediction is indeed confirmed by P-31{Na-23} and Na-23{P-31} rotational echo double resonance (REDOR) NMR results, which indicate that successive addition of WO3 to NaPO3 glass significantly diminishes the strength of phosphorus-sodium dipole-dipole couplings.

Electrical conduction mechanism and phase transition studies using dielectric properties and Raman spectroscopy in ferroelectric Pb0.76Ca0.24TiO3 thin films

We have studied the phase transition behavior of Pb0.76Ca0.24TiO3 thin films using Raman scattering and dielectric measurement techniques. We also have studied the leakage current conduction mechanism as a function of temperature for these thin films on platinized silicon substrates. A Pb0.76Ca0.24TiO3 thin film was prepared using a soft chemical process, called the polymeric precursor method. The results showed that the dependence of the dielectric constant upon the frequency does not reveal any relaxor behavior. However, a diffuse character-type phase transition was observed upon transformation from a cubic paraelectric phase to a tetragonal ferroelectric phase. The temperature dependency of Raman scattering spectra was investigated through the ferroelectric phase transition. The soft mode showed a marked dependence on temperature and its disappearance at about 598 K. on the other hand, Raman modes persist above the tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive above the phase transition temperature. The origin of these modes must be interpreted in terms of a local breakdown of cubic symmetry by some kind of disorder. The lack of a well-defined transition temperature suggested a diffuse-type phase transition. This result corroborate the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in the thin film. The leakage current density of the PCT24 thin film was studied at elevated temperatures, and the data were well fitted by the Schottky emission model. The Schottky barrier height of the PCT24 thin film was estimated to be 1.49 eV. (C) 2003 American Institute of Physics.

EXAFS and Raman spectroscopy study of binary indium fluoride glasses

Extended X-ray absorption fine spectroscopy (EXAFS) and Raman scattering studies of InF3-BaF2 and InF3-SrF2 binary glasses are reported. For all compositions, the local structure of the glasses is built with InF6 units. For all glasses studied, the indium neighbour's number and the In-F mean bond length are equal to the values of the InF3 crystalline phase (6 and 0.205 nm, respectively). © 1996 Chapman & Hall.

Complementary study on the electrical and structural properties of poly(3-alkylthiophene) and its copolymers synthesized on ITO by electrochemical impedance and Raman spectroscopy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The Relationship Between Cadwaladerite Al(OH)2Cl∙4H2O and Lesukite Al2(OH)5Cl∙2H2O as Investigated by SEM, PXRD, FTIR and Raman Spectroscopy

Cadwaladerite (Al(OH)2Cl∙4H2O) collected from Cerro Pintados, Chile described by Gordon in 1941 is designated as “doubtful” by the IMA. Material collected from the same locality in 2015 resembling the description of cadwaladerite gave a powder XRD pattern similar to lesukite (Al2(OH)5Cl∙2H2O). However, Gordon provided no X-ray data for his material from Cerro Pintados. In order to determine whether cadwaladerite and lesukite are the same mineral species, measurements were made on a suite of samples from various localities. A portion of the material collected by Gordon in 1941 was also obtained from the Mineralogical Museum of Harvard University. Type material of lesukite from a fumarolic environment at the Tolbachik Fissure in Kamchatka, Russia was obtained as well as lesukite from the Maria Mine, Chile (Arica Province) and a previously undescribed locality for lesukite (Barranaca del Sulfato, Mejillones Peninsula, Antofagasta Province). All samples are yellow to yellow-orange in colour and all exhibit small cubic crystals (up to 50µm), even Gordon’s cadwaladerite which was thought to be amorphous. The Chilean samples are all associated with halite and sometimes with anhydrite. These five samples were studied by SEM, FTIR, powder XRD, and Raman spectroscopy. A ratio of Al:Cl less than or equal to 1.3:1 was observed for all the samples, including measurements made on lesukite from the Russian locality Vergasova et al. studied in 1997, and determined to have a 2:1 ratio. SEM-EDS analyses also show all samples to have minor iron substitution, as well as copper substitution in two samples. FTIR spectra are very similar for all samples. Raman spectroscopy done on both samples collected in Cerro Pintados and the Russian lesukite gave similar spectra. Powder XRD analyses on all samples showed spectra identified to be lesukite, including Gordon’s cadwaladerite. Crystal cell parameters calculated from powder XRD ranged from 19.778Å to 19.878Å. Results using modern instrumental techniques confirm Gordon’s cadwaladerite, collected in 1939 and described in 1941, and lesukite are the same mineral species.

The Relationship Between Cadwaladerite Al(OH)2Cl∙4H2O and Lesukite Al2(OH)5Cl∙2H2O as Investigated by SEM, PXRD, FTIR and Raman Spectroscopy

Cadwaladerite (Al(OH)2Cl∙4H2O) collected from Cerro Pintados, Chile described by Gordon in 1941 is designated as “doubtful” by the IMA. Material collected from the same locality in 2015 resembling the description of cadwaladerite gave a powder XRD pattern similar to lesukite (Al2(OH)5Cl∙2H2O). However, Gordon provided no X-ray data for his material from Cerro Pintados. In order to determine whether cadwaladerite and lesukite are the same mineral species, measurements were made on a suite of samples from various localities. A portion of the material collected by Gordon in 1941 was also obtained from the Mineralogical Museum of Harvard University. Type material of lesukite from a fumarolic environment at the Tolbachik Fissure in Kamchatka, Russia was obtained as well as lesukite from the Maria Mine, Chile (Arica Province) and a previously undescribed locality for lesukite (Barranaca del Sulfato, Mejillones Peninsula, Antofagasta Province). All samples are yellow to yellow-orange in colour and all exhibit small cubic crystals (up to 50µm), even Gordon’s cadwaladerite which was thought to be amorphous. The Chilean samples are all associated with halite and sometimes with anhydrite. These five samples were studied by SEM, FTIR, powder XRD, and Raman spectroscopy. A ratio of Al:Cl less than or equal to 1.3:1 was observed for all the samples, including measurements made on lesukite from the Russian locality Vergasova et al. studied in 1997, and determined to have a 2:1 ratio. SEM-EDS analyses also show all samples to have minor iron substitution, as well as copper substitution in two samples. FTIR spectra are very similar for all samples. Raman spectroscopy done on both samples collected in Cerro Pintados and the Russian lesukite gave similar spectra. Powder XRD analyses on all samples showed spectra identified to be lesukite, including Gordon’s cadwaladerite. Crystal cell parameters calculated from powder XRD ranged from 19.778Å to 19.878Å. Results using modern instrumental techniques confirm Gordon’s cadwaladerite, collected in 1939 and described in 1941, and lesukite are the same mineral species.

Continuous statistical modelling for rapid detection of adulteration of extra virgin olive oil using mid infrared and Raman spectroscopic data

The main objective of this work was to develop a novel dimensionality reduction technique as a part of an integrated pattern recognition solution capable of identifying adulterants such as hazelnut oil in extra virgin olive oil at low percentages based on spectroscopic chemical fingerprints. A novel Continuous Locality Preserving Projections (CLPP) technique is proposed which allows the modelling of the continuous nature of the produced in-house admixtures as data series instead of discrete points. The maintenance of the continuous structure of the data manifold enables the better visualisation of this examined classification problem and facilitates the more accurate utilisation of the manifold for detecting the adulterants. The performance of the proposed technique is validated with two different spectroscopic techniques (Raman and Fourier transform infrared, FT-IR). In all cases studied, CLPP accompanied by k-Nearest Neighbors (kNN) algorithm was found to outperform any other state-of-the-art pattern recognition techniques.

TIME-RESOLVED RESONANCE RAMAN-SPECTROSCOPY AND RAMAN SPECTROELECTROCHEMISTRY OF (CO)(5)W[4,4'-BPY]W(CO)(5), PROBED IN THE VISIBLE AND NEAR-INFRARED

Time-resolved resonance Raman spectroscopy of the lowest energy excited state of the 4,4'-bipyridyl ligand-bridged complex, [(CO)(5)W(L)W(CO5] (1), and Raman spectroscopy of electrochemically reduced 1, both give bands characteristic of the the L(.-) species. This confirms that the ligand L is negatively charged in the lowest energy exicited state which is therefore metal-ligand charge transfer (MLCT) in character. Raman spectra of the radical anion of 1 excited in the far red (800 nm) exhibited a band near 2050 cm(-1) due to a vco symmetric CO stretching mode, compared to the corresponding band at 2070 cm(-1) in the spectrum of the parent, uncharged complex. The lower vco in the reduced complex supports the recent finding by time-resolved IR spectroscopy of a similar frequency decrease for nu(CO) in the longest lived (MLCT) excited state of 1 which was attributed to electron/hole localisation in this state on the IR time scale.

Chemistry, Raman and infrared spectroscopic characterization of the phosphate mineral reddingite: (MnFe)3(PO4)2(H2O,OH)3, a mineral found in lithium-bearing pegmatite

Detailed investigation of an intermediate member of the reddingite–phosphoferrite series, using infrared and Raman spectroscopy, scanning electron microcopy and electron microprobe analysis, has been carried out on a homogeneous sample from a lithium-bearing pegmatite named Cigana mine, near Conselheiro Pena, Minas Gerais, Brazil. The determined formula is (Mn1.60Fe1.21Ca0.01Mg0.01)∑2.83(PO4)2.12⋅(H2O2.85F0.01)∑2.86 indicating predominance in the reddingite member. Raman spectroscopy coupled with infrared spectroscopy supports the concept of phosphate, hydrogen phosphate and dihydrogen phosphate units in the structure of reddingite-phosphoferrite. Infrared and Raman bands attributed to water and hydroxyl stretching modes are identified. Vibrational spectroscopy adds useful information to the molecular structure of reddingite–phosphoferrite.

Raman and infrared spectroscopic study of kamphaugite-(Y)

We have studied the carbonate mineral kamphaugite-(Y)(CaY(CO3)2(OH)·H2O), a mineral which contains yttrium and specific rare earth elements. Chemical analysis shows the presence of Ca, Y and C. Back scattering SEM appears to indicate a single pure phase. The vibrational spectroscopy of kamphaugite-(Y) was obtained using a combination of Raman and infrared spectroscopy. Two distinct Raman bands observed at 1078 and 1088cm(-1) provide evidence for the non-equivalence of the carbonate anion in the kamphaugite-(Y) structure. Such a concept is supported by the number of bands assigned to the carbonate antisymmetric stretching mode. Multiple bands in the ν4 region offers further support for the non-equivalence of carbonate anions in the structure. Vibrational spectroscopy enables aspects of the structure of the mineral kamphaugite-(Y) to be assessed.

Characterization and identification of mixed-metal phosphates in soils: the application, of Raman spectroscopy

The development of protocols for the identification of metal phosphates in phosphate-treated, metal-contaminated soils is a necessary yet problematical step in the validation of remediation schemes involving immobilization of metals as phosphate phases. The potential for Raman spectroscopy to be applied to the identification of these phosphates in soils has yet to be fully explored. With this in mind, a range of synthetic mixed-metal hydroxylapatites has been characterized and added to soils at known concentrations for analysis using both bulk X-ray powder diffraction (XRD) and Raman spectroscopy. Mixed-metal hydroxylapatites in the binary series Ca-Cd, Ca-Pb, Ca-Sr and Cd-Pb synthesized in the presence of acetate and carbonate ions, were characterized using a range of analytical techniques including XRD, analytical scanning electron microscopy (SEM), infrared spectroscopy (IR), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and Raman spectroscopy. Only the Ca-Cd series displays complete solid solution, although under the synthesis conditions of this study the Cd-5(PO4)(3)OH end member could not be synthesized as a pure phase. Within the Ca-Cd series the cell parameters, IR active modes and Raman active bands vary linearly as a function of Cd content. X-ray diffraction and extended X-ray absorption fine structure spectroscopy (EXAFS) suggest that the Cd is distributed across both the Ca(1) and Ca(2) sites, even at low Cd concentrations. In order to explore the likely detection limits for mixed-metal phosphates in soils for XRD and Raman spectroscopy, soils doped with mixed-metal hydroxylapatites at concentrations of 5, 1 and 0.5 wt.% were then studied. X-ray diffraction could not confirm unambiguously the presence or identity of mixed-metal phosphates in soils at concentrations below 5 wt.%. Raman spectroscopy proved a far more sensitive method for the identification of mixed-metal hydroxylapatites in soils, which could positively identify the presence of such phases in soils at all the dopant concentrations used in this study. Moreover, Raman spectroscopy could also provide an accurate assessment of the degree of chemical substitution in the hydroxylapatites even when present in soils at concentrations as low as 0.1%.

Raman spectroscopy of gallium based hydrotalcites of formula Mg6Ga2(CO3)(OH)16•4H2O

Insight into the unique structure of hydrotalcites has been obtained using Raman spectroscopy. Gallium containing hydrotalcites of formula Mg4Ga2(CO3)(OH)12•4H2O (2:1 Ga-HT) to Mg8Ga2(CO3)(OH)20•4H2O (4:1 Ga-HT) have been successfully synthesised and characterized by X-ray diffraction and Raman spectroscopy. The d(003) spacing varied from 7.83 Å for the 2:1 hydrotalcite to 8.15 Å for the 3:1 gallium containing hydrotalcite. Raman spectroscopy complemented with selected infrared data has been used to characterise the synthesised gallium containing hydrotalcites of formula Mg6Ga2(CO3)(OH)16•4H2O. Raman bands observed at around 1046, 1048 and 1058 cm-1 were attributed to the symmetric stretching modes of the (CO32-) units. Multiple ν3 CO32- antisymmetric stretching modes are found at around 1346, 1378, 1446, 1464 and 1494 cm-1. The splitting of this mode indicates the carbonate anion is in a perturbed state. Raman bands observed at 710 and 717 cm-1 assigned to the ν4 (CO32-) modes support the concept of multiple carbonate species in the interlayer.