Raman and infrared study of phyllosilicates containing heavy metals (Sb,Bi): bismutoferrite and chapmanite

The kaolinite‐like phyllosilicate minerals bismutoferrite BiFe³⁺₂Si₂O₈(OH) and chapmanite SbFe³⁺₂Si₂O₈(OH) have been studied by Raman spectroscopy and complemented with infrared spectra. Tentatively interpreted spectra were related to their molecular structure. The antisymmetric and symmetric stretching vibrations of the Si O Si bridges, δ SiOSi and δ OSiO bending vibrations, ν (Si O_terminal)⁻ stretching vibrations, ν OH stretching vibrations of hydroxyl ions, and δ OH bending vibrations were attributed to the observed bands. Infrared bands in the range 3289–3470 cm⁻¹ and Raman bands in the range 1590–1667 cm⁻¹ were assigned to adsorbed water. O H···O hydrogen‐bond lengths were calculated from the Raman and infrared spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Thermo‐Raman spectroscopy of synthetic nesquehonite — implication for the geosequestration of greenhouse gases

Pure nesquehonite (MgCO₃·3H₂O)/Mg(HCO₃)(OH)·2H₂O was synthesised and characterised by a combination of thermo‐Raman spectroscopy and thermogravimetry with evolved gas analysis. Thermo‐Raman spectroscopy shows an intense band at 1098 cm⁻¹, which shifts to 1105 cm⁻¹ at 450 °C, assigned to the ν₁CO₃²⁻ symmetric stretching mode. Two bands at 1419 and 1509 cm⁻¹ assigned to the ν₃ antisymmetric stretching mode shift to 1434 and 1504 cm⁻¹ at 175 °C. Two new peaks at 1385 and 1405 cm⁻¹ observed at temperatures higher than 175 °C are assigned to the antisymmetric stretching modes of the (HCO₃)⁻ units. Throughout all the thermo‐Raman spectra, a band at 3550 cm⁻¹ is attributed to the stretching vibration of OH units. Raman bands at 3124, 3295 and 3423 cm⁻¹ are assigned to water stretching vibrations. The intensity of these bands is lost by 175 °C. The Raman spectra were in harmony with the thermal analysis data. This research has defined the thermal stability of one of the hydrous carbonates, namely nesquehonite. Thermo‐Raman spectroscopy enables the thermal stability of the mineral nesquehonite to be defined, and, further, the changes in the formula of nesquehonite with temperature change can be defined. Indeed, Raman spectroscopy enables the formula of nesquehonite to be better defined as Mg(OH)(HCO₃)·2H₂O. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopy of CaM2+Ge2O6 (M2+ = Mg,Mn, Fe,Co, Ni,Zn) clinopyroxenes

The Raman spectra of Ge‐clinopyroxenes CaM²⁺Ge₂O₆ (M²⁺ = Mg, Mn, Fe, Co, Ni, Zn), general formula M2M1T₂O₆, are reported for the first time. Their spectral features are discussed in comparison with corresponding Si‐pyroxenes. The vibrational wavenumbers of germanates may be roughly obtained by a scale factor of about ~0.8 by those of the corresponding silicates, due to the Ge‐Si mass difference. The main peaks in the germanate Raman spectra at ~850 and ~540 cm⁻¹ may be related to Ge‐O tetrahedral stretching and chain bending, respectively; minor peaks between 200 and 400 cm⁻¹ are ascribed to bending and stretching of the non‐tetrahedral cations. Within Ge‐pyroxenes, possible correlations between crystallographic parameters and the vibrational wavenumbers are investigated. The main stretching mode at ~850 cm⁻¹ shows wavenumber changes with M²⁺ substitutions, but no simple correlation can be found with M²⁺ cation mass or size. On the other hand, the chain bending wavenumber linearly decreases with increasing ionic radius of the M²⁺ cation: the expansion of the M1 polyhedron reduces the chain kinking angle and the Ge‐Ge distances correspondingly increase. Copyright © 2015 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the antimonate mineral brandholzite Mg[Sb2(OH)12]·6H2O

Raman spectra of brandholzite Mg[Sb₂(OH)₁₂]·6H₂O were studied, complemented with infrared spectra, and related to the structure of the mineral. An intense Raman sharp band at 618 cm⁻¹ is attributed to the SbO symmetric stretching mode. The low‐intensity band at 730 cm⁻¹ is ascribed to the SbO antisymmetric stretching vibration. Low‐intensity Raman bands were found at 503, 526 and 578 cm⁻¹. Corresponding infrared bands were observed at 527, 600, 637, 693, 741 and 788 cm⁻¹. Four Raman bands observed at 1043, 1092, 1160 and 1189 cm⁻¹ and eight infrared bands at 963, 1027, 1055, 1075, 1108, 1128, 1156 and 1196 cm⁻¹ are assigned to δ SbOH deformation modes. A complex pattern resulting from the overlapping band of the water and hydroxyl units is observed. Raman bands are observed at 3240, 3383, 3466, 3483 and 3552 cm⁻¹; infrared bands at 3248, 3434 and 3565 cm⁻¹. The Raman bands at 3240 and 3383 cm⁻¹ and the infrared band at 3248 cm⁻¹ are assigned to water‐stretching vibrations. The two higher wavenumber Raman bands observed at 3466 and 3552 cm⁻¹ and two infrared bands at 3434 and 3565 cm⁻¹ are assigned to the stretching vibrations of the hydroxyl units. Observed Raman and infrared bands in the OH stretching region are associated with O‐H···O hydrogen bonds and their lengths 2.72, 2.79, 2.86, 2.88 and 3.0 Å (Raman) and 2.73, 2.83 and 3.07 Å (infrared). Copyright © 2009 John Wiley & Sons, Ltd.     

Characterization of sodium alginate and its block fractions by surface‐enhanced Raman spectroscopy

The surface‐enhanced Raman scattering (SERS) of sodium alginates and their hetero‐ and homopolymeric fractions obtained from four seaweeds of the Chilean coast was studied. Alginic acid is a copolymer of β‐D ‐mannuronic acid (M) and α‐L guluronic acid (G), linked 1 → 4, forming two homopolymeric fractions (MM and GG) and a heteropolymeric fraction (MG). The SERS spectra were registered on silver colloid with the 632.8 nm line of a He Ne laser. The SERS spectra of sodium alginate and the polyguluronate fraction present various carboxylate bands which are probably due to the coexistence of different molecular conformations. SERS allows to differentiate the hetero‐ and homopolymeric fractions of alginic acid by characteristic bands. In the fingerprint region, all the poly‐D ‐mannuronate samples present a band around 946 cm⁻¹ assigned to C O stretching, and C C H and C O H deformation vibrations, a band at 863 cm⁻¹ assigned to deformation vibration of β‐C₁ H group, and one at 799–788 cm⁻¹ due to the contributions of various vibration modes. Poly‐L ‐guluronate spectra show three characteristic bands, at 928–913 cm⁻¹ assigned to symmetric stretching vibration of C O C group, at 890–889 cm⁻¹ due to C C H, skeletal C C, and C O vibrations, and at 797 cm⁻¹ assigned to α C₁ H deformation vibration. The heteropolymeric fractions present two characteristic bands in the region with the more important one being an intense band at 730 cm⁻¹ due to ring breathing vibration mode. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic investigations of natural jennite from Maroldsweisach,Bavaria, Germany

A full‐range pattern (100–3700 cm⁻¹) analysis of natural jennite was performed for the first time by Raman spectroscopy, applying a polarized laser at a wavelength of 532 nm. A prominent structural feature of jennite is the preferred orientation of Si‐tetrahedron and Ca‐octahedron chains parallel [010]. The latter ones are additionally coupled to H₂O molecules and OH groups. This arrangement leads to a strong dependence on orientation for the intensity ratios of mainly three different regions in the Raman spectra: 180–210, 950–1050 and 3100–3650 cm⁻¹. These sections can be assigned to Ca–O lattice vibrations, Q² Si–tetrahedron stretching and O–H vibrations of H₂O molecules and Ca–OH structures, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

Raman spectroscopic investigation of pure and ytterbium‐doped rare earth silicate crystals

Raman spectroscopy was used to study the molecular structure of a series of selected rare earth (RE) silicate crystals including Y₂SiO₅ (YSO), Lu₂SiO₅ (LSO), (Lu_0.5Y_0.5)₂SiO₅ (LYSO) and their ytterbium‐doped samples. Raman spectra show resolved bands below 500 cm⁻¹ region assigned to the modes of SiO₄ and oxygen vibrations. Multiple bands indicate the nonequivalence of the RE O bonds and the lifting of the degeneracy of the RE ion vibration. Low intensity bands below 500 cm⁻¹ are an indication of impurities. The (SiO₄)⁴⁻ tetrahedra are characterized by bands near 200 cm⁻¹ which show a separation of the components of ν₄ and ν₂, in the 500–700 cm⁻¹ region which are attributed to the distorting bending vibration and in the 880–1000 cm⁻¹ region which are attributed to the symmetric and antisymmetric stretching vibrational modes. The majority of the bands in the 300–610 cm⁻¹ region of Re₂SiO₅ were found to arise from vibrations involving both Si and RE ions, indicating that there is considerable mixing of Si displacements with Si O bending modes and RE O stretching modes. The Raman spectra of RE silicate crystals were analyzed in terms of the molecular structure of the crystals, which enabled separation of the bands attributed to distinct vibrational units. Copyright © 2007 John Wiley & Sons, Ltd.     

Raman spectrum of decrespignyite [(Y,REE)4Cu(CO3)4Cl(OH)5·2H2O] and its relation with those of other halogenated carbonates including bastnasite,hydroxybastnasite, parisite and northupite

Raman spectroscopy complemented with infrared spectroscopy has been used to study the rare‐earth‐based mineral decrespignyite [(Y,REE)₄Cu(CO₃)₄Cl(OH)₅· 2H₂O] and the spectrum compared with the Raman spectra of a series of selected natural halogenated carbonates from different origins including bastnasite, parisite and northupite. The Raman spectrum of decrespignyite displays three bands at 1056, 1070 and 1088 cm⁻¹ attributed to the CO₃²⁻ symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of the CO₃²⁻ symmetric stretching vibration varies with the mineral composition. The Raman spectrum of decrespignyite shows bands at 1391, 1414, 1489 and 1547 cm⁻¹, whereas the Raman spectra of bastnasite, parisite and northupite show a single band at 1433, 1420 and 1554 cm⁻¹, respectively, assigned to the ν₃ (CO₃)²⁻ antisymmetric stretching mode. The observation of additional Raman bands for the ν₃ modes for some halogenated carbonates is significant in that it shows distortion of the carbonate anion in the mineral structure. Four Raman bands are observed at 791, 815, 837 and 849 cm⁻¹, which are assigned to the (CO₃)²⁻ν₂ bending modes. Raman bands are observed for decrespignyite at 694, 718 and 746 cm⁻¹ and are assigned to the (CO₃)²⁻ν₄ bending modes. Raman bands are observed for the carbonate ν₄ in‐phase bending modes at 722 cm⁻¹ for bastnasite, 736 and 684 cm⁻¹ for parisite and 714 cm⁻¹ for northupite. Multiple bands are observed in the OH stretching region for decrespignyite, bastnasite and parisite, indicating the presence of water and OH units in the mineral structure. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the hydrogen‐arsenate mineral pharmacolite Ca(AsO3OH)·2H2O—implications for aquifer and sediment remediation

The removal of arsenate anions from aqueous media, sediments and wasted soils is of environmental significance. The reaction of gypsum with the arsenate anion results in pharmacolite mineral formation, together with related minerals. Raman and infrared (IR) spectroscopy have been used to study the mineral pharmacolite Ca(AsO₃OH)· 2H₂O. The mineral is characterised by an intense Raman band at 865 cm⁻¹ assigned to the ν₁ (AsO₃)²⁻ symmetric stretching mode. The equivalent IR band is found at 864 cm⁻¹. The low‐intensity Raman bands in the range from 844 to 886 cm⁻¹ provide evidence for ν₃ (AsO₃) antisymmetric stretching vibrations. A series of overlapping bands in the 300‐450 cm⁻¹ region are attributed to ν₂ and ν₄ (AsO₃) bending modes. Prominent Raman bands at around 3187 cm⁻¹ are assigned to the OH stretching vibrations of hydrogen‐bonded water molecules and the two sharp bands at 3425 and 3526 cm⁻¹ to the OH stretching vibrations of only weakly hydrogen‐bonded hydroxyls in (AsO₃OH)²⁻ units. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman microscopy of haidingerite Ca(AsO3OH)·H2O and brassite Mg(AsO3OH)·4H2O

Raman spectroscopy has been used to study the arsenate minerals haidingerite Ca(AsO₃OH)·H₂O and brassite Mg(AsO₃OH)·4H₂O. Intense Raman bands in the haidingerite spectrum observed at 745 and 855 cm⁻¹ are assigned to the (AsO₃OH)²⁻ν₃ antisymmetric stretching and ν₁ symmetric stretching vibrational modes. For brassite, two similarly assigned intense bands are found at 809 and 862 cm⁻¹. The observation of multiple Raman bands in the (AsO₃OH)²⁻ stretching and bending regions suggests that the arsenate tetrahedrons in the crystal structures of both minerals studied are strongly distorted. Broad Raman bands observed at 2842 cm⁻¹ for haidingerite and 3035 cm⁻¹ for brassite indicate strong hydrogen bonding of water molecules in the structure of these minerals. OH···O hydrogen‐bond lengths were calculated from the Raman spectra based on empirical relations. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectral investigations on the binary system (acetic acid N,N‐dimethyl formamide)

Raman spectra of acetic acid (AA), N,N‐dimethyl formamide (DMF) and their binary mixtures with varying mole fraction of the AA were recorded in the region 300–1750 cm⁻¹ to investigate the formation of self‐associated dimer and hydrogen‐bonded complexes in a mixed system. The observed spectral features of the CO stretching mode suggest the formation of self‐association with a smaller aggregation size, and also indicate the presence of repulsive interactions between AA and DMF. The existence of two kinds of AA molecules (free and complex) is elucidated from the splitting of the OC O deformation mode. The intermolecular hydrogen‐bond formation and the possibility of attractive interaction between AA and DMF are also examined from the observed spectral features in the CCO symmetric stretching mode of AA, and CN symmetric stretching mode of DMF. Copyright © 2006 John Wiley & Sons, Ltd.     

Transition of chromium oxyhydroxide nanomaterials to chromium oxide: a hot‐stage Raman spectroscopic study

The transition of disc‐like chromium hydroxide nanomaterials to chromium oxide nanomaterials has been studied by hot‐stage Raman spectroscopy. The structure and morphology of α‐CrO(OH) synthesised using hydrothermal treatment were confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The Raman spectrum of α‐CrO(OH) is characterised by two intense bands at 823 and 630 cm⁻¹ attributed to ν₁ Cr^III O symmetric stretching mode and the band at 1179 cm⁻¹ attributed to Cr^III OH δ deformation modes. No bands are observed above 3000 cm⁻¹. The absence of characteristic OH stretching vibrations may be due to short hydrogen bonds in the α‐CrO(OH) structure. Upon thermal treatment of α‐CrO(OH), new Raman bands are observed at 599, 542, 513, 396, 344 and 304 cm⁻¹, which are attributed to Cr₂O₃. This hot‐stage Raman study shows that the transition of α‐CrO(OH) to Cr₂O₃ occurs before 350 °C. Copyright © 2010 John Wiley & Sons, Ltd.     

A Raman spectroscopic study of the antimony mineral klebelsbergite Sb4O4(OH)2(SO4)

Many minerals based upon antimonite and antimonate anions remain to be studied. Most of the bands occur in the low wavenumber region, making the use of infrared spectroscopy difficult. This problem can be overcome by using Raman spectroscopy. The Raman spectra of the mineral klebelsbergite Sb₄O₄(OH)₂(SO₄) were studied and related to the structure of the mineral. The Raman band observed at 971 cm⁻¹ and a series of overlapping bands are observed at 1029, 1074, 1089, 1139 and 1142 cm⁻¹ are assigned to the SO₄²⁻ν₁ symmetric and ν₃ antisymmetric stretching modes, respectively. Two Raman bands are observed at 662 and 723 cm⁻¹, which are assigned to the Sb O ν₃ antisymmetric and ν₁ symmetric stretching modes, respectively. The intense Raman bands at 581, 604 and 611 cm⁻¹ are assigned to the ν₄ SO₄²⁻ bending modes. Two overlapping bands at 481 and 489 cm⁻¹ are assigned to the ν₂ SO₄²⁻ bending mode. Low‐intensity bands at 410, 435 and 446 cm⁻¹ may be attributed to O Sb O bending modes. The Raman band at 3435 cm⁻¹ is attributed to the O H stretching vibration of the OH units. Multiple Raman bands for both SO₄²⁻ and Sb O stretching vibrations support the concept of the non‐equivalence of these units in the klebelsbergite structure. It is proposed that the two sulfate anions are distorted to different extents in the klebelsbergite structure. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and Raman spectroscopic characterisation of the oxalate mineral wheatleyite Na2Cu2+(C2O4)2·2H2O

The mineral wheatleyite has been synthesised and characterised by Raman spectroscopy complimented with infrared spectroscopy. Two Raman bands at 1434 and 1470 cm⁻¹ are assigned to the ν_{(C O)} stretching mode and implies two independent oxalate anions. Two intense Raman bands observed at 904 and 860 cm⁻¹ are assigned to the ν(C C) stretching mode and support the concept of two non‐equivalent oxalate units in the wheatleyite structure. Two strong bands observed at 565 and 585 cm⁻¹ are assigned to the symmetric CCO in plane bending modes. The Raman band at 387 cm⁻¹ is attributed to the CuO stretching vibration and the bands at 127 and 173 cm⁻¹ to OCuO bending vibrations. A comparison is made with Raman spectra of selected natural oxalate bearing minerals. Oxalates are markers or indicators of environmental events. Oxalates are readily determined by Raman spectroscopy. Thus, deterioration of works of art, biogeochemical cycles, plant metal complexation, the presence of pigments and minerals formed in caves can be analysed. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopy of hydrogen‐arsenate group (AsO3OH) in solid‐state compounds: copper mineral phase geminite Cu(AsO3OH)·H2O from different geological environments

The participation of hydrogen‐arsenate group (AsO₃OH)²⁻ in solid‐state compounds may serve as a model example for explaining and clarifying the behaviour of As and other elements during weathering processes in natural environment. The mineral geminite, a hydrated hydrogen‐arsenate mineral of ideal formula Cu(AsO₃OH)·H₂O, has been studied by Raman and infrared spectroscopies. Two samples of geminite of different origin were investigated and the spectra proved quite similar. In the Raman spectra of geminite, six bands are observed at 741, 812, 836, 851, 859 and 885 cm⁻¹ (Salsigne, France), and 743, 813, 843, 853, 871 and 885 cm⁻¹ (Jáchymov, Czech Republic). The band at 851/853 cm⁻¹ is assigned to the ν₁ (AsO₃OH)²⁻ symmetric stretching mode; the other bands are assigned to the ν₃ (AsO₃OH)²⁻ split triply degenerate antisymmetric stretching mode. Raman bands at 309, 333, 345 and 364/310, 333 and 345 cm⁻¹ are attributed to the ν₂ (AsO₃OH)²⁻ bending mode, and a set of higher wavenumber bands (in the range 400–500 cm⁻¹) is assigned to the ν₄ (AsO₃OH)²⁻ split triply degenerate bending mode. A very complex set of overlapping bands is observed in both the Raman and infrared spectra. Raman bands are observed at 2289, 2433, 2737, 2855, 3235, 3377, 3449 and 3521/2288, 2438, 2814, 3152, 3314, 3448 and 3521 cm⁻¹. Two Raman bands at 2289 and 2433/2288 and 2438 cm⁻¹ are ascribed to the strong hydrogen bonded water molecules. The Raman bands at 3235, 3305 and 3377/3152 and 3314 cm⁻¹ may be assigned to the ν OH stretching vibrations of water molecules. Two bands at 3449 and 3521/3448 and 3521 cm⁻¹ are assigned to the OH stretching vibrations of the (AsO₃OH)²⁻ units. The lengths of the O H···O hydrogen bonds vary in the range 2.60–2.94 Å (Raman) and 2.61–3.07 Å (infrared). Two Raman and infrared bands in the region of the bending vibrations of the water molecules prove that structurally non‐equivalent water molecules are present in the crystal structure of geminite. Copyright © 2009 John Wiley & Sons, Ltd.     

On the potential of Raman‐spectroscopy‐based carbonate mass spectrometry

The potential for using Raman spectroscopy to measure stable oxygen isotope ratios (¹⁸O/¹⁶O) in carbonates is evaluated by measuring the Raman spectra and isotope ratios of a suite of 60 synthesized, ¹⁸O‐enriched calcite crystals ranging in composition from natural abundance (0.2 mole‐% ¹⁸O) to 1.2 mole‐% ¹⁸O. We determined the Raman‐inferred isotopic ratios (R_Raman) by fitting curves to the ν₁ symmetric stretching peak at 1086 cm⁻¹ and the smaller satellite peak, associated with the ν₁ stretching mode of singly substituted carbonate groups (C¹⁶O₂¹⁸O) at 1065 cm⁻¹. The ratio of the two peak areas shows a 1:1 correspondence with the ¹⁸O/¹⁶O ratios derived from standard mass spectrometry methods, confirming that the relative intensities of the ν₁ symmetric stretching peaks is a direct measure of the isotopic ratio in the carbonates. The 1‐sigma uncertainties of the R_Raman values of the individual crystals were 0.00079 (384‰ PDB) and 0.00043 (210‰ PDB) for the four‐crystal sample means. This level of uncertainty is much too high to provide significant estimates of natural variability; however, there are multiple prospects for improving the accuracy and precision of the technique. Carbon isotope ratios in carbonates cannot be measured by our approach, but our results highlight the potential of Raman‐based isotope ratio measurement for C and other elements in minerals and organic compounds. Copyright © 2012 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the antimonate mineral bottinoite Ni[Sb2(OH)12]·6H2O and in comparison with brandholzite Mg[Sb5+2(OH)12]·6H2O

Raman spectroscopy was used to study the mineral bottinoite and a comparison with the Raman spectra of brandholzite was made. An intense sharp Raman band at 618 cm⁻¹ is attributed to the SbO symmetric stretching mode. The low intensity band at 735 cm⁻¹ is ascribed to the SbO antisymmetric stretching vibration. Low intensity Raman bands were found at 501, 516 and 578 cm⁻¹. Four Raman bands observed at 1045, 1080, 1111 and 1163 cm⁻¹ are assigned to δ SbOH deformation modes. A complex pattern resulting from the overlapping band of the water and hydroxyl units is observed. Raman bands are observed at 3223, 3228, 3368, 3291, 3458 and 3510 cm⁻¹. The first two Raman bands are assigned to water stretching vibrations. The two higher wavenumber Raman bands observed at 3466 and 3552 cm⁻¹ and two infrared bands at 3434 and 3565 cm⁻¹ are assigned to the stretching vibrations of the hydroxyl units. Observed Raman and infrared bands are connected with O H···O hydrogen bonds and their lengths 2.72, 2.79, 2.86, 2.88 and 3.0 Å (Raman) and 2.73, 2.83 and 3.07 Å (infrared). Copyright © 2010 John Wiley & Sons, Ltd.     

Raman and infrared spectroscopic study of the molybdate‐containing uranyl mineral calcurmolite

Raman and infrared spectra of calcurmolite were recorded and interpreted from the uranium and molybdenum polyhedra, water molecules and hydroxyls point of view. U O bond lengths in uranyl and Mo O bond lengths in MoO₆ octahedra were calculated and O H…O bond lengths were inferred from the spectra. The mineral calcurmolite is characterised by bands assigned to the vibrations of the UO₂ units. These units provide intense Raman bands at 930, 900 and 868 and 823 cm⁻¹. These bands are attributed to the anti‐symmetric and symmetric stretching modes of the UO₂ units, respectively. Raman bands at 794, 700, 644, 378 and 354 cm⁻¹ are attributed to vibrations of the MoO₄ units. The bands at 693 and 668 cm⁻¹ are assigned to the anti‐symmetric and symmetric A_g modes of the terminal MO₂ units. Similar bands are observed at 797 and 773 cm⁻¹ for koechlinite and 798 and 775 cm⁻¹ for lindgrenite. It is probable that some of the bands in the low wavenumber region are attributable to the bending modes of MO₂ units. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the phosphate mineral churchite‐(Y) YPO4·2H2O

Raman spectroscopy has been used to study the rare‐earth mineral churchite‐(Y) of formula (Y,REE)(PO₄) ·2H₂O, where rare‐earth element (REE) is a rare‐earth element. The mineral contains yttrium and, depending on the locality, a range of rare‐earth metals. The Raman spectra of two churchite‐(Y) mineral samples from Jáchymov and Medvědín in the Czech Republic were compared with the Raman spectra of churchite‐(Y) downloaded from the RRUFF data base. The Raman spectra of churchite‐(Y) are characterized by an intense sharp band at 975 cm⁻¹ assigned to the ν₁ (PO₄³⁻) symmetric stretching mode. A lower intensity band observed at around 1065 cm⁻¹ is attributed to the ν₃ (PO₄³⁻) antisymmetric stretching mode. The (PO₄³⁻) bending modes are observed at 497 cm⁻¹ (ν₂) and 563 cm⁻¹ (ν₄). Some small differences in the band positions between the four churchite‐(Y) samples from four different localities were found. These differences may be ascribed to the different compositions of the churchite‐(Y) minerals. Copyright © 2009 John Wiley & Sons, Ltd.     

Spectroscopic analysis of a dye–mineral composite–a Raman and FT‐IR study

In this investigation, we address the question of how organic thioindigo binds to inorganic palygorskite to form a pigment similar to Maya Blue. We also address how such binding, if it occurs, might be affected by varying the proportion of dye relative to that of the mineral, and by varying the length of heating time used in preparation of the pigment. In addition to samples of palygorskite and thioindigo both alone, four synthetic pigment samples were prepared; two samples of 8 wt.% dye, one heated at 170 °C for 3 h and one at 170 °C for 9 h, and two samples of 16 wt.% dye, one heated at 170 °C for 3 h and one at 170 °C for 9 h. All samples were examined using Fourier transform‐infrared (FT‐IR) and FT‐Raman spectroscopy. For the pigment samples, FT‐IR peaks at 1627 cm⁻¹ are attributed to a downshifted CO stretching mode of thioindigo due to dye–clay interaction. This interpretation is corroborated by FT‐Raman CO peaks with 14 cm⁻¹ shifts to lower wavenumber for the pigment relative to thioindigo alone. Additional Raman scattering between 550 cm⁻¹ and 650 cm⁻¹ also suggests dye–clay interaction through metal–oxygen bonding. We are thus led to the possibility of mostly hydrogen bonding between silanol and carbonyl at lower dye concentration, with a predominance of metal–oxygen bonding at higher dye concentration. Copyright © 2008 John Wiley & Sons, Ltd.