A reinvestigation of phase equilibria in the system Al2O3-SiO2-ZnO

The phase equilibria and liquidus temperatures in the binary SiO2-ZnO system and in the ternary Al2O3-SiO2-ZnO system at low Al2O3 concentrations have been experimentally determined using the equilibration and quenching technique followed by electron probe X-ray microanalysis. In the SiO2-ZnO system, two binary eutectics involving the congruently melting willemite (Zn2SiO4) were found at 1448 +/- 5 degrees C and 0.52 +/- 0.01 mole fraction ZnO and at 1502 +/- 5 degrees C and 0.71 +/- 0.01 mole fraction ZnO, respectively. The two ternary eutectics involving willemite previously reported in the Al2O3SiO2-ZnO system were found to be at 1315 +/- 5 degrees C and 1425 +/- 25 T, respectively. The compositions of the eutectics are 0.07, 0.52, and 0.41 and 0.05, 0.28, and 0.67 mole fraction Al2O3, SiO2, and ZnO, respectively. The results of the present investigation are significantly different from the results of previous studies.

Phase equilibria in the system Fe-Zn-O at intermediate conditions between metallic-iron saturation and air

The phase equilibria in the FeO-Fe2O3-ZnO system have been experimentally investigated at oxygen partial pressures between metallic iron saturation and air using a specially developed quenching technique, followed by electron probe X-ray microanalysis (EPMA) and then wet chemistry for determination of ferrous and ferric iron concentrations. Gas mixtures of H-2, N-2, and CO2 or CO and CO2 controlled the atmosphere in the furnace. The determined metal cation ratios in phases at equilibrium were used for the construction of the 1200 degrees C isothermal section of the Fe-Zn-O system. The univariant equilibria between the gas phase, spinel, wustite, and zincite was found to be close to pO(2) = 1 center dot 10(-8) atm at 1200 degrees C. The ferric and ferrous iron concentrations in zincite and spinel at equilibrium were also determined at temperatures from 1200 degrees C to 1400 degrees C at pO(2) = 1 center dot 10(-6) atm and at 1200 degrees C at pO(2) values ranging from 1 center dot 10(-4) to 1 center dot 10(-8) atm. Implications of the phase equilibria in the Fe-Zn-O system for the formation of the platelike zincite, especially important for the Imperial Smelting Process (ISP), are discussed.

Phase equilibria in the Fe-Zn-O system at conditions relevant to zinc sintering and smelting

Zincite and spinel phases are present in the complex slag systems encountered in zinc/lead sintering and zinc smelting processes. These phases form extensive solid solutions and are stable over a wide range of compositions, temperatures and oxygen partial pressures. Accurate information on the stability of these phases is required in order to develop thermodynamic models of these slag systems. Phase equilibria in the Fe–Zn–O system have been experimentally studied for a range of conditions, between 900°C and 1580°C and oxygen partial pressures (pO2) between air and metallic iron saturation, using equilibration and quenching techniques. The compositions of the phases were measured using Electron probe X-ray microanalysis (EPMA). The ferrous and ferric bulk iron concentrations were determined using a specially developed wet-chemical analysis procedure based on the use of ammonium metavanadate. XRD was used to confirm phase identification. A procedure was developed to overcome the problems associated with evaporation of zinc at low pO2 values and to ensure the achievement of equilibria. An isothermal section of the system FeO–Fe2O3–ZnO at high ZnO concentrations at 1200°C was constructed. The maximum solubilities of iron and zinc in zincite and spinel phases in equilibrium were determined at pO2 = 1 × 10-6 atm at 1200°C and 1300°C. The morphology of the zincite crystals sharply changes in air between 1200–1300°C from rounded to plate-like. This is shown to be associated with significant increase in total iron concentration, the additional iron being principally in the form of ferric iron. Calculations performed by FactSage with a thermodynamically optimised database have been compared with the experimental results.

Effect of Al2O3 and Cr2O3 on loquidus temperatures in the cristobalite and tridymite primary phase fields of the MgO-"FeO"-SiO2 ststem in equilibrium with metallic iron

The effects of alumina and chromite impurities on the liquidus temperatures in the cristobalite/tridymite (SiO2) primary phase fields in the MgO-FeO-SiO, system in equilibrium with metallic iron have been investigated experimentally. Using high temperature equilibration and quenching followed by electron probe X-ray microanalysis (EPMA), liquiclus isotherms have been determined in the temperatures range 1 673 to 1 898 K. The results are presented in the form of pseudo-ternary sections of the MgO-FeO-SiO, system at 2, 3 and 5 wt% Al2O3, 2 wt% Cr2O3, and 2 wt% Cr2O3+2 wt% Al2O3. The study enables the liquidus to be described for a range of SiO2/MgO and MgO/FeO ratios. It was found that liquiclus temperatures in the cristobalite and tridymite primary phase fields, decrease significantly with the addition of Al2O3 and Cr2O3.

Raman microscopy of the molybdate minerals koechlinite, iriginite and lindgrenite

A series of molybdate bearing minerals including wulfenite, powellite, lindgrenite and iriginite have been analysed by Raman microscopy. These minerals are closely related and often have related paragenesis. Raman microscopy enables the selection of individual crystals of these minerals for spectroscopic analysis even though several of the minerals can be found in the same matrix because of the paragenetic relationships between the minerals. The molybdenum bearing minerals lindgrenite, iriginite and koechlinite were studied by scanning electron microscopy and compositionally analysed by EDX methods using an electron probe before Raman spectroscopic analyses. The Raman spectra are assigned according to factor group analysis and related to the structure of the minerals. These minerals have characteristically different Raman spectra.

Micas in experimentally shocked gneiss

Biotites and muscovites from a gneiss have been experimentally shocked between 18 and 70 GPa using powder-propellant guns at NASA Johnson Space Center and at the California Institute of Technology. This study shows that shock in biotite and muscovite can produce homogeneous and devolatilized glasses within microseconds. Shock-deformed micas display fracturing, kinking, and complex extinction patterns over the entire pressure range investigated. However, these deformation features are not a sensitive pressure indicator. Localized melting of micas begins at 33 GPa and goes to completion at 70 GPa. Melted biotite and muscovite are optically opaque, but show extensive microvesiculation and flow when observed with the SEM. Electron diffraction confirms that biotite and muscovite have transformed to a glass. The distribution of vesicles in shock-vitrified mica shows escape of volatiles within the short duration of the shock experiment. Experimentally shocked biotite and muscovite undergo congruent melting. Compositions of the glasses are similar to the unshocked micas except for volatiles (H2O loss and K loss). These unusual glasses derived from mica may be quenched by rapid cooling conditions during the shock experiment. Based on these results, the extremely low H2O content of tektites may be reconciled with a terrestrial origin by impact. Release of volatiles in shock-melted micas affects the melting behavior of coexisting dry silicates during the short duration of the shock experiment. Transportation and escape of volatiles released from shock-melted micas may provide plausible mechanisms for the origin of protoatmospheres on terrestrial planets, hydrothermal activity on phyllosilicate-rich meteorite parent bodies, and fluid entrapment in meteorites.

Mineralogy of chondritic interplanetary dust particles

From a mineralogical survey of approximately 30 chondritic micrometeorites collected from the lower stratosphere and studied in detail using current electron microscopy techniques, it is concluded that these particles represent a unique group of extraterrestrial materials. These micrometeorites differ significantly in form and texture from components of carbonaceous chondrites and contain some mineral assemblages which do not occur in any meteorite class. Electron microscope investigations of chondritic micrometeorites have established that these materials (1) are extraterrestrial in origin, (2) existed in space as small objects, (3) endured minimal alteration by planetary processes since formation, and (4) can suffer minimal pulse heating (<600°C) on entering earth's atmosphere. The probable sources for chondritic interplanetary dust particles (IDPs) are cometary and asteroidal debris and, perhaps to a lesser extent, interstellar regions. These sources have not been conclusively linked to any specific mineralogical subset of IDP, although the chondritic porous (CP) aggregate is considered of likely cometary origin. Chondritic IDPs occur in two predominant mineral assemblages: (1) carbonaceous phases and phyllosilicates and (2) carbonaceous phases and nesosilicates or inosilicates, although particles with both types of silicate assemblages are observed. Olivines, pyroxenes, layer silicates, and carbon-rich phases are the most commonly occurring minerals in many chondritic IDPs. Other phases often observed in variable proportions include sulphides, spinels, metals, metal carbides, carbonates, and minor amounts of sulphates and phosphates. Individual mineral grain sizes range from micrometers (primarily pyroxenes and olivines) to nanometers, with the predominant size for all phases less than 100 nm. Specific mineral characteristics for particular chondritic IDPs provide an indication of processes which may have occurred prior to collection in the earth's stratosphere. For example, pyroxene mineralogy in some chondritic aggregates is consistent with condensation from a vapor phase and, we consider, with condensation in a turbulent solar nebula at relatively low temperatures (<1000°C). Carbonaceous phases present in other CP aggregates have been used to imply low-temperature formation processes such as Fischer-Tropsch synthesis (∼530°C) or carbonization and graphitization (∼315°C). Alteration processes have been implicated in the formation of some layer silicates in CP aggregates and may have involved hydrocryogenic alteration at <0°C. In general, interpretations of transformation processes on submicrometer-size minerals in chondritic IDPs are consistent with formation at a radius equivalent to the asteroid belt or greater during the later stages of solar nebula evolution using currently available models.

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.

Characterization of the sulphate mineral amarantite Fe3 2 3+ (SO4)O 7H2O using infrared, Raman spectroscopy and thermogravimetry

The mineral amarantite Fe23+(SO4)O∙7H2O has been studied using a combination of techniques including thermogravimetry, electron probe analyses and vibrational spectroscopy. Thermal analysis shows decomposition steps at 77.63, 192.2, 550 and 641.4°C. The Raman spectrum of amarantite is dominated by an intense band at 1017 cm-1 assigned to the SO42- ν1 symmetric stretching mode. Raman bands at 1039, 1054, 1098, 1131, 1195 and 1233 cm-1 are attributed to the SO42- ν3 antisymmetric stretching modes. Very intense Raman band is observed at 409 cm-1 with shoulder bands at 399, 451 and 491 cm-1 are assigned to the v2 bending modes. A series of low intensity Raman bands are found at 543, 602, 622 and 650 cm-1 are assigned to the v4 bending modes. A very sharp Raman band at 3529 cm-1 is assigned to the stretching vibration of OH units. A series of Raman bands observed at 3025, 3089, 3227, 3340, 3401 and 3480 cm-1 are assigned to water bands. Vibrational spectroscopy enables aspects of the molecular structure of the mineral amarantite to be ascertained.

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.

Thermal analysis and vibrational spectroscopic characterization of the boro silicate mineral datolite – CaBSiO4(OH)

The objective of this work is to determine the thermal stability and vibrational spectra of datolite CaBSiO4(OH) and relate these properties to the structure of the mineral. The thermal analysis of datolite shows a mass loss of 5.83% over a 700–775 °C temperature range. This mass loss corresponds to 1 water (H2O) molecules pfu. A quantitative chemical analysis using electron probe was undertaken. The Raman spectrum of datolite is characterized by bands at 917 and 1077 cm−1 assigned to the symmetric stretching modes of BO and SiO tetrahedra. A very intense Raman band is observed at 3498 cm−1 assigned to the stretching vibration of the OH units in the structure of datolite. BOH out-of-plane vibrations are characterized by the infrared band at 782 cm−1. The vibrational spectra are based upon the structure of datolite based on sheets of four- and eight-membered rings of alternating SiO4 and BO3(OH) tetrahedra with the sheets bonded together by calcium atoms.

Assessment of the molecular structure of natrodufrénite – NaFe2+Fe3+5(PO4)4(OH)6•2(H2O), a secondary pegmatite phosphate mineral from Minas Gerais, Brazil

The mineral natrodufrénite a secondary pegmatite phosphate mineral from Minas Gerais, Brazil, has been studied by a combination of scanning electron microscopy and vibrational spectroscopic techniques. Electron probe analysis shows the formula of the studied mineral as (Na0.88Ca0.12)∑1.00(Mn0.11Mg0.08Ca0.04Zr0.01Cu0.01)∑0.97(Al0.02)∑4.91(PO4)3.96(OH6.15F0.07)6.22⋅2.05(H2O). Raman spectroscopy identifies an intense peak at 1003 cm−1 assigned to the ν1 symmetric stretching mode. Raman bands are observed at 1059 and 1118 cm−1 and are attributed to the ν3 antisymmetric stretching vibrations. A comparison is made with the spectral data of other hydrate hydroxy phosphate minerals including cyrilovite and wardite. Raman bands at 560, 582, 619 and 668 cm−1 are assigned to the ν4 bending modes and Raman bands at 425, 444, 477 and 507 cm−1 are due to the ν2 bending modes. Raman bands in the 2600–3800 cm−1 spectral range are attributed to water and OH stretching vibrations. Vibrational spectroscopy enables aspects of the molecular structure of natrodufrénite to be assessed.