Vibrational spectroscopic study of the antimonate mineral bindheimite Pb2Sb2O6(O,OH)

Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the antimonate mineral bindheimite Pb₂Sb₂O₆(O,OH). The mineral is characterised by an intense Raman band at 656 cm⁻¹ assigned to SbO stretching vibrations. Other lower intensity bands at 664, 749 and 814 cm⁻¹ are also assigned to stretching vibrations. This observation suggests the non-equivalence of SbO units in the structure. Low intensity Raman bands at 293, 312 and 328 cm⁻¹ are assigned to the OSbO bending vibrations. Infrared bands at 979, 1008, 1037 and 1058 cm⁻¹ may be assigned to δOH deformation modes of SbOH units. Infrared bands at 1603 and 1640 cm⁻¹ are assigned to water bending vibrations, suggesting that water is involved in the bindheimite structure. Broad infrared bands centred upon 3250 cm⁻¹ supports this concept. Thus the true formula of bindheimite is questioned and probably should be written as Pb₂Sb₂O₆(O,OH,H₂O).     

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.     

Ion beam sputter deposition of TiO<Subscript>2</Subscript> films using oxygen ions

TiO₂ thin films were grown by ion beam sputter deposition (IBSD) using oxygen ions, with the ion energy and geometrical parameters (ion incidence angle, polar emission angle, and scattering angle) being varied systematically. Metallic Ti and ceramic TiO₂ served as target materials. The thin films were characterized concerning thickness, growth rate, surface topography, structural properties, mass density, and optical properties. It was found that the scattering geometry has the main impact on the film properties. Target material, ion energy, and ion incidence angle have only a marginal influence. Former studies on reactive IBSD of TiO₂ using Ar and Xe ions reported equivalent patterns. Nevertheless, the respective ion species distinctively affects the film properties. For instance, mass density and the refractive index of the TiO₂ thin films are remarkably lower for sputtering with oxygen ions than for sputtering with Ar or Xe ions. The variations in the thin film properties are tentatively attributed to the angular and the energy distribution of the film-forming particles, especially, to those of the backscattered primary particles.     

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.     

A thermoanalytical assessment of an organoclay

High resolution thermogravimetric analysis (TG) has attracted much attention in the synthesis of organoclays and its applications. In this study, organoclays were synthesised through ion exchange of a single cationic surfactant for sodium ions, and characterised by methods including X-ray diffraction (XRD) and TG. The changes of surface properties in montmorillonite (MMT) and organoclays intercalated with surfactant were determined using XRD through the changes in the basal spacing. The TG was applied in this study to investigate more information of the configuration and structural changes in the organoclays with thermal decomposition. There are four different decompositions steps in differential thermogravimetric curves. The obtained TG steps are relevant to the arrangement of the surfactant molecules intercalated in MMT and the thermal analysis indicates the thermal stability of surfactant modified clays. This investigation provides new insights into the properties of organoclays and is important in the synthesis and processing of organoclays for environmental applications.