A vibrational spectroscopic study of the phosphate mineral cyrilovite Na(Fe3+)3(PO4)2(OH)4·2(H2O) and in comparison with wardite

Vibrational spectroscopy enables subtle details of the molecular structure of cyrilovite to be determined. Single crystals of a pure phase from a Brazilian pegmatite were used. Cyrilovite is the Fe3+ member of the wardite group. The infrared and Raman spectroscopy were applied to compare the structure of cyrilovite with that of wardite. The Raman spectrum of cyrilovite in the 800–1400 cm−1 spectral range shows two intense bands at 992 and 1055 cm−1 assigned to the ν1View the MathML source symmetric stretching vibrations. A series of low intensity bands at 1105, 1136, 1177 and 1184 cm−1 are assigned to the ν3View the MathML source antisymmetric stretching modes. The infrared spectrum of cyrilovite in the 500–1300 cm−1 shows much greater complexity than the Raman spectrum. Strong infrared bands are found at 970 and 1007 cm−1 and are attributed to the ν1View the MathML source symmetric stretching mode. Raman bands are observed at 612 and 631 cm−1 and are assigned to the ν4 out of plane bending modes of the View the MathML source unit. In the 2600–3800 cm−1 spectral range, intense Raman bands for cyrilovite are found at 3328 and 3452 cm−1 with a broad shoulder at 3194 cm−1 and are assigned to OH stretching vibrations. Sharp infrared bands are observed at 3485 and 3538 cm−1. Raman spectroscopy complimented with infrared spectroscopy has enabled the structure of cyrilovite to be ascertained and compared with that of wardite.

SEM-EDX, Raman and infrared spectroscopic characterization of the phosphate mineral frondelite (Mn2+)(Fe3+)4(PO4)3(OH)5

We have analyzed a frondelite mineral sample from the Cigana mine, located in the municipality of Conselheiro Pena, a well-known pegmatite in Brazil. In the Cigana pegmatite, secondary phosphates, namely eosphorite, fairfieldite, fluorapatite, frondelite, gormanite, hureaulite, lithiophilite, reddingite and vivianite are common minerals in miarolitic cavities and in massive blocks after triphylite. The chemical formula was determined as (Mn0.68, Fe0.32)(Fe3+)3,72(PO4)3.17(OH)4.99. The structure of the mineral was assessed using vibrational spectroscopy. Bands attributed to the stretching and bending modes of PO4 3- and HOPO3 3- units were identified. The observation of multiple bands supports the concept of symmetry reduction of the phosphate anion in the frondelite structure. Sharp Raman and infrared bands at 3581 cm−1 is assigned to the OH stretching vibration. Broad Raman bands at 3063, 3529 and 3365 cm−1 are attributed to water stretching vibrational modes.

Infrared and Raman spectroscopic characterisation of the sulphate mineral creedite – Ca3Al2SO4(F,OH)·2H2O – and in comparison with the alums

The mineral creedite is a fluorinated hydroxy hydrated sulphate of aluminium and calcium of formula Ca3Al2SO4(F,OH)·2H2O. The mineral has been studied by a combination of electron probe analysis to determine the molecular formula of the mineral and the structure assessed by vibrational spectroscopy. The spectroscopy of creedite may be compared with that of the alums. The Raman spectrum of creedite is characterised by an intense sharp band at 986 cm−1 assigned to the View the MathML source ν1 (Ag) symmetric stretching mode. Multiple bands of creedite in the antisymmetric stretching region support the concept of a reduction in symmetry of the sulphate anion. Multiple bands are also observed in the bending region with the three bands at 601, 629 and 663 cm−1 assigned to the View the MathML source ν4 (Ag) bending modes. The observation of multiple bands at 440, 457 and 483 cm−1 attributed to the View the MathML source ν2 (Bg) bending modes supports the concept that the symmetry of the sulphate is reduced by coordination to the water bonded to the Al3+ in the creedite structure. The splitting of the ν2, ν3 and ν4 modes is attributed to the reduction of symmetry of the SO4 and it is proposed that the sulphate coordinates to water in the hydrated aluminium in bidentate chelation.

Infrared and Raman spectroscopic characterization of the phosphate mineral leucophosphite - K(Fe3+)2(PO4)2(OH)·2(H2O)

The phosphate mineral leucophosphite K(Fe2)3þ(PO4)2(OH) · 2H2O has been characterized by SEM-EDS, Raman, and infrared spectro- scopic measurements. The mineral is predominantly a K and Fe phosphate with some minor substitution of Al in the Fe3þ site. Raman bands at 994 and 1058 cm-1 are assigned to the symmetric stretching modes of PO3- and HPO2- units. The Raman bands at 1104, 1135, and 1177 cm-1 are assigned to the PO3- and HPO2- antisymmetric stretching modes. Raman and infrared spectra in the 2600–3800 cm-1 region show a complex set of overlapping bands, which may be resolved into the component bands. The Raman bands observed at 3325, 3355, and 3456 cm-1 are attributed to water stretching vibrations, and in the infrared spectrum, bands at 3237, 3317, and 3453 cm-1 are assigned to water stretching bands.

Infrared and Raman spectroscopic characterization of the silicate-carbonate mineral carletonite – KNa4Ca4Si8O18(CO3)4(OH,F) H2O

Abstract An assessment of the molecular structure of carletonite a rare phyllosilicate mineral with general chemical formula given as KNa4Ca4Si8O18(CO3)4(OH,F)·H2O has been undertaken using vibrational spectroscopy. Carletonite has a complex layered structure. Within one period of c, it contains a silicate layer of composition NaKSi8O18·H2O, a carbonate layer of composition NaCO3·0.5H2O and two carbonate layers of composition NaCa2CO3(F,OH)0.5. Raman bands are observed at 1066, 1075 and 1086 cm−1. Whether these bands are due to the CO32- ν1 symmetric stretching mode or to an SiO stretching vibration is open to question. Multiple bands are observed in the 300–800 cm−1 spectral region, making the attribution of these bands difficult. Multiple water stretching and bending modes are observed showing that there is much variation in hydrogen bonding between water and the silicate and carbonate surfaces.

Pt/Nanograined ZnO/SiC Schottky diode based hydrogen and propene sensor

A nanostructured Schottky diode was fabricated to sense hydrogen and propene gases in the concentration range of 0.06% to 1%. The ZnO sensitive layer was deposited on SiC substrate by pulse laser deposition technique. Scanning electron microscopy and X-ray diffraction characterisations revealed presence of wurtzite structured ZnO nanograins grown in the direction of (002) and (004). The nanostructured diode was investigated at optimum operating temperature of 260 °C. At a constant reverse current of 1 mA, the voltage shifts towards 1% hydrogen and 1% propene were measured as 173.3 mV and 191.8 mV, respectively.

Thermoanalytical study of the minerals apophyllite-(KF) KCa4Si8O20F·8H2O and apophyllite-(KOH) KCa4Si8O20(F,OH)·8H2O

The name apophyllite refers to a specific group of phyllosilicates, a class of minerals that also includes the micas and are a class of minerals of similar chemical makeup that comprise a solid solution series, and includes the members apophyllite-(KF), apophyllite-(KOH) and apophyllite-(NaF). Fluorapophyllite apophyllite-(KF) and hydroxyapophyllite apophyllite-(KOH) are different minerals only because of the difference in percentages of fluorine to hydroxyl ions. Three apophyllite minerals have been characterised by thermogravimetric analysis and infrared spectroscopy. Dehydration takes place in several steps. Major mass losses occur at around 205–220 °C and at 400–429 °C. Minor mass losses are observed around 242–292 °C. It is proposed that dehydration occurs in the first decomposition step. Water is lost over the temperature range 125–250, 250–325 and 325–525 °C with the loss of 4.5, 0.5 and 3.0 mol of water. Water functions as zeolitic water and is also coordinated to the silica surfaces.

Vibrational spectroscopy of the mineral meyerhofferite CaB3O3(OH)5·H2O – An assessment of the molecular structure

Meyerhofferite is a calcium hydrated borate mineral with ideal formula: CaB3O3(OH)5�H2O and occurs as white complex acicular to crude crystals with length up to �4 cm, in fibrous divergent, radiating aggregates or reticulated and is often found in sedimentary or lake-bed borate deposits. The Raman spectrum of meyerhofferite is dominated by intense sharp band at 880 cm�1 assigned to the symmetric stretching mode of trigonal boron. Broad Raman bands at 1046, 1110, 1135 and 1201 cm�1 are attributed to BOH in-plane bending modes. Raman bands in the 900–1000 cm�1 spectral region are assigned to the antisymmetric stretching of tetrahedral boron. Distinct OH stretching Raman bands are observed at 3400, 3483 and 3608 cm�1. The mineral meyerhofferite has a distinct Raman spectrum which is different from the spectrum of other borate minerals, making Raman spectroscopy a very useful tool for the detection of meyerhofferite in sedimentary and lake bed deposits.

Vibrational spectroscopy of the phosphate mineral kovdorskite – Mg2PO4(OH)⋅3H2O

The mineral kovdorskite Mg2PO4(OH)�3H2O was studied by electron microscopy, thermal analysis and vibrational spectroscopy. A comparison of the vibrational spectroscopy of kovdorskite is made with other magnesium bearing phosphate minerals and compounds. Electron probe analysis proves the mineral is very pure. The Raman spectrum is characterized by a band at 965 cm�1 attributed to the PO3� 4 m1 symmetric stretching mode. Raman bands at 1057 and 1089 cm�1 are attributed to the PO3�4 m3 antisymmetric stretching modes. Raman bands at 412, 454 and 485 cm�1 are assigned to the PO3�4 m2 bending modes. Raman bands at 536, 546 and 574 cm�1 are assigned to the PO3�4 m4 bending modes. The Raman spectrum in the OH stretching region is dominated by a very sharp intense band at 3681 cm�1 assigned to the stretching vibration of OH units. Infrared bands observed at 2762, 2977, 3204, 3275 and 3394 cm�1 are attributed to water stretching bands. Vibrational spectroscopy shows that no carbonate bands are observed in the spectra; thus confirming the formula of the mineral as Mg2PO4(OH)�3H2O.

Vibrational spectroscopic characterization of the phosphate mineral series eosphorite–childrenite–(Mn,Fe)Al(PO4)(OH)2·(H2O)

The phosphate mineral series eosphorite–childrenite–(Mn,Fe)Al(PO4)(OH)2·(H2O) has been studied using a combination of electron probe analysis and vibrational spectroscopy. Eosphorite is the manganese rich mineral with lower iron content in comparison with the childrenite which has higher iron and lower manganese content. The determined formulae of the two studied minerals are: (Mn0.72,Fe0.13,Ca0.01)(Al)1.04(PO4, OHPO3)1.07(OH1.89,F0.02)·0.94(H2O) for SAA-090 and (Fe0.49,Mn0.35,Mg0.06,Ca0.04)(Al)1.03(PO4, OHPO3)1.05(OH)1.90·0.95(H2O) for SAA-072. Raman spectroscopy enabled the observation of bands at 970 cm−1 and 1011 cm−1 assigned to monohydrogen phosphate, phosphate and dihydrogen phosphate units. Differences are observed in the area of the peaks between the two eosphorite minerals. Raman bands at 562 cm−1, 595 cm−1, and 608 cm−1 are assigned to the �4 bending modes of the PO4, HPO4 and H2PO4 units; Raman bands at 405 cm−1, 427 cm−1 and 466 cm−1 are attributed to the �2 modes of these units. Raman bands of the hydroxyl and water stretching modes are observed. Vibrational spectroscopy enabled details of the molecular structure of the eosphorite mineral series to be determined.

The molecular structure of the phosphate mineral senegalite Al2(PO4)(OH)3⋅3H2O – A vibrational spectroscopic study

We have studied the mineral senagalite, a hydrated hydroxy phosphate of aluminium with formula Al2(PO4)(OH)3⋅3H2O using a combination of electron microscopy and vibrational spectroscopy. Senegalite crystal aggregates shows tabular to prismatic habitus and orthorhombic form. The Raman spectrum is dominated by an intense band at 1029 cm−1 assigned to the PO43- ν1 symmetric stretching mode. Intense Raman bands are found at 1071 and 1154 cm−1 with bands of lesser intensity at 1110, 1179 and 1206 cm−1 and are attributed to the PO43- ν3 antisymmetric stretching vibrations. The infrared spectrum shows complexity with a series overlapping bands. A comparison is made with spectra of other aluminium containing phosphate minerals such as augelite and turquoise. Multiple bands are observed for the phosphate bending modes giving support for the reduction of symmetry of the phosphate anion. Vibrational spectroscopy offers a means for the assessment of the structure of senagalite.

Vibrational spectroscopic characterization of the phosphate mineral kulanite Ba(Fe2+,Mn2+,Mg)2(Al,Fe3+)2(PO4)3(OH)3

The mineral kulanite BaFe2Al2(PO4)3(OH)3, a barium iron aluminum phosphate, has been studied by using a combination of electron microscopy and vibrational spectroscopy. Scanning electron microscopy with EDX shows the mineral is homogenous with no other phases present. The Raman spectrum is dominated by an intense band at 1022 cm−1 assigned to the PO43-ν1 symmetric stretching mode. Low intensity Raman bands at 1076, 1110, 1146, 1182 cm−1 are attributed to the PO43-ν3 antisymmetric stretching vibrations. The infrared spectrum shows a complex spectral profile with overlapping bands. Multiple phosphate bending vibrations supports the concept of a reduction in symmetry of the phosphate anion. Raman spectrum at 3211, 3513 and 3533 cm−1 are assigned to the stretching vibrations of the OH units. Vibrational spectroscopy enables aspects on the molecular structure of kulanite to be assessed.

Vibrational spectroscopy of the phosphate mineral lazulite – (Mg, Fe)Al2(PO4)2·(OH)2 found in the Minas Gerais, Brazil

This research was done on lazulite samples from the Gentil mine, a lithium bearing pegmatite located in the municipality of Mendes Pimentel, Minas Gerais, Brazil. Chemical analysis was carried out by electron microprobe analysis and indicated a magnesium rich phase with partial substitution of iron. Traces of Ca and Mn, (which partially replaced Mg) were found. The calculated chemical formula of the studied sample is: (Mg0.88, Fe0.11)Al1.87(PO4)2.08(OH)2.02. The Raman spectrum of lazulite is dominated by an intense sharp band at 1060 cm-1 assigned to PO stretching vibrations of of tetrahedral [PO4] clusters presents into the HPO2/4- units. Two Raman bands at 1102 and 1137 cm-1 are attributed to both the HOP and PO antisymmetric stretching vibrations. The two infrared bands at 997 and 1007 cm-1 are attributed to the m1 PO3/4- symmetric stretching modes. The intense bands at 1035, 1054, 1081, 1118 and 1154 cm-1 are assigned to the v3PO3/4- antisymmetric stretching modes from both the HOP and tetrahedral [PO4] clusters. A set of Raman bands at 605, 613, 633 and 648 cm-1 are assigned to the m4 out of plane bending modes of the PO4, HPO4 and H2PO4 units. Raman bands observed at 414, 425, 460, and 479 cm-1 are attributed to the m2 tetrahedral PO4 clusters, HPO4 and H2PO4 bending modes. The intense Raman band at 3402 and the infrared band at 3403 cm-1 are assigned to the stretching vibration of the OH units. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral lazulite to be understood.

Vibrational spectroscopic characterization of the phosphate mineral bermanite–Mn2+Mn23+(PO4)2(OH)2.4(H2O)

Bermanite Mn2þMn3þ2 ðPO4Þ2ðOHÞ2 � 4ðH2OÞ is a mixed valent hydrated hydroxy phosphate mineral. The mineral is reddish-brown and occurs in crystal aggregates and as lamellar masses. Bermanite is a common mineral in granitic pegmatites. The chemical composition of bermanite was obtained using EDS techniques. We have studied the molecular structure of bermanite using vibrational spectroscopy. The mineral is characterized by a Raman doublet at 991 and 999 cm-1 attributed to the phosphate stretching mode of two non-equivalent phosphate units. Raman bands at 1071, 1117 and 1142 cm-1 are assigned to the phosphate antisymmetric stretching modes. The hydroxyl stretching spectral region is complex with overlapping bands attributed to water and hydroxyl stretching vibrations. Vibrational spectroscopy proves most useful for the study of the mineral bermanite.

Infrared and Raman spectroscopic characterization of the borate mineral colemanite – CaB3O4(OH)3·H2O – implications for the molecular structure

Colemanite CaB3O4(OH)3 H2O is a secondary borate mineral formed from borax and ulexite in evaporate deposits of alkaline lacustrine sediments. The basic structure of colemanite contains endless chains of interlocking BO2(OH) triangles and BO3(OH) tetrahedrons with the calcium, water and extra hydroxide units interspersed between these chains. The Raman spectra of colemanite is characterized by an intense band at 3605 cm-1 assigned to the stretching vibration of OH units and a series of bands at 3182, 3300, 3389 and 3534 cm-1 assigned to water stretching vibrations. Infrared bands are observed in similar positions. The BO stretching vibrations of the trigonal and tetrahedral boron are characterized by Raman bands at 876, 1065 and 1084 cm-1. The OBO bending mode is defined by the Raman band at 611 cm-1. It is important to characterize the very wide range of borate minerals including colemanite because of the very wide range of applications of boron containing minerals.