A Raman spectroscopic study on the active site of sodium cations in the structure of Na2Ti3O7 during the adsorption of Sr2+ and Ba2+ cations

A detailed study on the structural deformation of trititanate nanofibers after the adsorption of divalent strontium (Sr) and barium (Ba) cations was conducted by using Raman spectroscopy, X‐ray diffraction (XRD) and transmission electron microscopy (TEM). It was found that the Raman bands at 309 cm⁻¹ corresponding to very long Ti O bonds (2.2 Å) and at 883 cm⁻¹ corresponding to the very short Ti O bonds (1.7 Å) decreased in intensity after the adsorption of Ba²⁺ and Sr²⁺ cations. Additionally, the band at 922 cm⁻¹ corresponding to an intermediate length Ti O bond was observed to weaken with the adsorption of divalent cations, indicating that the TiO₆ octahedra in Na₂Ti₃O₇ are more regular. These results suggest that the active sodium (Na⁺) cations in Na₂Ti₃O₇ should be located at the corner of the TiO₆ octahedral slabs, i.e. the plane (003). This was further confirmed by a large decrease of diffraction intensity of the plane (003) observed in the XRD pattern. Copyright © 2010 John Wiley & Sons, Ltd.     

A Raman spectroscopic study on the allocation of ammonium adsorbing sites on H2Ti3O7 nanofibre and its structural derivation during calcination

The adsorption behaviour of ammonium ions and the structural features of layered proton trititanate were characterised by using Raman spectroscopy, X‐ray diffraction (XRD) and transmission electron microscopy. It revealed that the intensity of the Raman band at 309 cm⁻¹, assigned to very long Ti O bonds (0.22 nm), reduced, whereas the band at 890 cm⁻¹, assigned to very short Ti O bonds (0.17 nm), increased slightly after the adsorption of ammonium ions (NH₄⁺). The adsorption of ammonium ions enlarged the interlayer distance of the (200) plane. Ammonium ions were located at the corner of the TiO₆ octahedral slabs. This was further confirmed by XRD, with an increased intensity of the (201 ) plane being observed. Copyright © 2010 John Wiley & Sons, Ltd.     

Structural phase transition due to La substitution in Bi4Ti3O12

The structure of Bi_4?x La _x Ti₃O₁₂ (BLaTx) as a function of La content from x = 0.00 to 1.25 was studied by Raman spectroscopy and X-ray diffraction (XRD). It was observed that the Raman modes evolve discontinuously at about x = 1.00, which indicates a structural phase transition. Specifically, the B _2g and B _3g Raman modes shown evidences to coalesce into E _g modes with increasing La content. The evolution of Raman modes corresponds to the weakening of ferroelectric orthorhombic lattice distortion with increasing La substitution when x ≤ 1.00 and the final transition into the paraelectric tetragonal structure at higher La content. XRD and electrical measurement results confirm this phase transition by the observation that diffraction peaks from (200) and (020) planes of BLaT0.75 coalesce into one peak in BLaT1.25 and by the corresponding disappearance of remanent polarisation. The impact of La substitution on electrical properties of BLaTx is discussed briefly.     

Raman spectroscopic study of the antimonate mineral lewisite (Ca,Fe, Na)2(Sb,Ti)2O6(O,OH)7

The mineral lewisite, (Ca, Fe, Na)₂(Sb, Ti)₂O₆(O, OH)₇, an antimony-bearing mineral, has been studied by Raman spectroscopy. A comparison is made with the Raman spectra of other minerals, including bindheimite, stibiconite, and roméite. The mineral lewisite is characterised by an intense sharp band at 517 cm^?1 with a shoulder at 507 cm^?1 assigned to SbO stretching modes. Raman bands of medium intensity for lewisite are observed at 300, 356, and 400 cm^?1. These bands are attributed to OSbO bending vibrations. Raman bands in the OH stretching region are observed at 3200, 3328, 3471 cm^?1, with a distinct shoulder at 3542 cm^?1. The latter is assigned to the stretching vibration of OH units. The first three bands are attributed to water stretching vibrations. The observation of bands in the 3200–3500 cm^?1 region suggests that water is involved in the lewisite structure. If this is the case then the formula may be better written as (Ca, Fe²⁺, Na)₂(Sb, Ti)₂(O, OH)₇ xH₂O.     

Raman spectroscopic study of the selenite mineral mandarinoite Fe2Se3O9·6H2O

Selenites and tellurites may be subdivided according to formula and structure. There are five groups, based upon the formulae (a) A(XO₃), (b) A(XO₃·) xH₂O, (c) A₂(XO₃)₃·xH₂O, (d) A₂(X₂O₅) and (e) A(X₃O₈). Of the selenites, molybdomenite is an example of type (a); chalcomenite, clinochalcomenite, cobaltomenite and ahlfeldite are minerals of type (b); mandarinoite Fe₂Se₃O₉·6H₂O is an example of type (c). Raman spectroscopy has been used to characterise the mineral mandarinoite. The intense, sharp band at 814 cm⁻¹ is assigned to the symmetric stretching (Se₃O₉)⁶⁻ units. Three Raman bands observed at 695, 723 and 744 cm⁻¹ are attributed to the ν₃ (Se₃O₉)⁶⁻ anti‐symmetric stretching modes. Raman bands at 355, 398 and 474 cm⁻¹ are assigned to the ν₄ and ν₂ bending modes. Raman bands are observed at 2796, 2926, 3046, 3189 and 3507 cm⁻¹ and are assigned to OH stretching vibrations. The observation of multiple OH stretching vibrations suggests the non‐equivalence of water in the mandarinoite structure. The use of the Libowitzky empirical function provides hydrogen bond distances of 2.633(9) Å (2926 cm⁻¹), 2.660(0) Å (3046 cm⁻¹), 2.700(0) Å (3189 cm⁻¹) and 2.905(3) Å (3507 cm⁻¹). The sharp, intense band at 3507 cm⁻¹ may be due to hydroxyl units. It is probable that some of the selenite units have been replaced by hydroxyl units. Copyright © 2008 John Wiley & Sons, Ltd.     

Pressure effect on the Raman and photoluminescence spectra of Eu3+-doped Na2Ti6O13 nanorods

Eu³⁺-doped Na₂Ti₆O₁₃ (Na₂Ti₆O₁₃:Eu) nanorods with diameters of 30 nm and lengths 400 nm were synthesized by hydrothermal and heat treatment methods. Raman spectra at ambient conditions indicated a pure monoclinic phase (space group C2/m) of the nanorods. The relations between structural and optical properties of Na₂Ti₆O₁₃:Eu nanorods under high pressures were obtained by photoluminescence and Raman spectra. Two structural transition points at 1.39 and 15.48 GPa were observed when the samples were pressurized. The first transition point was attributed to the crystalline structural distortion. The later transition point was the result of pressure-induced amorphization, and the high-density amorphous (HDA) phase formed after 15.48 GPa was structurally related to the monoclinic baddeleyite structured TiO₂ (P2₁/c). However, the site symmetry of the local environment around the Eu³⁺ ions in Na₂Ti₆O₁₃ increased with the rising pressure. These above results indicate the occurrence of short-range order for the local asymmetry around the Eu³⁺ ions and long-range disorder for the crystalline structure of Na₂Ti₆O₁₃:Eu nanorods by applying pressure. After releasing the pressure from 22.74 GPa, the HDA phase is transformed to low-density amorphous form, which is attributed to be structurally related to the α-PbO₂-type TiO₂.     

Raman spectra of mirabilite,Na2SO4·10H2O and the rediscovered metastable heptahydrate,Na2SO4·7H2O

Salt crystallisation in pores is known to cause serious damage to masonry. Sodium sulphate, often regarded as one of the most damaging salts, has a rich hydrate chemistry including one rediscovered metastable hydrate and a new high pressure octahydrate plus five known polymorphs of the anhydrous phase. The difficulty in working with these hydrates lies in their strong tendency to dehydrate or to convert to the stable phase, in the case of the heptahydrate. We present Raman spectra and a table of peak wavenumbers for randomly oriented crystals of mirabilite and the metastable heptahydrate, sufficient to distinguish between these phases that have SO₄ν₁ values of 989.3 and 987.6 cm⁻¹, respectively. Mirabilite has a Raman spectrum very similar to the free sulphate anion in solution, which is probably due to the mobility of oxygen atoms within the sulphate tetrahedron. The oxygen atoms in the heptahydrate sulphate groups have no partial occupancy, and predicted peak splitting is observed in the region 400–1200 cm⁻¹. 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.     

Phonon anomalies and structural transition in spin ice Dy2Ti2O7: a simultaneous pressure‐dependent and temperature‐dependent Raman study

We revisit the assignment of Raman phonons of rare‐earth titanates by performing Raman measurements on single crystals of O¹⁸ isotope‐rich spin ice and nonmagnetic pyrochlores and compare the results with their O¹⁶ counterparts. We show that the low‐wavenumber Raman modes below 250 cm⁻¹ are not due to oxygen vibrations. A mode near 200 cm⁻¹, commonly assigned as F_2g phonon, which shows highly anomalous temperature dependence, is now assigned to a disorder‐induced Raman active mode involving Ti⁴⁺ vibrations. Moreover, we address here the origin of the ‘new’ Raman mode, observed below T_C ~ 110 K in Dy₂Ti₂O₇, through a simultaneous pressure‐dependent and temperature‐dependent Raman study. Our study confirms the ‘new’ mode to be a phonon mode. We find that dT_C/dP = + 5.9 K/GPa. Temperature dependence of other phonons has also been studied at various pressures up to ~8 GPa. We find that pressure suppresses the anomalous temperature dependence. The role of the inherent vacant sites present in the pyrochlore structure in the anomalous temperature dependence is also discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

Correlating Raman peak shifts with phase transformation and defect densities: a comprehensive TEM and Raman study on silicon

Silicon is the most often used material in micro electromechanical systems (MEMS). Detailed understanding of its mechanical properties as well as the microstructure is crucial for the reliability of MEMS devices. In this paper, we investigate the microstructure changes upon indentation of single crystalline (100) oriented silicon by transmission electron microscopy (TEM) and Raman microscopy. TEM cross sections were prepared by focused ion beam (FIB) at the location of the indent. Raman microscopy and TEM revealed the occurrence of phase transformations and residual stresses upon deformation. Raman microscopy was also used directly on the cross‐sectional TEM lamella and thus microstructural details could be correlated to peak shape and peak position. The results show, however, that due to the implanted Ga⁺ ions in the lamella the silicon Raman peak is shifted significantly to lower wavenumbers. This hinders a quantitative analysis of residual stresses in the lamella. Furthermore, Raman microscopy also possesses the ability to map deformation structures with a lateral resolution in the submicron range. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic study of layered quaternary ferrite Ba12Fe28Ti15O84

Ba–Fe–Ti oxides are nowadays attracting considerable interest for the production of permanent magnets and microwave devices, due to their high dielectric constant. Among these materials, recently the quaternary ferrite Ba₁₂Fe₂₈Ti₁₅O₈₄ (BFT) was discovered to possess ferrimagnetic properties at room temperature with a main magnetic transition at about 420?K and complete disappearance of magnetisation above 700?K. In this study, we report for the first time on the Raman spectrum of BFT samples prepared with different methods. Raman spectra were recorded in dependence of temperature and a preliminary assignment of modes was attempted. Coupling the Raman results with previous magnetic studies allowed gaining more insight on the structural mechanism at play in correspondence of the main magnetic transition.     

Raman spectroscopic study of the mixed anion mineral yecoraite Bi5Fe3O9(Te4+O3)(Te6+O4)2·9H2O

Tellurates are rare minerals as the tellurate anion is readily reduced to the tellurite ion. Often minerals with both tellurate and tellurite anions are found. An example of such a mineral containing tellurate and tellurite is yecoraite. Raman spectroscopy has been used to study this mineral, the exact structure of which is unknown. Two Raman bands at 796 and 808 cm⁻¹ are assigned to the ν₁(TeO₄)²⁻ symmetric and ν₃(TeO₃)²⁻ antisymmetric stretching modes and Raman bands at 699 cm⁻¹ are attributed to the ν₃(TeO₄)²⁻ antisymmetric stretching mode and the band at 690 cm⁻¹ to the ν₁(TeO₃)²⁻ symmetric stretching mode. The intense band at 465 cm⁻¹ with a shoulder at 470 cm⁻¹ is assigned the (TeO₄)²⁻ and (TeO₃)²⁻ bending modes. Prominent Raman bands are observed at 2878, 2936, 3180 and 3400 cm⁻¹. The band at 3936 cm⁻¹ appears quite distinct and the observation of multiple bands indicates the water molecules in the yecoraite structure are not equivalent. The values for the OH stretching vibrations listed provide hydrogen bond distances of 2.625 Å (2878 cm⁻¹), 2.636 Å (2936 cm⁻¹), 2.697 Å (3180 cm⁻¹) and 2.798 Å (3400 cm⁻¹). This range of hydrogen bonding contributes to the stability of the mineral. A comparison of the Raman spectra of yecoraite with that of tellurate containing minerals kuranakhite, tlapallite and xocomecatlite is made. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the selenite mineral: ahlfeldite,NiSeO3·2H2O

Raman spectroscopy has been used to study the selenite mineral ahlfeldite. A comparison is made with the Raman spectra of chalcomenite, cobaltomenite and clinochalcomenite. Selenite minerals are characterised by the position of the symmetric stretching mode which is observed at higher wavenumbers than the anti‐symmetric stretching mode. The selenite ion has C_3v symmetry and four modes, 2A₁ and 2E. These modes are observed at 813, 472 cm⁻¹ (A₁) and 685, 710, 727 and 367 and 396 cm⁻¹ (E). Bands assigned to the water stretching vibrations are observed for ahlfeldite at 3385 cm⁻¹, for chalcomenite at 2953, 3184 and 3506 cm⁻¹ and for clinochalcomenite at 2909, 3193 and 3507 cm⁻¹. A comparison of the Raman spectra of chalcomenite, clinochalcomenite and cobaltomenite is made. The position of these bands enabled hydrogen bond distances in the selenite structure to be estimated. Hydrogen bond distances for ahlfeldite, chalcomenite and clinochalcomenite were determined to be similar. Copyright © 2008 John Wiley & Sons, Ltd.     

Vibrational spectroscopic study of Sr2ZnTeO6 double perovskites

Sr₂ZnTeO₆ ceramics were prepared by the solid‐state route and their vibrational phonon modes were investigated using optical spectroscopic techniques, for the first time. X‐ray diffraction (XRD) and Raman and infrared spectroscopies were employed to investigate the structures of these perovskite materials and the results analysed together with group‐theoretical predictions. The number and behaviour of the first‐order modes observed in both spectroscopic techniques are in agreement with the calculations for a tetragonal I4/m space group. The complete set of the optical phonon modes was determined, and the intrinsic dielectric properties of the materials were evaluated, allowing us to discuss their potential application in microwave (MW) circuitry. Copyright © 2009 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.     

Raman spectroscopic study of the tellurite minerals: graemite CuTeO3·H2O and teineite CuTeO3·2H2O

Tellurites may be subdivided according to formula and structure. There are five groups based upon the formulae (a) A(XO₃), (b) A(XO₃)·xH₂O, (c) A₂(XO₃)₃·xH₂O, (d) A₂(X₂O₅) and (e) A(X₃O₈). Raman spectroscopy has been used to study the tellurite minerals teineite and graemite; both contain water as an essential element of their stability. The tellurite ion should show a maximum of six bands. The free tellurite ion will have C_3v symmetry and four modes, 2A₁ and 2 E. Raman bands for teineite at 739 and 778 cm⁻¹ and for graemite at 768 and 793 cm⁻¹ are assigned to the ν₁ (TeO₃)²⁻ symmetric stretching mode while bands at 667 and 701 cm⁻¹ for teineite and 676 and 708 cm⁻¹ for graemite are attributed to the ν₃ (TeO₃)²⁻ antisymmetric stretching mode. The intense Raman band at 509 cm⁻¹ for both teineite and graemite is assigned to the water librational mode. Raman bands for teineite at 318 and 347 cm⁻¹ are assigned to the (TeO₃)²⁻ν₂(A₁) bending mode and the two bands for teineite at 384 and 458 cm⁻¹ may be assigned to the (TeO₃)²⁻ν₄(E) bending mode. Prominent Raman bands, observed at 2286, 2854, 3040 and 3495 cm⁻¹, are attributed to OH stretching vibrations. The values for these OH stretching vibrations provide hydrogen bond distances of 2.550(6) Å (2341 cm⁻¹), 2.610(3) Å (2796 cm⁻¹) and 2.623(2) Å (2870 cm⁻¹) which are comparatively short for secondary minerals. Copyright © 2008 John Wiley & Sons, Ltd.     

High-temperature Raman spectroscopic study of vanadoborate Na_3VO_2B_6O_(11)

Raman spectra of a vanadoborate(Na3VO2B6O11) crystal from room temperature up to the melting point have been recorded. The main internal vibrational modes of the crystal have been assigned. It was found that all the Raman bands exhibit decreases in frequency and the widths of the Raman bands increase with the increase of temperature. However,no phase transition was observed under 525℃. The micro-structure of its melt was studied by quantum chemistry ab initio calculation. The continuous three-dimensional network of the crystal collapsed and transformed into VO_4 and VBO_6 clusters during the melting process with an isomerization reaction from four-coordinated boron to a three-coordinated species.     

Raman spectroscopy study of Na2MoO4·2H2O and Na2MoO4 under hydrostatic pressure

Raman spectroscopy measurements of polycrystalline Na₂MoO₄·2H₂O (NMHO) and Na₂MoO₄ (NM) under hydrostatic pressure (from 0 to 10 GPa) were performed. This study allowed us to monitor the stretching and bending vibrations of MoO₄ ions as well as the translational modes as a function of pressure. The pressure dependence of the wavenumbers of the modes indicates that the Na₂MoO₄·2H₂O undergoes two phase transitions at about ∼3 and ∼4 GPa. When releasing pressure, we have observed that the original spectrum is recovered, thereby pointing to a reversible process. The Na₂MoO₄ (NM) starting phase was found to be stable up to 10 GPa. The pressure‐dependent Raman data for NM did not reveal any structural modification. The influence of the pressure‐transmitting medium on the phase transitions is also discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl mineral natrouranospinite (Na2,Ca)[(UO2)(AsO4)]2· 5H2O

Raman spectra of natrouranospinite complemented with infrared spectra were studied and related to the structure of the mineral. Observed bands were assigned to the stretching and bending vibrations of (UO₂)²⁺ and (AsO₄)³⁻ units and of water molecules. U O bond lengths in uranyl and O H···O hydrogen bond lengths were calculated from the Raman and infrared spectra. Copyright © 2009 John Wiley & Sons, Ltd.