An application of near-infrared and mid-infrared spectroscopy to the study of selected minerals

Near-infrared spectroscopy is a somewhat unutilised technique for the study of minerals. The technique has the ability to determine water content, hydroxyl groups and transition metals. In this paper we show the application of NIR spectroscopy to the study of selected minerals. The structure and spectral properties of two Cu-tellurite minerals graemite and teineite are compared with bismuth containing tellurite mineral smirnite by the application of NIR and IR spectroscopy. The position of Cu2+ bands and their splitting in the electronic spectra of tellurites are in conformity with octahedral geometry distortion. The spectral pattern of smirnite resembles graemite and the observed band at 10855 cm-1 with a weak shoulder at 7920 cm-1 is identified as due to Cu2+ ion. Any transition metal impurities may be identified by their bands in this spectral region. Three prominent bands observed in the region of 7200-6500 cm-1 are the overtones of water whilst the weak bands observed near 6200 cm-1in tellurites may be attributed to the hydrogen bonding between (TeO3)2- and H2O. The observation of a number of bands centred at around 7200 cm-1 confirms molecular water in tellurite minerals. A number of overlapping bands in the low wavenumbers 4500-4000 cm-1 is the result of combinational modes of (TeO3)2−ion. The appearance of the most intense peak at 5200 cm-1 with a pair of weak bands near 6000 cm-1 is a common feature in all the spectra and is related to the combinations of OH vibrations of water molecules, and bending vibrations ν2 (δ H2O). Bending vibrations δ H2O observed in the IR spectra shows a single band for smirnite at 1610 cm-1. The resolution of this band into number of components is evidenced for non-equivalent types of molecular water in graemite and teineite. (TeO3)2- stretching vibrations are characterized by three main absorptions at 1080, 780 and 695 cm-1.

Thermally activated seawater neutralised red mud used for the removal of arsenate, vanadate and molybdate from aqueous solutions.

The effectiveness of using thermally activated hydrotalcite materials has been investigated for the removal of arsenate, vanadate, and molybdate in individual and mixed solutions. Results show that increasing the Mg,Al ratio to 4:1 causes an increase in the percentage of anions removed from solution. The order of affinity of the three anions analysed in this investigation is arsenate, vanadate, and molybdate. By comparisons with several synthetic hydrotalcite materials, the hydrotalcite structure in the seawater neutralised red mud (SWN-RM) has been determined to consist of magnesium and aluminium with a ratio between 3.5:1 and 4:1. Thermally activated seawater neutralised red mud removes at least twice the concentration of anionic species than thermally activated red mud alone, due to the formation of 40 to 60 % Bayer hydrotalcite during the neutralisation process.

Smectite flocculation structure modified by AI13 macromolecules; as revealed by the Transmission X-ray Microscopy (TXM)

The aggregate structure which occurs in aqueous smectitic suspensions is responsible for poor water clarification, difficulties in sludge dewatering and the unusual rheological behaviour of smectite rich soils. These macroscopic properties are dictated by the 3-D structural arrangement of smectite finest fraction within flocculated aggregates. Here, we report results from a relatively new technique, Transmission X-ray Microscopy (TXM), which makes it possible to investigate the internal structure and 3-D tomographic reconstruction of the smectite clay aggregates modified by Al13 keggin macro-molecule [Al13(O)4(OH)24(H2O)12 ]7+. Three different treatment methods were shown resulted in three different micro-structural environments of the resulting flocculation.

Vibrational spectroscopy of intercalated kaolinites. Part I

The industrial application of kaolinite is closely related to its reactivity and surface properties. The reactivity of kaolinite can be tested by intercalation, i.e. via the insertion of low molecular weight organic compounds between the kaolinite layers resulting in the formation of a nano-layered organo-complex. Although intercalation of kaolinite is an old and ongoing research topic, there is a limited knowledge available on the reactivity of different kaolinites, the mechanism of complex formation as well as on the structure of the complexes formed. Grafting and incorporation of exfoliated kaolinite in polymer matrices and other potential applications can open new horizons in the study of kaolinite intercalation. This paper attempts to summarize (without completion) the most recent achievements in the study of kaolinite organo-complexes obtained with the most common intercalating compounds like urea, potassium acetate, dimethyl sulphoxide, formamide and hydrazine using vibrational spectroscopy combined with X-ray powder diffraction and thermal analysis.

A Review of the Vibrational Spectroscopic Studies of Arsenite, Antimonite, and Antimonate Minerals

This review focuses on the vibrational spectroscopy of the compounds and minerals containing the arsenite, antimonite and antimonate anions. The review collects and correlates the published data.

PDMS spreading morphological patterns on substrates of different hydrophilicity in air vacuum and water

In paper has been to investigate the morphological patterns and kinetics of PDMS spreading on silicon wafer using combination of techniques like ellipsometry, atomic force microscope (AFM), scanning electron microscope (SEM) and optical microscopy. A macroscopic silicone oil drops as well as PDMS water based emulsions were studied after deposition on a flat surface of silicon wafer in air, water and vacuum. our own measurements using an imaging ellipsometer, which also clearly shows the presence of a precursor film. The diffusion constant of this film, measured with a 60 000 cS PDMS sample spreading on a hydrophilic silicon wafer, is Df = 1.4  10-11 m2/s. Regardless of their size, density and method of deposition, droplets on both types of wafer (hydrophilic and hydrophobic) flatten out over a period of many hours, up to 3 days. During this process neighbouring droplets may coalesce, but there is strong evidence that some of the PDMS from the droplets migrates into a thin, continuous film that covers the surface in between droplets. The thin film appears to be ubiquitous if there has been any deposition of PDMS. However, this statement needs further verification. One question is whether the film forms immediately after forced drying, or whether in some or all cases it only forms by spreading from isolated droplets as they slowly flatten out.

Raman spectroscopic study of the mineral finnemanite Pb5(As3+O3)3Cl

The arsenite minerals finnemanite Pb5(As3+O3)3Cl been studied by Raman spectroscopy. The most intense Raman band at 871 cm-1 is assigned to the ν1 (AsO3)3- symmetric stretching vibration. Three Raman bands at 898, 908 and 947 cm-1 are assigned to the ν3 (AsO3)3- antisymmetric stretching vibration. The observation of multiple antisymmetric stretching vibrations suggest that the (AsO3)3- units are not equivalent in the molecular structure of finnemanite. Two Raman bands at 383 and 399 cm-1 are assigned to the ν2 (AsO3)3- bending modes. DFT calculations enabled the position of AsO32- symmetric stretching mode at 839 cm-1, the antisymmetric stretching mode at 813 cm-1, and the deformation mode at 449 cm-1 to be calculated. Raman bands are observed at 115, 145, 162, 176, 192, 216 and 234 cm-1 as well. The two most intense bands are observed at 176 and 192 cm-1. These bands are assigned to PbCl stretching vibrations and result from transverse/ longitudinal splitting. The bands at 145 and 162 cm-1 may be assigned to Cl-Pb-Cl bending modes.

Raman spectroscopic study of the arsenite minerals leiteite ZnAs2O4 , reinerite Zn3(AsO3)2 and cafarsite Ca5(Ti,Fe,Mn)7(AsO3)12.4H2O

The selected arsenite minerals leiteite, reinerite and cafarsite have been studied by Raman spectroscopy. DFT calculations enabled the position of AsO22- symmetric stretching mode at 839 cm-1, the antisymmetric stretching mode at 813 cm-1, and the deformation mode at 449 cm-1 to be calculated. The Raman spectrum of leiteite shows bands at 804 and 763 cm-1 assigned to the As2O42- symmetric and antisymmetric stretching modes. The most intense Raman band of leiteite is the band at 457 cm-1 and is assigned to the ν2 As2O42- bending mode. A comparison of the Raman spectrum of leiteite is made with the arsenite minerals reinerite and cafarsite.

Characterization of electron trapping in dye-sensitized solar cells by near-IR transmittance measurements

In situ near-IR transmittance measurements have been used to characterize the density of trapped electrons in dye-sensitized solar cells (DSCs). Measurements have been made under a range experimental conditions including during open circuit photovoltage decay and during recording of the IV characteristic. The optical cross section of electrons at 940 nm was determined by relating the IR absorbance to the density of trapped electrons measured by charge extraction. The value, σn = 5.4 × 10-18 cm2, was used to compare the trapped electron densities in illuminated DSCs under open and short circuit conditions in order to quantify the difference in the quasi Fermi level, nEF. It was found that nEF for the cells studied was 250 meV over wide range of illuminat on intensities. IR transmittance measurements have also been used to quantify shifts in conduction band energy associated with dye adsorption.

A comparison of different methods to determine diffusion length in dye-sensitized solar cells

A new steady state method for determination of the electron diffusion length in dye-sensitized solar cells (DSCs) is described and illustrated with data obtained using cells containing three different types of electrolyte. The method is based on using near-IR absorbance methods to establish pairs of illumination intensity for which the total number of trapped electrons is the same at open circuit (where all electrons are lost by interfacial electron transfer) as at short circuit (where the majority of electrons are collected at the contact). Electron diffusion length values obtained by this method are compared with values derived by intensity modulated methods and by impedance measurements under illumination. The results indicate that the values of electron diffusion length derived from the steady state measurements are consistently lower than the values obtained by the non steady-state methods. For all three electrolytes used in the study, the electron diffusion length was sufficiently high to guarantee electron collection efficiencies greater than 90%. Measurement of the trap distributions by near-IR absorption confirmed earlier observations of much higher electron trap densities for electrolytes containing Li+ ions. It is suggested that the electron trap distributions may not be intrinsic properties of the TiO2 nanoparticles, but may be associated with electron-ion interactions.

A Raman spectroscopic study of the antimonite mineral peretaite Ca(SbO)4(OH)2(SO4)2•2H2O

Raman spectra of mineral peretaite Ca(SbO)4(OH)2(SO4)2•2H2O were studied, and related to the structure of the mineral. Raman bands observed at 978 and 980 cm-1 and a series of overlapping bands observed at 1060, 1092, 1115, 1142 and 1152 cm-1 are assigned to the SO42- ν1 symmetric and ν3 antisymmetric stretching modes. Raman bands at 589 and 595 cm-1 are attributed to the SbO symmetric stretching vibrations. The low intensity Raman bands at 650 and 710 cm-1 may be attributed to SbO antisymmetric stretching modes. Raman bands at 610 cm-1 and at 417, 434 and 482 cm-1 are assigned to the SO42- 4 and 2 bending modes, respectively. Raman bands at 337 and 373 cm-1 are assigned to O-Sb-O bending modes. Multiple Raman bands for both SO42- and SbO stretching vibrations support the concept of the non-equivalence of these units in the coquandite structure.

Characterisation of Ni carbonate-bearing minerals by UV-Vis-NIR spectroscopy

Four nickel carbonate-bearing minerals from Australia have been investigated to study the effect of Ni for Mg substitution. The spectra of nullaginite, zaratite, widgiemoolthalite and takovite show three main features in the range of 26,720–25,855 cm−1 (ν1-band), 15,230–14,740 cm−1 (ν2-band) and 9,200–9,145 cm−1 (ν3-band) which are characteristic of divalent nickel in six-fold coordination. The Crystal Field Stabilization Energy (CFSE) of Ni2+ in the four carbonates is calculated from the observed 3A2g(3F) → 3T2g(3F) transition. CFSE is dependent on mineralogy, crystallinity and chemical composition (Al/Mg-content). The splitting of the ν1- and ν3-bands and non-Gaussian shape of ν3-band in the minerals are the effects of Ni-site distortion from regular octahedral. The effect of structural cation substitutions (Mg2+, Ni2+, Fe2+ and trivalent cations, Al3+, Fe3+) in the carbonate minerals is noticed on band shifts. Thus, electronic bands in the UV–Vis–NIR spectra and the overtones and combination bands of OH and carbonate ion in NIR show shifts to higher wavenumbers, particularly for widgiemoolthalite and takovite.

Optical absorption, infrared, Raman and EPR spectral studies on natural Iowaite mineral

Natural iowaite, magnesium–ferric oxychloride mineral having light green color originating from Australia has been characterized by EPR, optical, IR, and Raman spectroscopy. The optical spectrum exhibits a number of electronic bands due to both Fe(III) and Mn(II) ions in iowaite. From EPR studies, the g values are calculated for Fe(III) and g and A values for Mn(II). EPR and optical absorption studies confirm that Fe(III) and Mn(II) are in distorted octahedral geometry. The bands that appear both in NIR and Raman spectra are due to the overtones and combinations of water and carbonate molecules. Thus EPR, optical, and Raman spectroscopy have proven most useful for the study of the chemistry of natural iowaite and chemical changes in the mineral.

Raman spectroscopic study of the antimony containing mineral partzite Cu2Sb2(O,OH)7

Raman spectroscopy of the mineral partzite Cu2Sb2(O,OH)7 complimented with infrared spectroscopy were studied and related to the structure of the mineral. The Raman spectrum shows some considerable complexity with a number of overlapping bands observed at 479, 520, 594, 607 and 620 cm-1 with additional low intensity bands found at 675, 730, 777 and 837 cm-1. Raman bands of partzite in the spectral region 590 to 675 cm-1 are attributable the ν1 symmetric stretching modes. The Raman bands at 479 and 520 cm-1 are assigned to the ν3 antisymmetric stretching modes. Raman bands at 1396 and 1455 cm-1 are attributed to SbOH deformation modes. A complex pattern resulting from the overlapping band of the water and OH units is found. Raman bands are observed at 3266, 3376, 3407, 3563, 3586 and 3622 cm-1. The first three bands are assigned to water stretching vibrations. The three higher wavenumber bands are assigned to the stretching vibrations of the OH units. It is proposed that based upon observation of the Raman spectra that water is involved in the structure of partzite. Thus the formula Cu2Sb2(O,OH)7 may be better written as Cu2Sb2(O,OH)7 •xH2O

Raman spectroscopic study of the multi-anion mineral dixenite CuMn2+14Fe3+(AsO3)5(SiO4)2(AsO4)(OH)6

The mixed anion mineral dixenite has been studied by Raman spectroscopy, complimented with infrared spectroscopy. The Raman spectrum of dixenite shows bands at 839 and 813 cm-1 assigned to the (AsO3)3- symmetric and antisymmetric stretching modes. The most intense Raman band of dixenite is the band at 526 cm-1 and is assigned to the ν2 AsO33- bending mode. DFT calculations enabled the position of AsO22- symmetric stretching mode at 839 cm-1, the antisymmetric stretching mode at 813 cm-1, and the deformation mode at 449 cm-1 to be calculated. Raman bands at 1026 and 1057 cm-1 are assigned to the SiO42- symmetric stretching vibrations and at 1349 and 1386 cm-1 to the SiO42- antisymmetric stretching vibrations. Both Raman and infrared spectra indicate the presence of water in the structure of dixenite. This brings into question the commonly accepted formula of dixenite as CuMn2+14Fe3+(AsO3)5(SiO4)2(AsO4)(OH)6. The formula may be better written as CuMn2+14Fe3+(AsO3)5(SiO4)2(AsO4)(OH)6•xH2O.