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.

Corona ions from overhead transmission voltage powerlines : effect on DC e-field and ambient particle concentration levels

Along with their essential role in electricity transmission and distribution, some powerlines also generate large concentrations of corona ions. This study aimed at comprehensive investigation of corona ions, vertical dc e-field, ambient aerosol particle charge and particle number concentration levels in the proximity of some high/sub-transmission voltage powerlines. The influence of meteorology on the instantaneous value of these parameters, and the possible existence of links or associations between the parameters measured were also statistically investigated. The presence of positive and negative polarities of corona ions was associated with variation in the mean vertical dc e-field, ambient ion and particle charge concentration level. Though these variations increased with wind speed, their values also decreased with distance from the powerlines. Predominately positive polarities of ions were recorded up to a distance of 150 m (with the maximum values recorded 50 m downwind of the powerlines). At 200 m from the source, negative ions predominated. Particle number concentration levels however remained relatively constant (103 particle cm-3) irrespective of the sampling site and distance from the powerlines. Meteorological factors of temperature, humidity and wind direction showed no influence on the electrical parameters measured. The study also discovered that e-field measurements were not necessarily a true representation of the ground-level ambient ion/particle charge concentrations.

The effect of metamictization on the Raman spectroscopy of the uranyl titanate mineral davidite (La,Ce)(Y,U,Fe2+)(Ti,Fe3+)20(O,OH)38

Raman spectra of the uranyl titanate mineral davidite-(La) (La,Ce)(Y,U,Fe2+)(Ti,Fe3+)20(O,OH)38 were analysed and related to the mineral structure. Observed bands are attributed to the TiO and (UO2)2+ stretching and bending vibrations, U-OH bending vibrations, H2O and (OH)- stretching, bending and libration modes. U-O bond lengths in uranyls and O-H…O bond lengths are calculated from the wavenumbers assigned to the stretching vibrations. Raman bands of davidite-(La) are in harmony with those of the uranyl oxyhydroxides. The mineral davidite-(La) is metamict as is evidenced by the intensity of the UO stretching and bending modes being of lower intensity than expected and with bands that are significantly broader.

Raman spectroscopy of selected borate minerals of the pinakiolite group

The Raman spectra of a series of related minerals of the pinakiolite group of minerals have been collected and the spectra related to the mineral structure. These minerals are based upon an isolated BO33- ion. The site symmetry is reduced from D3h to C1. Intense Raman bands are observed for the minerals takeuchiite, pinakiolite, fredrikssonite and azoproite at 1084, 1086, 1086 and 1086 cm-1. These bands are assigned to the ν1 BO33- symmetric stretching mode. Low intensity Raman bands are observed for the minerals at 1345, 1748; 1435, 1748; 1435, 1750; 1436, 1749 cm-1. One probable assignment is to ν3 BO33- antisymmetric stretching mode. Intense Raman bands of takeuchiite, pinakiolite, fredrikssonite and azoproite at 712 cm-1 attributed to the ν2 out-of-plane bending mode. Importantly, through the comparison of the Raman spectra, the molecular structure of borate minerals with ill-defined structures can be obtained.

Evidence of multiwall carbon nanotube deformation caused by poly(3-hexylthiophene) adhesion

We show that when a soft polymer like Poly(3-hexyl-thiophene) wraps multiwall nanotubes by coiling around the main axis, a localized deformation of the nanotube structure is observed. High resolution transmission electron microscopy shows that radial compressions of about 4% can take place, and could possibly lead to larger interlayer distance between the nanotube inner walls and reduce the innermost nanotube radius. The mechanical stress due to the polymer presence was confirmed by Raman spectroscopic observation of a gradual upshift of the carbon nanotube G-band when the polymer content in the composites was progressively increased. Vibrational spectroscopy also indicates that charge transfer from the polymer to the nanotubes is responsible for a peak frequency relative downshift for high P3HT-content samples. Continuously acquired transmission electron microscopy images at rising temperature show the MWCNT elastic compression and relaxation due to polymer rearrangement on the nanotube surface.

Single crystal Raman spectroscopy of natural leiteite ZnAs2O4 and in comparison with the synthesised mineral

The oriented single crystal Raman spectrum of leiteite has been obtained and the spectra related to the structure of the mineral. The intensities of the observed bands vary according to orientation allowing them to be assigned to either Ag or Bg modes. Ag bands are generally the most intense in the CAAC spectrum, followed by ACCA, CBBC, and ABBA whereas Bg bands are generally the most intense in the CBAC followed by ABCA. The CAAC and ACCA spectra are identical, as are those obtained in the CBBC and ABBA orientations. Both cross-polarised spectra are identical. Band assignments were made with respect to bridging and non-bridging As-O bonds.

Raman spectroscopy of gallium- and zinc-based hydrotalcites

Insight into the unique structure of hydrotalcites (HTs) has been obtained using Raman spectroscopy. Gallium-contg. HTs of formula Zn4 Ga2(CO3)(OH)12 · xH2O (2:1 ZnGa-HT), Zn6 Ga2(CO3)(OH)16 · xH2O (3:1 ZnGa-HT) and Zn8 Ga2(CO3)(OH)18 · xH2O (4:1 ZnGa-HT) have been successfully synthesized and characterised by X-ray diffraction (XRD) and Raman spectroscopy. The d(003) spacing varies from 7.62 Å for the 2:1 ZnGa-HT to 7.64 Å for the 3:1 ZnGa-HT. The 4:1 ZnGa-HT showed a decrease in the d(003) spacing, compared to the 2:1 and 3:1 compds. Raman spectroscopy complemented with selected IR data has been used to characterize the synthesized gallium-contg. HTs. Raman bands obsd. at around 1050, 1060 and 1067 cm-1 are attributed to the sym. stretching modes of the (CO32-) units. Multiple ν3 (CO32-) antisym. stretching modes are found between 1350 and 1520 cm-1, confirming multiple carbonate species in the HT structure. The splitting of this mode indicates that the carbonate anion is in a perturbed state. Raman bands obsd. at 710 and 717 cm-1 and assigned to the ν4 (CO32-) modes support the concept of multiple carbonate species in the interlayer.

Single-crystal Raman spectroscopy of natural schafarzikite FeSb2O4 from Pernek, Slovak Republic

The single crystal Raman spectra of natural mineral schafarzikite FeSb2O4 from the Pernek locality of the Slovak Republic are presented for the first time. Raman spectra of natural mineral apuanite Fe2+Fe43+Sb4O12S, originating from the Apuan Alps in Italy, as well as spectra of synthetic ZnSb2O4 and arsenite mineral trippkeite CuAs2O4 are also presented for the first time. The spectra of the antimonite minerals are characterized by a strong band in the region 660 – 680 cm-1 with shoulders on either side, and a band of medium intensity near 300 cm-1. The spectrum of the arsenite mineral is characterized by a medium band near 780 cm-1 with a shoulder on the high wavenumber side and a strong band at 370 cm-1. Assignments are proposed based on the spectral comparison between the compounds, symmetry modes of the bands and prior literature. The single crystal spectra of schafarzikite showed good mode separation, allowing bands to be assigned a symmetry species of A1g, B1g, B2g or Eg.

An infrared study of adsorption of paranitrophenol on mono, di and trialkyl surfactant intercalated organoclays

Infrared spectroscopy has been used to study the adsorption of paranitrophenol on mono, di and tri alkyl surfactant intercalated montmorillonite. Organoclays were obtained by the cationic exchange of mono, di and tri alkyl chain surfactants for sodium ions [hexadecyltrimethylammonium bromide (HDTMAB), dimethyldioctadecylammonium bromide (DDOAB), methyltrioctadecylammonium bromide (MTOAB)] in an aqueous solution with Na-montmorillonite. Upon formation of the organoclay, the properties change from strongly hydrophilic to strongly hydrophobic. This change in surface properties is observed by a decrease in intensity of the OH stretching vibrations assigned to water in the cation hydration sphere of the montmorillonite. As the cation is replaced by the surfactant molecules the paranitrophenol replaces the surfactant molecules in the clay interlayer. Bands attributed to CH stretching and bending vibrations change for the surfactant intercalated montmorillonite. Strong changes occur in the HCH deformation modes of the methyl groups of the surfactant. These changes are attributed to the methyl groups locking into the siloxane surface of the montmorillonite. Such a concept is supported by changes in the SiO stretching bands of the montmorillonite siloxane surface. This study demonstrates that paranitrophenol will penetrate into the untreated clay interlayer and replace the intercalated surfactant in surfactant modified clay, resulting in the change of the arrangement of the intercalated surfactant.

Spatially offset Raman spectroscopy (SORS) for the analysis and detection of packaged pharmaceuticals and concealed drugs

Spatially offset Raman spectroscopy (SORS) is a powerful new technique for the non-invasive detection and identification of concealed substances and drugs. Here, we demonstrate the SORS technique in several scenarios that are relevant to customs screening, postal screening, drug detection and forensics applications. The examples include analysis of a multi-layered postal package to identify a concealed substance; identification of an antibiotic capsule inside its plastic blister pack; analysis of an envelope containing a powder; and identification of a drug dissolved in a clear solvent, contained in a non-transparent plastic bottle. As well as providing practical examples of SORS, the results highlight several considerations regarding the use of SORS in the field, including the advantages of different analysis geometries and the ability to tailor instrument parameters and optics to suit different types of packages and samples. We also discuss the features and benefits of SORS in relation to existing Raman techniques, including confocal microscopy, wide area illumination and the conventional backscattered Raman spectroscopy. The results will contribute to the recognition of SORS as a promising method for the rapid, chemically-specific analysis and detection of drugs and pharmaceuticals.

Characterisation of organoclays and adsorption of p-nitrophenol : environmental application

Organoclays were synthesised through ion exchange of a single surfactant for sodium ions, and characterised by a range of method including X-ray diffraction (XRD), BET, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and transmission electron microscopy (TEM). The change in surface properties of montmorillonite and organoclays intercalated with the surfactant, tetradecyltrimethylammonium bromide (TDTMA) were determined using XRD through the change in basal spacing and the expansion occurred by the adsorbed p-nitrophenol. The changes of interlayer spacing were observed in TEM. In addition, the surface measurement such as specific surface area and pore volume was measured and calculated using BET method, this suggested the loaded surfactant is highly important to determine the sorption mechanism onto organoclays. The collected results of XPS provided the chemical composition of montmorillonite and organoclays, and the high-resolution XPS spectra offered the chemical states of prepared organoclays with binding energy. Using TGA and FT-IR, the confirmation of intercalated surfactant was investigated. The collected data from various techniques enable an understanding of the changes in structure and surface properties. This study is of importance to provide mechanisms for the adsorption of organic molecules, especially in contaminated environmental sites and polluted waters.

The application of Raman spectroscopy to the study of the uranyl mineral coconinoite Fe2Al2(UO2)2(PO4)4(SO4)(OH)2•20H2O

Raman spectra of the uranyl containing mineral coconinoite, Fe2Al2(UO2)2(PO4)4(SO4)(OH)2•20H2O, are presented and compared with the mineral’s infrared spectra. Bands connected with (UO2)2+, (PO4)3- , (SO4)2-, (OH)- and H2O stretching and bending vibrations, are assigned. Approximate U-O bond lengths in uranyl, (UO2)2+, and O-H...O hydrogen bond lengths are calculated from the wavenumbers of the U-O stretching vibrations and (OH)- and H2O stretching vibrations, respectively, and compared with published data for similar natural and synthetic compounds.

Raman spectroscopy of newberyite Mg(PO3OH)•3H2O – a cave mineral

Newberyite Mg(PO3OH)•3H2O is a mineral found in caves such as from Moorba cave, Jurien Bay, Western Australia, the Skipton Lava tubes (SW of Ballarat, Victoria, Australia) and in the Petrogale Cave (Madura , Eucla, Western Australia). Because these minerals contain oxyanions, hydroxyl units and water, the minerals lend themselves to spectroscopic analysis. Raman spectroscopy can investigate the complex paragenetic relationships existing between a number of ‘cave’ minerals. The intense sharp band at 982 cm-1 is assigned to the PO43- ν1 symmetric stretching mode. Low intensity Raman bands at 1152, 1263 and 1277 cm-1 are assigned to the PO43- ν3 antisymmetric stretching vibrations. Raman bands at 497 and 552 cm-1 are attributed to the PO43- ν4 bending modes. An intense Raman band for newberyite at 398 cm-1 with a shoulder band at 413 cm-1 is assigned to the PO43- ν2 bending modes. The values for the OH stretching vibrations provide hydrogen bond distances of 2.728Å (3267 cm-1), 2.781Å (3374cm-1), 2.868Å (3479 cm-1), and 2.918Å (3515 cm-1). Such hydrogen bond distances are typical of secondary minerals. Estimates of the hydrogen-bond distances have been made from the position of the OH stretching vibrations and show a wide range in both strong and weak bonds.

Raman spectroscopy of stercorite H(NH4)Na(PO4)•4H2O – a cave mineral from Petrogale Cave, Madura, Eucla, Western Australia

Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the mineral stercorite H(NH4)Na(PO4)·4H2O. The mineral stercorite originated from the Petrogale Cave, Madura, Eucla, Western Australia. This cave is one of many caves in the Nullarbor Plain in the South of Western Australia. These caves have been in existence for eons of time and have been dated at more than 550 million years old. The mineral is formed by the reaction of bat guano chemicals on calcite substrates. A single Raman band at 920 cm−1 defines the presence of phosphate in the mineral. Antisymmetric stretching bands are observed in the infrared spectrum at 1052, 1097, 1135 and 1173 cm−1. Raman spectroscopy shows the mineral is based upon the phosphate anion and not the hydrogen phosphate anion. Raman and infrared bands are found and assigned to PO43−, H2O, OH and NH stretching vibrations. The detection of stercorite by Raman spectroscopy shows that the mineral can be readily determined; as such the application of a portable Raman spectrometer in a ‘cave’ situation enables the detection of minerals, some of which may remain to be identified.