Liquidus Phase Research Articles

Origin of Platinum Group Minerals (PGM) Inclusions in Chromite Deposits of the Urals

This paper reviews a database of about 1500 published and 1000 unpublished microprobe analyses of platinum-group minerals (PGM) from chromite deposits associated with ophiolites and Alaskan-type complexes of the Urals. Composition, texture, and paragenesis of unaltered PGM enclosed in fresh chromitite of the ophiolites indicate that the PGM formed by a sequence of crystallization events before, during, and probably after primary chromite precipitation. The most important controlling factors are sulfur fugacity and temperature. Laurite and Os–Ir–Ru alloys are pristine liquidus phases crystallized at high temperature and low sulfur fugacity: they were trapped in the chromite as solid particles. Oxygen thermobarometry supports that several chromitites underwent compositional equilibration down to 700 °C involving increase of the Fe3/Fe2 ratio. These chromitites contain a great number of PGM including—besides laurite and alloys—erlichmanite, Ir–Ni–sulfides, and Ir–Ru sulfarsenides formed by increasing sulfur fugacity. Correlation with chromite composition suggests that the latest stage of PGM crystallization might have occurred in the subsolidus. If platinum-group elements (PGE) were still present in solid chromite as dispersed atomic clusters, they could easily convert into discrete PGM inclusions splitting off the chromite during its re-crystallization under slow cooling-rate. The presence of primary PGM inclusions in fresh chromitite of the Alaskan-type complexes is restricted to ore bodies crystallized in equilibrium with the host dunite. The predominance of Pt–Fe alloys over sulfides is a strong indication for low sulfur fugacity, thereby early crystallization of laurite is observed only in one deposit. In most cases, Pt–Fe alloys crystallized and were trapped in chromite between 1300 and 1050 °C. On-cooling equilibration to ~900 °C may produce lamellar unmixing of different Pt–Fe phases and osmium. Precipitation of the Pt–Fe alloys locally is followed by an increase of sulfur fugacity leading to crystallize erlichmanite and Ir–Rh–Ni–Cu sulfides, occurring as epitaxic overgrowth on the alloy. There is evidence that the system moved quickly into the stabilization field of Pt–Fe alloys by an increase of the oxygen fugacity marked by an increase of the magnetite component in the chromite. In summary, the data support that most of the primary PGM inclusions in the chromitites of the Urals formed in situ, as part of the chromite precipitation event. However, in certain ophiolitic chromitites undergoing annealing conditions, there is evidence for subsolidus crystallization of discrete PGM from PGE atomic-clusters occurring in the chromite. This mechanism of formation does not require a true solid solution of PGE in the chromite structure.

Experimentally determined effects of olivine crystallization and melt titanium content on iron isotopic fractionation in planetary basalts

Olivine is the most abundant mantle mineral at depths relevant to oceanic crust production through melting. It is also a liquidus phase for a wide range of mafic and ultramafic magma compositions. We have experimentally investigated the effects of olivine crystallization and melt composition on the fractionation of Fe isotopes in igneous systems. To test whether there is a melt compositional control on Fe isotopic fractionation, we have conducted nuclear resonant inelastic X-ray scattering (NRIXS) measurements on a suite of synthetic glasses ranging from 0.4 to 16.3 wt.% TiO2. The resulting force constants are similar to those of the reduced (fO2 = IW) terrestrial basalt, andesite, and dacite glasses reported by Dauphas et al. (2014), indicating that there is no measurable effect of titanium composition on Fe isotopic fractionation in the investigated compositional range. We have also conducted olivine crystallization experiments and analyzed the Fe isotopic composition of the experimental olivines and glasses using solution MC-ICPMS. Olivine and glass separates from a given experimental charge have the same iron isotopic composition within error. This result is robust in both the high-Ti glass (Apollo 14 black) and low-Ti glass (Apollo 14 VLT) compositions, and at the two oxygen fugacities investigated (IW−1, IW+2). Additionally, we have determined that Fe loss in reducing one-atmosphere gas-mixing experiments occurs not only as loss to the Re wire container, but also as evaporative loss, and each mechanism of experimental Fe loss has an associated Fe isotopic fractionation.We apply our results to interpreting Fe isotopic variations in the lunar mare basalts and lunar dunite 72415-8. Our experimental results indicate that neither melt TiO2 composition nor equilibrium olivine crystallization can explain the observed difference in the iron isotopic composition of the lunar mare basalts. Additionally, equilibrium iron isotopic fractionation between olivine and melt cannot account for the “light” iron isotopic composition of lunar dunite 72415-8, unless the melt from which it is crystallizing was already enriched in light iron isotopes. Our results support models of diffusive fractionation to explain the light iron isotopic compositions measured in olivine from a variety of rock types and reduced (fO2 = IW−1 to IW+2) igneous environments (e.g., lunar dunite and basalts, terrestrial peridotites and basalts, martian shergottites).

Melting Phase Relations and Element Partitioning in MORB to Lowermost Mantle Conditions

AbstractMelting phase relations and crystal‐melt element partitioning in a mid‐oceanic ridge basalt bulk composition were studied to 135 GPa using laser‐heated diamond‐anvil cell techniques. Using field‐emission‐type electron microprobe (FE‐EPMA), transmission electron microscope (TEM), and laser ablation‐inductively‐coupled plasma mass spectrometer (LA‐ICP‐MS), we obtained comprehensive analyses of major and trace elements in coexisting melt and solid phases. CaSiO3‐perovskite (Ca‐pv) was found to be the liquidus phase throughout the lower mantle pressure range. Whereas silica, followed by Mg‐perovskite, are the second and third crystallizing phases to pressures exceeding 100 GPa, postperovskite, closely followed by seifertite, succeed Ca‐pv at 135 GPa. The partitioning of trace elements between Ca‐pv and melts exhibited a strong pressure effect, possibly due to a combination of high compressibility of cations compared to the lattice site in Ca‐pv and melt compressional effects. The Ca‐pv/melt partition coefficients for Na and K (DNa and DK) increase with increasing pressure, with DNa close to unity and DK greater than unity at lowermost mantle pressures. Also, DNd becomes larger (or identical within uncertainty) than DSm in the deep lower mantle. Partial melt formed by 51% partial melting of mid‐oceanic ridge basalt at 135 GPa showed marked iron‐enrichment and should thus have negative buoyancy at the base of the mantle. The density of residual solid is almost identical to the PREM density, and therefore, it is likely to be involved in mantle convection and recycled to the surface.

Crystallization of the lunar magma ocean and the primordial mantle-crust differentiation of the Moon

We present crystallization experiments on silicate melt compositions related to the lunar magma ocean (LMO) and its evolution with cooling. Our approach aims at constraining the primordial internal differentiation of the Moon into mantle and crust. We used graphite capsules in piston cylinder (1.35–0.80 GPa) and internally-heated pressure vessels (<0.50 GPa), over 1580–1020 °C, and produced melt compositions using a stepwise approach that reproduces fractional crystallization. Using our new experimental dataset, we define phase equilibria and equations predicting the saturation of liquidus phases, magma temperature, and crystal/melt partitioning for major elements relevant for the crystallization of the LMO. These empirical expressions are then used in a forward model that predicts the liquid line of descent and crystallization products of a 600 km-thick magma ocean. Our results show that the effects of changes in the bulk composition on the sequence of crystallization are minor. Our experiments also show the crystallization of a silica phase at ca. 1080 °C and we suggest that this phase might have contributed to the building of the lower anorthositic crust. Calculation of crustal thickness clearly shows that a thin crust similar to that revealed by GRAIL cannot have been generated through solidification of whole Moon magma ocean. We discuss the role of magma ocean depth, trapped liquid fraction (with implication for the alumina budget in the mantle and the crust), and the efficiency of plagioclase flotation in producing the thin crust. We also constrain the potential range of pyroxene compositions that could be incorporated into the crust and show that delayed crustal building during ca. 4% LMO crystallization on the nearside of the Moon may explain the dichotomy for Mg-number. Finally, we show that the LMO can produce magnesian anorthosites during the first stages of plagioclase crystallization.

Experimental and thermodynamic assessment of the Gd-Ti-Zr phase diagram

The phase diagram of the ternary Gd-Ti-Zr system has been investigated. The phase equilibria behave as a pseudo-binary Gd-(Ti, Zr) system with the solid state been characterized by the coexistence of elemental Gd and (Ti, Zr) solid solution phase with low solubility (< 1 at%) of the other elements. A continuous eutectic line connects the eutectic points of the binary Gd-Ti and Gd-Zr terminal systems. The stable miscibility gap of the liquid phase of the Gd-Ti system extends up to 15 at%Zr into the ternary alloy system. The liquidus line and phase sequence were experimentally assessed for Gd20Ti40Zr40, Gd40Ti20Zr40 and Gd40Ti50Zr10 by in situ high energy synchrotron X-ray diffraction at elevated temperatures. Based on the experimental data a thermodynamic description of the ternary Gd-Ti-Zr system is derived.

Phase Equilibria of Pantelleria Trachytes (Italy): Constraints on Pre-eruptive Conditions and on the Metaluminous to Peralkaline Transition in Silicic Magmas

The relationships between trachytes and peralkaline rhyolites (i.e. pantellerites and comendites), which occur in many continental rift systems, oceanic islands and continental intraplate settings, is unclear. To fill this gap, we have performed phase equilibrium experiments on two representative metaluminous trachytes from Pantelleria to determine both their pre-eruptive equilibration conditions (pressure, temperature, H2O content and redox state) and liquid lines of descent. Experiments were performed in the temperature range 750-950 °C, pressure 0·5-1·5 kbar and fluid saturation conditions with XH2O [=H2O/(H2O+CO2)] ranging between zero and unity. Redox conditions were fixed below the nickel-nickel oxide buffer (NNO). The results show that at 950 °C and melt water contents (H2Omelt) close to saturation, trachytes are at liquidus conditions at all pressures. Clinopyroxene is the liquidus phase, being followed by iron-rich olivine and alkali feldspar. Comparison of experimental and natural phases (abundances and compositions) yields the following pre-eruptive conditions: P=160·5 kbar, T=925±25 °C, H2Omelt = 261 wt %, and fO2 between NNO- 0·5 and NNO- 2. A decrease in temperature from 950 °C to 750 °C, as well as of H2Omelt, promotes a massive crystallization of alkali feldspar to over 80 wt %. Iron-bearing minerals show gradual iron enrichment when T and fO2 decrease, trending towards the compositions of the phenocrysts of natural pantellerites. Despite the metaluminous character of the bulk-rock compositions, residual glasses obtained after 80 wt % crystallization evolve toward comenditic compositions, owing to profuse alkali feldspar crystallization, which decreases the Al2O3 of the melt, leading to a consequent increase in the peralkalinity index [PI = molar (Na2O+K2 O)/Al2 O3 ]. This is the first experimental demonstration that peralkaline felsic derivatives can be produced by low-pressure fractional crystallization of metaluminous mafic magmas. Our results show that the pantelleritic magmas of basalt-trachyte-rhyolite igneous suites require at least 95 wt % of parental basalt crystallization, consistent with trace element evidence. Redox conditions, through their effect on Fe-Ti oxide stabilities, control the final iron content of the evolving melt.

Phase Equilibrium Investigation for CaO-SiO&lt;sub&gt;2&lt;/sub&gt;-5wt.%MgO-20wt.%Al&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;3&lt;/sub&gt;-TiO&lt;sub&gt;2&lt;/sub&gt; System Relevant to Ti-bearing Slag System

In order to resolve the lack of thermodynamic information for the comprehensive unilization of Ti-bearing blast furnace slag, the phase diagram relevant to the Ti-bearing slag composition was widely investigated. In the present work, the phase equilibrium relationships were investigated for the CaO-SiO2-5wt.%MgO-20wt.%Al2O3-TiO2 phase diagram system. The equilibrium phases were experimentally determined at 1300°C and 1400°C using the high temperature equilibrium technique followed by X-Ray Fluorescence (XRF), X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM) and Energy Dispersive X-ray spectroscope (EDX) analysis. The liquid phase (L), melilite solid solution ((2CaO·MgO·2SiO2, 2CaO·Al2O3·SiO2)ss) phase, perovskite (CaO·TiO2) phase, Al–Ti diopside phase and pseudobrookite solid solution (MgO·TiO2, Al2O3·TiO2)ss phase were found. Based on the experimental results, the 1300°C to 1500°C liquidus lines and phase diagram were constructed for the specified region of the CaO-SiO2-5wt.%MgO-20wt.%Al2O3-TiO2 system.

Mineralogy of silicate inclusions in the Elga IIE iron meteorite

The petrography, mineral modal data and major and trace element compositions of 15 silicate inclusions in the Elga iron meteorite (chemical group IIE) show that these inclusions represent chemically homogeneous zoned objects with highly variable structures, reflecting the sequence of crystallization of a silicate melt during cooling of the metal host. The outer zones of inclusions at the interface with their metal host have a relatively medium-grained hypocrystalline texture formed mainly by Cr-diopside and merrillite crystals embedded in high-silica glass, whereas the central zones have a fine-grained hypocrystalline texture. Merrillite appears first on the liquidus in the outer zones of the silicate inclusions. Na and REE concentrations in merrillite from the outer zones of inclusions suggest that it may have crystallized as α-merrillite in the temperature range of 1300–1700°С. Merrillite tends to preferentially accumulate Eu without Sr. Therefore, strongly fractionated REE patterns are not associated with prolonged differentiation of the silicate melt source but depend on crystallization conditions of Н-chondrite droplets in a metallic matrix. The systematic decrease in Mg# with increasing Fe/Mn in bronzite may indicate partial reduction of iron during crystallization of the inclusion melt. The modal and bulk compositions of silicate inclusions in the Elga meteorite, as well as the chemical composition of phases are consistent with the model equilibrium crystallization of a melt, corresponding to 25% partial melting of H-chondrite, and the crystallizing liquidus phase, merrillite, and subsequent quenching at about 1090°С. Despite a high alkali content of the average weighted bulk inclusion composition, La/Hf and Rb/Th fall within the field of H chondrites, suggesting their common source. Our results reveal that silicate inclusions in the Elga (IIE) iron meteorite originated by mixing of two impact melts, ordinary chondrite and Ni-rich iron with а IIE composition, which were produced by impact event under near-surface conditions on a partially differentiated parent asteroid.

Petrogenesis of D'Orbigny‐like angrite meteorites and the role of spinel in the angrite source

AbstractAngrite meteorites are samples of early planetesimal magmatic rocks, distinguished from more typical “basaltic eucrites” by compositions that are silica undersaturated, relatively oxidized, and with high CaO/Al2O3. The latter is not expected from nebular, chondritic materials that might form a primitive mantle, such as a source enriched in refractory inclusions with fixed CaO/Al2O3 (e.g., CV chondrite). Here we present results of “reversal” crystallization experiments for two possible parental angrite compositions (approximating the D'Orbigny meteorite) to investigate the role of spinel as a sink for Al2O3. This mineral has previously been produced with angritic melts during “forward” melting of CV chondrite and may be abundant in the angrite source. At oxidizing conditions, we confirm that spinel is a liquidus phase and that angritic magmas form near the olivine‐anorthite‐spinel‐liquid peritectic. A stability gap separates Al‐rich liquidus spinels and lower temperature spinels, the latter of which are similar to those in basaltic eucrites. Al‐rich spinel is likely more abundant in the angritic source than other Fe‐rich core‐forming components such as metal or sulfide, and a CV chondrite‐like composition generates most features of angrite magmas by fractionation of observed olivine and liquidus spinel. Direct CaO excess, via carbonate addition, is therefore limited. In this model, discrepancies remain for Li, Sc, Cr(‐Al), and Ba, which may record local accretion conditions or early processing. The possible role of spinel as a sink for 26Al may have strong influence on the thermal evolution of the angrite parent body.

The thickness of the crystal mush on the floor of the Bushveld magma chamber

The thickness of the crystal mush on magma chamber floors can be constrained using the offset between the step-change in the median value of dihedral angles formed at the junctions between two grains of plagioclase and a grain of another phase (typically clinopyroxene, but also orthopyroxene and olivine) and the first appearance or disappearance of the liquidus phase associated with the step-change in median dihedral angle. We determined the mush thickness in the Rustenburg Layered Suite of the Bushveld Complex at clinopyroxene-in (in Lower Main Zone) and magnetite-in (in Upper Zone). We also examined an intermittent appearance of cumulus apatite in Upper Zone, using both the appearance and disappearance of cumulus apatite. In all cases, the mush thickness does not exceed 4 m. These values are consistent with field observations of a mechanically rigid mush at the bases of both magnetitite and chromitite layers overlying anorthosite. Mush thickness of the order of a few metres suggests that neither gravitationally-driven compaction nor compositional convection within the mush layer is likely to have been important processes during solidification: adcumulates in the Bushveld are most likely to have formed at the top of the mush during primary crystallisation. Similarly, it is unlikely either that migration of reactive liquids occurs through large stretches of stratigraphy, or that layering is formed by mechanisms other than primary accumulation.

Rift-associated ultramafic lamprophyre (damtjernite) from the middle part of the Lower Cretaceous (125 Ma) succession of Kutch, northwestern India: Tectonomagmatic implications

Mineralogical, geochemical and isotopic (Sr and Nd) studies on the recently reported ca. 124 Ma ‘anorogenic lamproite’ dyke from the Palanpur area, Kutch seismogenic rift zone, northwestern India, are presented. We propose a new classification for the dyke as a damtjernite (ultramafic lamprophyre; UML) based on its porphyritic-panidiomorphic texture, abundance of phlogopite, presence of nepheline in the groundmass, and the composition of liquidus phases such as olivine, phlogopite, magnetite, and clinopyroxene (diopside). The Palanpur UML is primitive (Mg# = 74–77), silica-undersaturated (SiO2 <40 wt.%), potassic to slightly sodic in nature, and is strikingly similar to the ∼69 Ma UML dykes and sills of the Tethyan Indus suture zone, which are considered as the earliest yet known manifestations of the Deccan Large Igneous Province (LIP). Bulk-rock (87Sr/86Sr)i (0.70460–0.70461) and ɛNd(t) (+2.56 to −0.69) of the Palanpur UML signify derivation from a slightly depleted mantle source similar to that of asthenospheric magmas such as OIB. This is further attested to by the high incompatible trace element ratios (viz., La/Ba, Nb/U, Nb/La and Ta/Yb) that are typical of plume-type magmas. However, the Neoproterozoic TDM depleted mantle Nd model ages (∼655–919 Ma) also necessitate some involvement of a lithospheric mantle component in its genesis. High bulk-rock Fe2O3t and TiO2 contents require the involvement of a fertile peridotitic mantle source, whereas high La/Yb (60–80) implies a control by residual garnet. Higher Rb/Sr and lower Ba/Rb suggest phlogopite as a residual phase and high Nb and lower La/Sm favour carbonatite, rather than silicate melt as metasomatising agent. Low degrees of partial melting of a primitive garnet lherzolite mantle can account for the observed REE patterns in the Palanpur UML. The Palanpur UML shares a temporal similarity to the Kerguelen plume-derived Rajmahal basalts and associated alkaline rocks from the eastern India. The tectonomagmatic significance of its emplacement during the mid-Cretaceous vis-à-vis various models involving the timing of eruption of the Deccan and the Rahmahal Traps and the rifting in the Kutch basin induced by far-field plate reorganization is evaluated.

Petrological and experimental evidence for differentiation of water-rich magmas beneath St. Kitts, Lesser Antilles

St. Kitts lies in the northern Lesser Antilles, a subduction-related intraoceanic volcanic arc known for its magmatic diversity and unusually abundant cognate xenoliths. We combine the geochemistry of xenoliths, melt inclusions and lavas with high pressure–temperature experiments to explore magma differentiation processes beneath St. Kitts. Lavas range from basalt to rhyolite, with predominant andesites and basaltic andesites. Xenoliths, dominated by calcic plagioclase and amphibole, typically in reaction relationship with pyroxenes and olivine, can be divided into plutonic and cumulate varieties based on mineral textures and compositions. Cumulate varieties, formed primarily by the accumulation of liquidus phases, comprise ensembles that represent instantaneous solid compositions from one or more magma batches; plutonic varieties have mineralogy and textures consistent with protracted solidification of magmatic mush. Mineral chemistry in lavas and xenoliths is subtly different. For example, plagioclase with unusually high anorthite content (An≤100) occurs in some plutonic xenoliths, whereas the most calcic plagioclase in cumulate xenoliths and lavas are An97 and An95, respectively. Fluid-saturated, equilibrium crystallisation experiments were performed on a St. Kitts basaltic andesite, with three different fluid compositions (XH2O = 1.0, 0.66 and 0.33) at 2.4 kbar, 950–1025 °C, and fO2 = NNO − 0.6 to NNO + 1.2 log units. Experiments reproduce lava liquid lines of descent and many xenolith assemblages, but fail to match xenolith and lava phenocryst mineral compositions, notably the very An-rich plagioclase. The strong positive correlation between experimentally determined plagioclase-melt KdCa–Na and dissolved H2O in the melt, together with the occurrence of Al-rich mafic lavas, suggests that parental magmas were water-rich (> 9 wt% H2O) basaltic andesites that crystallised over a wide pressure range (1.5–6 kbar). Comparison of experimental and natural (lava, xenolith) mafic mineral composition reveals that whereas olivine in lavas is predominantly primocrysts precipitated at low-pressure, pyroxenes and spinel are predominantly xenocrysts formed by disaggregation of plutonic mushes. Overall, St. Kitts xenoliths and lavas testify to mid-crustal differentiation of low-MgO basalt and basaltic andesite magmas within a trans-crustal, magmatic mush system. Lower crustal ultramafic cumulates that relate parental low-MgO basalts to primary, mantle -derived melts are absent on St. Kitts.

Phase equilibria study of the ZnO–‘FeO’–SiO2–MgO system at Po2 10−8 atm

ABSTRACTExperimental studies on the liquidus temperature and phase relations of the ZnO–‘FeO’–SiO2–MgO system have been investigated at Po2 10−8 atm related to the copper smelting slag. The experimental technique applied in present study involves master slag preparation, high-temperature equilibration, quenching and EPMA analysis. The impact of MgO content on the liquidus temperature and partitioning behaviour of ZnO has been evaluated. It was found that the presence of MgO content in the slag can significantly increase liquidus temperature in spinel primary phase field and narrow the full liquid area at a given operating temperature. The ZnO and MgO concentrations in the liquid phase are higher than those in the spinel phase. The present study provides more accurate information for copper smelting slags and optimisation of the thermodynamic modelling.

Crystal growth and disequilibrium distribution of oxygen isotopes in an igneous Ca-Al-rich inclusion from the Allende carbonaceous chondrite

TS34 is a Type B1 Ca-Al-rich inclusion (CAI) from the Allende CV3 chondrite, consisting of spinel, melilite, Ti-Al-rich clinopyroxene (fassaite) and minor anorthite in an igneous texture. Oxygen and magnesium isotopic compositions were measured by secondary ion mass spectrometry in spots of known chemical composition in all major minerals in TS34. Using the sequence of formation from dynamic crystallization experiments and from chemical compositions of melilite and fassaite, the oxygen isotopic evolution of the CAI melt was established. Oxygen isotopic compositions of the constituent minerals plot along the carbonaceous chondrite anhydrous mineral line. The spinel grains are uniformly 16O-rich (Δ17O=−22.7±1.7‰, 2SD), while the melilite grains are uniformly 16O-poor (Δ17O=−2.8±1.8‰) irrespective of their åkermanite content and thus their relative time of crystallization. The fassaite crystals exhibit growth zoning overprinting poorly-developed sector zoning; they generally grow from Ti-rich to Ti-poor compositions. The fassaite crystals also show continuous variations in Δ17O along the inferred directions of crystal growth, from 16O-poor (Δ17O∼−3‰) to 16O-rich (Δ17O∼−23‰), covering the full range of oxygen isotopic compositions observed in TS34. The early-crystallized 16O-poor fassaite and the melilite are in oxygen isotope equilibrium and formed simultaneously. The correlation of oxygen isotopic compositions with Ti content in the fassaite imply that the oxygen isotopic composition of the CAI melt evolved from 16O-poor to 16O-rich during fassaite crystallization, presumably due to oxygen isotope exchange with a surrounding 16O-rich nebular gas. Formation of spinel, the liquidus phase in melts of this composition, predates crystallization of all other phases, so its 16O-rich composition is a relic of an earlier stage. Anorthite exhibits oxygen isotopic compositions between Δ17O∼−2‰ and −9‰, within the range of those of fassaite, indicating co-crystallization of these two minerals during the earliest to intermediate stage of fassaite growth. The melilite and fassaite yield an 26Al–26Mg mineral isochron with an initial value of (26Al/27Al)0=(5.003±0.075)×10−5, corresponding to a relative age of 0.05±0.02Myr from the canonical Al–Mg age of CAIs. These data demonstrate that both 16O-rich and 16O-poor reservoirs existed in the solar nebula at least ∼0.05Myr after the birth of the Solar System.

Enhancement of photoluminescence from iron disilicide on Si(111) substrates with Au layers by controlling microstructures

The photoluminescence (PL) spectrum of iron disilicide (β-FeSi2) was enhanced by increasing the density of epitaxial grains grown at 650 °C on Si(111) substrates with a Au layer. The Au–Si liquidus phase obtained from the Au–Si eutectic reaction contributed to the formation of epitaxial β-FeSi2 grains on the Si(111) surface. The density of the epitaxial β-FeSi2 grains on the Si(111) surface decreased with increasing thickness of the Au layer, while the grain size increased from 0.5–2 to 20–50 µm. It is suggested that the excitation volume of the β-FeSi2 is a key point that determines the PL intensity.

The influence of chemical composition on microstructure, hardness and electrical conductivity of Ag-Bi-In alloys at 100 °C

Considering possible applications and scarceness of literature data, Ag-Bi-In system was investigated in terms of microstructure, mechanical and electrical properties of ternary alloys from an isothermal section at 100oC. Based on the experimentally obtained results hardness and electrical conductivity of all ternary alloys from the ternary Ag-Bi-In system at 100oC were predicted. In addition, the selected isothermal section was further thermodynamically assessed and experimentally studied using scanning electron microscopy (SEM) with energy dispersive spectrometry (EDS), X-ray powder diffraction (XRD) analysis and light optical microscopy (LOM). Phase transition temperatures of alloys with overall compositions along vertical sections x(Ag)=0.5 as well as liquidus temperatures were experimentally determined by DTA. The experimentally obtained results were compared with literature data and with the results of thermodynamic calculation of phase equilibria based on CALPHAD method and corrected data for Ag-In binary system. Calculated liquidus projection, invariant equilibria and phase diagram of the Ag-Bi-In ternary system are presented as well.

Melting relations in the MgO–MgSiO3 system up to 70 GPa

Melting experiments in a binary system MgO–MgSiO3 were performed up to 70 GPa using a CO2 laser heated diamond anvil cell. The quenched samples were polished and analyzed by a dualbeam focused ion beam (FIB) and a field emission scanning electron microscope (FE-SEM), respectively. The liquidus phase and the eutectic composition were determined on the basis of textual and chemical analyses of sample cross sections. Our experimental results show that the eutectic composition is the Si/Mg molar ratio of ~0.76 at 35 GPa and it decreases with increasing pressure. Above 45 GPa, it becomes relatively constant at about 0.64–0.65 Si/Mg molar ratio. Using our experimental data collected at a wide pressure range up to 70 GPa together with previous experimental data, we have constructed a thermodynamic model of the eutectic composition of the MgO–MgSiO3 system. The eutectic composition extrapolated to the pressure and temperature conditions at the base of the mantle is about 0.64 Si/Mg molar ratio. The modeled eutectic composition is quite consistent with a previous prediction from ab initio calculations (de Koker et al. in Earth Planet Sci Lett 361:58–63, 2013), suggesting that the simple assumption of a non-ideal regular solution model can well describe the melting relation of the MgO–MgSiO3 system at high pressure. Our results show that the liquidus phase changes from MgO-periclase to MgSiO3-bridgmanite at 35 GPa for the simplified pyrolite composition (~0.7 Si/Mg molar ratio), while MgSiO3-bridgmanite is the liquidus phase at the entire lower mantle conditions for the chondritic composition (~0.84 Si/Mg molar ratio).

Liquidus temperatures and phase equilibria in the BaCl2–MCl–BaO systems

The liquidus temperatures of the BaO–BaCl2–MCl systems (with M = alkali metal) are determined by thermal analysis. The caloric effects observed during melting of the barium-containing chloride eutectic with barium oxide additions are studied. A chemical mechanism of barium oxide dissolution in the melts is confirmed. X-ray diffraction patterns taken for the melt solidified after experiment indicate the presence of barium oxychloride Ba4OCl6 in the solid phase. It is shown that the significant increase in the liquidus temperature in adding the barium oxide to barium-containing chloride molten mixtures is related to substantial changes in their composition and structure.

Synthesis and Photocatalytic Properties of Iron Disilicide/SiC Composite Powder

ABSTRACTSemiconducting iron disilicide (β-FeSi2) island grains of 50-100 nanometers in size were formed on the surface of Au-coated 3C-SiC powder by metal-organic chemical vapor deposition. On the surface of 3C-SiC powder, the Au-Si liquidus phase was obtained via a Au-Si eutectic reaction, which contributed to the formation of the β-FeSi2 island grains. This β-FeSi2/SiC composite powder could evolve hydrogen (H2) from methyl-alcohol aqueous solution under irradiation of visible light with wavelengths of 420-650 nm.

Experimental and thermodynamic description of ternary Bi-Cu-Ga system

Phase diagram of the Bi-Cu-Ga ternary system has been investigated experimentally with 27 alloys and analytically by using a Calphad method. Thirteen annealed alloys at 200?C were investigated by using scanning electron microscopy (SEM) with energy dispersive spectrometry (EDS), and X-ray powder diffraction (XRD) methods. Temperatures of phase transformation were determined with 14 alloys which are lying along three vertical sections Bi-Cu0.5Ga0.5, Cu-Bi0.5Ga0.5 and Ga-Bi0.5Cu0.5 by using differential thermal analysis (DTA). Based on the experimental result and by using Calphad method, ternary phase diagrams were constructed with a new description of liquidus phase. Calculated phase diagram and experimentally obtained results are in good agreement. Liquidus projection and invariant reaction were calculated by using new thermodynamic parameters for liquidus phase.