Raman spectroscopic study of the mixed anion sulphate–arsenate mineral parnauite Cu9[(OH)10|SO4|(AsO4)2]·7H2O

The mixed anion mineral parnauite Cu₉[(OH)₁₀|SO₄|(AsO₄)₂]·7H₂O has been studied by Raman spectroscopy. Characteristic bands associated with arsenate, sulphate and hydroxyl units are identified. Broad bands are observed and are resolved into component bands. Two intense bands at 859 and 830 cm⁻¹ are assigned to the ν₁ (AsO₄)³⁻ symmetric stretching and ν₃ (AsO₄)³⁻ antisymmetric stretching modes. The comparatively sharp band at 976 cm⁻¹ is assigned to the ν₁ (SO₄)²⁻ symmetric stretching mode and a broad‐spectral profile centered upon 1097 cm⁻¹ is attributed to the ν₃ (SO₄)²⁻ antisymmetric stretching mode. A comparison of the Raman spectra is made with other arsenate‐bearing minerals such as carminite, clinotyrolite, kankite, tilasite and pharmacosiderite. Copyright © 2009 John Wiley & Sons, Ltd.     

In situ SEOP polarised He neutron spin filter for incident beam polarisation and polarisation analysis on neutron scattering instruments

We discuss the development and characterisation of a new in situ spin exchange optical pumping (SEOP) based ³He neutron spin filter polarisation device. We present results from a recent test of the prototype system developed with the Institut Laue-Langevin. The polariser was installed on the polarised reflectometer CRISP at ISIS in the analyser position. The ³He was pumped continuously in situ on the beamline. The system also integrated a ³He adiabatic fast passage spin flipper that allowed reversal of the ³He and therefore neutron polarisation state, allowing for measurement of all four polarisation cross-sections. The system was run for a number of days reaching a ³He polarisation of 63%.     

Infrared and infrared emission spectroscopy of gallium oxide α-GaO(OH) nanostructures

Infrared spectroscopy has been used to study nano- to micro-sized gallium oxyhydroxide α-GaO(OH), prepared using a low temperature hydrothermal route. Rod-like α-GaO(OH) crystals with average length of 2.5 μm and width of 1.5 μm were prepared when the initial molar ratio of Ga to OH was 1:3. β-Ga₂O₃ nano and micro-rods were prepared through the calcination of α-GaO(OH). The initial morphology of α-GaO(OH) is retained in the β-Ga₂O₃ nanorods.The combination of infrared and infrared emission spectroscopy complimented with dynamic thermal analysis were used to characterise the α-GaO(OH) nanotubes and the formation of β-Ga₂O₃ nanorods. Bands at around 2903 and 2836 cm⁻¹ are assigned to the –OH stretching vibration of α-GaO(OH) nanorods. Infrared bands at around 952 and 1026 cm⁻¹ are assigned to the Ga–OH deformation modes of α-GaO(OH). A significant number of bands are observed in the 620–725 cm⁻¹ region and are assigned to GaO stretching vibrations.     

Characterisation of red mud by UV-vis-NIR spectroscopy

The characterisation of red mud has been studied by diffuse reflectance spectroscopy in the UV-vis-NIR region (DRS). For the first time the ferric ion responsible for the bands has been identified from electronic spectroscopy. It contains valuable amounts of oxidised iron (Fe(3+)) and aluminium hydroxide. The NIR peak at around 11,630 cm(-1) (860 nm) with a split of two components and a pair of sharp bands near 500 nm (20000 cm(-1)) in the visible spectrum are attributed to Fe(3+) ion in distorted sixfold coordinations. The observation of identical spectral patterns (both electronic and vibrational spectra) of red mud before and after seawater neutralisation (SWN) confirmed that there is no effect of seawater neutralisation on structural cation substitutions such as Al(3+), Fe(3+), Fe(2+), Ti(3+), etc.     

Modification of fibrous silicates surfaces with organic derivatives: an infrared spectroscopic study

This contribution explores the interaction of the fibrous silicates, palygorskite, sepiolite and chrysotile with a wide range of organic agents. Infrared spectroscopy (IR) methods are essential for the characterization of solid surfaces and for the investigation of the kind of bonds formed between the surface of these silicates and the organic moieties. Thus, when sepiolite or palygorskite are treated, e.g., with polyurethanes, alcohols, isocyanates, amines or pyridines, specific SiNHC or SiOC bonds are derived from the linkage of the differently located OH groups in these fibrous silicates with the organic moieties. On the other hand, more stable, covalent SiOSiC bondings are formed when the fibrous silicates, especially chrysotile, are reacted with heterofunctional silylating agents like chlorosilanes or ethoxysilanes carrying, alkyl, alkenyl or aryl groups. Such reactions may occur in the presence or absence of HCl. An absorption band at 960 cm(-1)--which we assigned to SiOH groups--is detected only in the presence of HCl. The evolution of this band is related to the degree of grafting of the organic radicals with the silanol groups of the silicates. HCl-generated silanol groups are the main bridges for the coupling of organosilyl groups on chrysotile and other silicates by covalent bonding, leading the way to the preparation of interesting new materials, including fibrous sheet polymers.     

Correlation of process parameters and properties of TiO<Subscript>2</Subscript> films grown by ion beam sputter deposition from a ceramic target

The correlation between process parameters and properties of TiO₂ films grown by ion beam sputter deposition from a ceramic target was investigated. TiO₂ films were grown under systematic variation of ion beam parameters (ion species, ion energy) and geometrical parameters (ion incidence angle, polar emission angle) and characterized with respect to film thickness, growth rate, structural properties, surface topography, composition, optical properties, and mass density. Systematic variations of film properties with the scattering geometry, namely the scattering angle, have been revealed. There are also considerable differences in film properties when changing the process gas from Ar to Xe. Similar systematics were reported for TiO₂ films grown by reactive ion beam sputter deposition from a metal target [C. Bundesmann et al., Appl. Surf. Sci. 421, 331 (2017)]. However, there are some deviations from the previously reported data, for instance, in growth rate, mass density and optical properties.     

The Garfield and Uley nontronites--an infrared spectroscopic comparison

FTIR and Infrared emission spectroscopy (IES) has been used to characterise the Uley (Australian) and Garfield nontronites. These clay minerals are characterised by a strong emission band at 3570 cm(-1) attributed to the FeFeOH unit. Dehydroxylation is followed by the loss of intensity of this band as a function of temperature. Dehydroxylation is also followed by the loss of intensity of the FeFeOH deformation vibration at 843 cm(-1). IES shows that the dehydroxylation occurs as a continuous process in comparison to DTA/TGA studies where the dehydroxylation occurs abruptly at 425 degrees C. Water in these high iron bearing smectites have been observed through the stretching mode at 3430 cm(-1) and the bending mode at 1630 cm(-1). Different types of water are identified in the nontronite structure by the analysis of the band profile in the 1590-1680 cm(-1) region. Low frequency vibrations show that the Uley green nontronite is similar to the Garfield nontronite. The brown Uley nontronite is closer to the Hohen-Hagen nontronite. The Uley nontronites may, therefore, be used spectroscopically to replace other nontronites as a reference clay mineral.     

Near-infrared spectroscopic study of nontronites and ferruginous smectite

The existence of life on planets such as Mars depend upon the presence of water. This water may not necessarily be as liquid or crystalline water but may be as interlayer water such as is found in smectitic clays. One group of smectites, relevant to the search for interplanetary life are those which have a high iron content, known as nontronites. Near-IR reflectance spectroscopy has been used to show the presence of water and hydroxyl units in these minerals. Three near-IR spectral regions are identified, (a) the high frequency region between 6400 and 7400 cm(-1) attributed to the first overtone of the hydroxyl stretching mode; (b) the 4800-5400 cm(-1) region attributed to water combination modes; and (c) the 4000-4800 cm(-1) region attributed to the combination of the stretching and deformation modes of the FeFeOH units of nontronite. Two types of hydroxyl groups were identified using near-IR spectroscopy, hydroxyl units coordinated to the iron, and hydroxyl groups from water in the nontronite structure. The first hydroxyls are characterised by several bands, firstly in the 7055-7098 cm(-1) region assigned to the first overtone of the AlFeOH stretching unit, secondly in the 6958-6878 cm(-1) region attributed to the FeFeOH unit. The overtone of the hydroxyl stretching frequency of water was observed at around 6800 cm(-1). These observations show that nontronites can be a source of water that may support life.     

Raman spectroscopy of potassium acetate-intercalated kaolinites at liquid nitrogen temperature

Raman microscopy has been used to study low and high defect kaolinites and their potassium acetate intercalated complexes at 298 and 77 K. Raman spectroscopy shows significant differences in the spectra of the hydroxyl-stretching region of the two types of kaolinites, which is also reflected in the spectroscopy of the hydroxyl-stretching region of the intercalation complexes. Additional bands to the normally observed kaolinite hydroxyl stretching frequencies are observed for the low and high defect kaolinites at 3605 and 3602 cm(-1) at 298 K. Upon cooling to liquid nitrogen temperature, these bands are observed at 3607 and 3604 cm(-1), thus indicating a weakening of the hydrogen bond formed between the inner surface hydroxyls and the acetate ion. Upon cooling to liquid nitrogen temperature, the frequency of the inner hydroxyls shifted to lower frequencies. Collection of Raman spectra at liquid nitrogen temperature did not give better band separation compared to the room temperature spectra as the bands increased in width and shifted closer together.     

Infrared spectroscopic study of natural hydrotalcites carrboydite and hydrohonessite

Infrared spectroscopy has proven most useful for the study of anions in the interlayer of natural hydrotalcites. A suite of naturally occurring hydrotalcites including carrboydite, hydrohonessite, reevesite, motukoreaite and takovite were analysed. Variation in the hydroxyl stretching region was observed and the band profile is a continuum of states resulting from the OH stretching of the hydroxyl and water units. Infrared spectroscopy identifies some isomorphic substitution of sulphate for carbonate through an anion exchange mechanism for the minerals carrboydite and hydrohonessite. The infrared spectra of the CO3 and SO4 stretching region of takovite is complex because of band overlap. For this mineral some sulphate has replaced the carbonate in the structure. In the spectra of takovites, a band is observed at 1346 cm(-1) and is attributed to the carbonate anion hydrogen bonded to water in the interlayer. Infrared spectroscopy has proven most useful for the study of the interlayer structure of these natural hydrotalcites.