Composition Of Inclusions Research Articles

Evolution of inclusions in novel cryogenic high-Mn austenitic steel weld metal with cerium addition

Cerium (Ce) was effectively transitioned into the high-Mn austenitic steel weld metal under submerged arc welding by adding cerium dioxide and calcium silicon reducing agents into flux. The evolution behaviours of the composition, number density and size of inclusions in weld metal with different Ce contents were systematically investigated by thermodynamic calculation and experiments. The results show that the number density of inclusions increased and average size decreased with the increase of Ce content from 0 to 0.087 wt-%. Meanwhile, and the percentage of inclusions number with size less than 0.80 μm increased from 79.28% to 91.43%. The evolutionary process of inclusions was Al2O3 → Al11O18Ce → CeAlO3 → Ce2O3 → Ce2O2S with the increase of Ce content in the present weld metal. In particular, Ce-O-S-Al inclusion was extracted by in-situ sample preparation method, which proved its internal structure and evolution process. The complete formation model of Ce-Al-O-S system was also established.

Evolution of inclusion populations in Al-killed steel during the steelmaking process

The increasing demand for higher steel inclusion cleanliness has motivated control over the formation and evolution of inclusions during the production process. To generate knowledge of the formation and evolution of inclusions during the production of Al-killed steel slabs, the evolution of the chemical composition and size distribution of inclusions throughout the process, including ladle furnace (LF) treatment and continuous casting (CC), was studied. Liquid steel sampling was conducted throughout the process. The chemical composition was measured using the EDS technique, and the size distribution analysis was performed with the population density function (PDF) approach. The upper tail of the size distributions was analyzed by generalized extreme value (GEV) theory. Evolution of the chemical composition of inclusions involved the following path: solid Al2O3 solid Al2O3-MgO partly liquid Al2O3–MgO–CaO fully liquid Al2O3–MgO–CaO. The PDF analysis accounted for the evolution of the size distribution, which was supposed to be driven by the balance of the coalescence/growth and collision/breakage of inclusions and their removal. Finally, the GEV approach allowed us to describe the evolution of large inclusions and compare inclusion populations in terms of survival probability.

The role of fluid mixing in the formation of vein-type Zn-Pb deposits in eastern Guizhou Province, SW China: Insights from elemental compositions and chlorine isotopes of fluid inclusions

• Multiple fluid sources are identified by variation range of Cl isotopes and Cl/Br ratios from. • Vein-type Zn-Pb mineralization is triggered by mixing of evaporated seawater and magmatic hydrothermal fluids . • Quantitative model shows that the mixing volume ratios of both sources are between 1:9 and 4:6. Numerous hydrothermal vein-type Zn–Pb deposits worldwide are characterized by low-temperature metallogeny, no spatial relationship with plutons, and strong water-rock interaction, which result in the difficulty of constraining the fluid origin and the process of ore formation by traditional geochemistry. In this study, we employ chemical and chlorine isotopic composition of bulk fluid inclusions from ore-bearing and ore-barren quartz veins to constrain the possible sources of ore-forming fluids and the process of metal precipitation in the hydrothermal systems of the economic vein-type mineralization in eastern Guizhou Province, SW China. Our new geochemical data are indicative of two end-members in the systems, one identified in the ore-bearing veins with high K/Na, Li/Na, Cl/Br ratios, and δ 37 Cl values representing magmatic hydrothermal fluids, another distinguished in the ore-barren veins with low Cl/Br ratios and δ 37 Cl values representing evaporated seawater. We conclude there is a systematic variation of these geochemical data as the results of the mixing between the former and the latter end-member. In the meantime, the mixing is quantitively assessed to study the mixing volume ratios of both end-members. Based on our data and our own previous study, a genetic fluid mixing model involving the magmatic hydrothermal fluids related to deep magma activity and the evaporated seawater is established for the formation of the vein-type Zn–Pb deposits. This study provides a novel geochemical approach for recognizing hydrothermal mineralizing systems.

The effect of Ce addition on purification and inclusion modification of CoCrFeNiMn high entropy alloy

This study focuses on purification and inclusion modification mechanism of equiatomic CoCrFeNiMn high entropy alloys with addition of various cerium (within the range of 0–0.0445 %) smelted by Vacuum Arc Melting (VAM), It was found that there are three types of inclusions in CoCrFeNiMn alloys: Mn(S, Se), AB2O4 spinel type, mixed type (Mn(S, Se) wraps AB2O4), and the average size of the three types of inclusions are 1.1 µm, 5.6 µm, and 4.8 µm, respectively. The addition of cerium can significantly reduce the oxygen content, as well as the sulfur content and selenium content are declined, the inclusions are refined and spheroidized simultaneously. The oxygen content, sulfur content and selenium content were reduced from 150 ppm, 46 ppm, and 105 ppm to 5–7 ppm, 22 ppm, and 80 ppm, respectively. When the cerium content is 0.0012 %, some of the inclusions are modified into three types of inclusions: Mn(S, Se) + Ce2O3, Mn(S, Se) + CeCrO3 and Mn(S, Se) + Ce2O3 + CeCrO3, while the average size of some unmodified AB2O4 spinel inclusions was reduced to 3.1 µm, and the average size of mixed inclusions was dropped to 2.6 µm. When the cerium content is 0.019 %, the inclusions in the alloy are completely modified into Ce2O2(S, Se) + Ce2(S, Se)3. Furthermore, the number density and area fraction of the inclusions are descended from 216.92 mm−2 and 0.1150 % of no cerium alloys to 121.64 mm−2 and 0.0602 %, the inclusions are well spheroidized, and the average size of cerium inclusions is 2.2 µm. Finally, the mechanism on the modification by cerium was discussed based on the composition evolution of inclusion during solidification with Factsage calculation and experimental results. The compositions of inclusions were also analyzed based on the inclusion evolution model.

Formation, cooling history and age of impact events on the IIE iron parent body: Evidence from the Miles meteorite

Most iron meteorites formed in planetary cores during differentiation, but the IIE iron meteorites have chemical and physical features that are inconsistent with this origin. By combining mineral chemistry, mineral modes and three-dimensional petrography, we reconstruct the bulk chemistry of the felsic silicate-bearing Miles IIE iron meteorite and demonstrate that the silicate inclusion compositions are similar to partial melts produced experimentally from an H chondrite composition. We use the reconstructed bulk composition, mineralogy and thermodynamic modelling to show that melting above ∼1200°C under reducing conditions formed metal (Fe-Ni alloy) and felsic silicate partial melts. Upon cooling, the melts crystallized Mg-rich pyroxenes, Na- and K-rich feldspars, and tridymite. Importantly, this mechanism enriches cosmochemically volatile elements (i.e., those with a 50% condensation temperature of ∼430–830°C, like Na and K) to the level found in the felsic silicate inclusions.The presence of crystallographically disordered srilankite (only stable above 1160°C) and an absence of Widmanstätten texture require both high peak temperatures and rapid cooling, which cannot be explained by core formation. Instead they point to small melt volumes, a transient heat pulse, and small thermal mass, and imply efficient physical segregation of silicate and metallic melts through buoyancy separation followed by rapid cooling that arrested the separation of metal and silicate liquid phases. In situ 207Pb/206Pb age of 4542.3 ± 4.0 Ma in Zr-oxide and phosphate minerals dates the melting event that formed the silicate inclusions. This age aligns with the earliest ages found in other IIE iron meteorite silicates and requires a heating event ∼25 million years after the solar system formed. We found 39Ar/40Ar ages of 3495 ± 52 Ma (low-T) and 4303 ± 7 Ma (high-T) in a K-feldspar grain, with the 3495 Ma age aligning with later thermal events recorded in other IIE iron meteorites. Dating reveals the complex petrogenetic and thermal history of Miles and the IIE iron meteorites. This is the first IIE iron meteorite found to record evidence of heating at 4.5 and 3.5 Ga likely from impact events.We propose that high-velocity impact(s) into an iron-rich, porous chondritic parent body at ∼4.54 Ga produced immiscible metal and silicate melts that cooled rapidly and trapped low density silicate inclusions within high density metal. Other IIE irons that formed at lower peak temperatures (900–1000°C) contain chondritic silicate inclusions and relict chondrules, supporting this conceptual model. This petrogenesis is consistent with thermodynamic modelling, experimental data and the wide range of peak temperatures and cooling rates observed in the IIE iron meteorites.

Results of 147Sm–143Nd (ID-TIMS) and U–Pb (SHRIMP-II) Dating of Rocks and Minerals of the Chromite-Bearing Kluchevskoy Ophiolite Massif (the Eastern Segment of the Urals) and Their Geological Interpretation

The Urals is one of the reference mobile belts of the mafic type characterized by a wide development of ophiolites which are associated with numerous deposits of chromites of significant industrial importance. In this regard, the estimation of the age of the rocks of the ophiolite association will be useful for analyzing the regularities of the formation of chromite deposits. This work presented the results of age dating of the rocks of the chromite-bearing Kluchevskoy mafic–ultramafic massif, one of the most representative of all the ophiolite-type massifs in the Urals, by two isotopic methods. The U–Pb (SHRIMP-II, VSEGEI) dating of the zircon dominated assemblage from rocks of different composition of both crustal and mantle sections of the Kluchevskoy ophiolite massif yielded similar dates ranging from 456 to 441 Ma. The study of the composition of silicate inclusions in zircon grains of this assemblage showed that they are represented by typical metamorphic minerals: low-T amphibole, albite, and an epidote-group mineral. The P–T conditions of zircon crystallization established via the examination of the composition of minerals in these inclusions showed that the crystallization of the predominant fraction of zircons coincides in time with the lower epidote–amphibolite and upper green-schist facies metamorphism of rocks happening under the decompression conditions, i.e., during their exhumation from the deep crustal level (8–13 km). A small amount of zircons of late generation showed a wide spread in age (277.4–318.1 Ma). The time of their crystallization corresponds to the stage of metamorphism associated with the collision orogeny in the Ural mobile belt. The more ancient 147Sm–143Nd age of 514 Ma should be assumed as the formation time of the rocks (or its upper age boundary).

A complex patchwork of magma bodies that fed the Bishop Tuff supereruption (Long Valley Caldera, CA, United States): Evidence from matrix glass major and trace-element compositions

The geologic record reveals events in which enormous volumes (100–1000s of km3) of magma were erupted in a matter of days to months. Yet, the architecture of magmatic systems that feed supereruptions can only be investigated through the study of ancient systems. For more than 40 years, the Bishop Tuff (Long Valley, California) has been the archetypal example of a single, zoned magma body that fed a supereruption. Early-erupted material is pyroxene-free and crystal poor (< 20 wt%), presumably erupted from the upper parts of the magma body; late-erupted material is orthopyroxene and clinopyroxene-bearing, commonly more crystal rich (up to 30 wt% crystals), and presumably tapped magma from the lower portions of the magma body. Fe-Ti oxide compositions suggest higher crystallization temperatures for late-erupted magmas (as high as 820°C) than for early-erupted magmas (as low as 700°C). Pressures derived from major-element compositions of glass inclusions were used to suggest an alternative model of lateral juxtaposition of two main magma bodies—each one feeding early-erupted and late-erupted units. Yet, this interpretation has proven controversial. We present a large dataset of matrix glass compositions for 227 pumice clasts that span the stratigraphy of the deposit. We calculate crystallization pressures based on major-element glass compositions using rhyolite-MELTS geobarometry and crystallization temperatures based on Zr in glass using zircon-saturation geothermometry. Additionally, we apply the same methods to 1,538 major-element and 615 trace-element analyses from a dataset from the literature. The results overwhelmingly demonstrate that the variations in crystallization temperature and pressure are not consistent with vertical stratification of a single magma body. All crystallization pressures and temperatures are very similar, with modes of ∼150 MPa and ∼730°C. Our results support lateral juxtaposition of three main magma bodies. Magmas represented by smaller stratigraphic units crystallized at similar pressures as the main bodies, which suggests coexistence of larger and smaller magma bodies at the time of eruption. We compare our findings with results for other very large eruptions and supereruptions. We argue that supereruptions typically mobilize a complex patchwork of magma bodies that reside within specific levels of the crust. These eruptions reveal the architecture of the crust during moments of high abundance of eruptible magma, revealing crustal states that differ from what is inferred for magmatic systems currently present on Earth.

Geological Constraints on the Genesis of Jagpura Au-Cu Deposit NW India: Implications from Magnetite-Apatite Mineral Chemistry, Fluid Inclusion and Sulfur Isotope Study

The Jagpura Au-Cu deposit is situated within the Aravalli craton in the northwestern part of India. In the present work, petrography, mineral chemistry, fluid inclusion and sulfur isotopic compositions were used to study the Jagpura Au-Cu deposit. The ore mineral association of the deposit is arsenopyrite, loellingite, chalcopyrite, pyrrhotite and pyrite, along with native gold, magnetite and apatite. The gold fineness ranges from 914–937‰ (avg. 927‰). The presence of Au-Bi-Te phases, pyrite (>1 Co/Ni ratio), magnetite (≥1 Ni/Cr ratio, <1 Co/Ni ratio) and apatite (>1 F/Cl ratio) suggest the hydrothermal origin Au-Cu mineralization. A fluid inclusion study indicates the different episodes of fluid immiscibility with the homogenization temperatures varying between 120–258 °C and salinities range within the 8.86–28.15 wt% NaCl eq. The sulfur isotopic composition of sulfides varies from 8.98 to 14.58‰ (avg. 11.16‰). It is inferred that the variation in the sulfur isotopic compositions of sulfides is due to the cooling and dilution of the metalliferous fluid of mixed origin, derived from the basement meta-sedimentary rocks and the high saline basinal fluid. The iron oxide-copper-gold-apatite associations, structural control of mineralization, pervasive hydrothermal alteration, fluid salinity and sulfur isotope compositions indicate that the Jagpura Au-Cu deposit is similar to the iron oxide-copper-gold (IOCG)-iron oxide-apatite (IOA)types of deposits. Based on the ore geochemistry and the trace elements systematic of magnetite, the deposit is further classified as an IOCG-IOA type: IOCG-Co (reduced) subtype.

A case of Te-rich low-sulfidation epithermal Au-Ag deposits in a calc-alkaline magmatic arc, NE China

Tellurium-bearing low-sulfidation epithermal Au-Ag deposits are significant producers of gold, silver, and potentially strategic elements if mineral processing methods are optimized for recovery. Although these deposits are generally related to alkaline magmatism, our study documents an unusual occurrence of Te-rich low-sulfidation epithermal systems in the North Heilongjiang Belt in northeast China that is spatially and temporally associated with calc-alkaline magmatism and tectonic extension in a continental arc‐setting.In the North Heilongjiang Belt, Te-bearing Au-Ag deposits are usually sited in dilatant zones, mostly along extensional NW structures or at their intersections with deep‐seated NE-striking faults such as the Nenjiang-Heihe and Jiayin-Mudanjiang lineaments. Of these deposits, Sandaowanzi is well‐known for its bonanza gold grades. These faults localized andesitic to rhyolitic volcano-plutonic centers that evolved from mantle‐derived mafic melts to intermediate compositions due to differentiation and crustal assimilation as documented by their mineralogy and Sr, Nd, and Pb isotope compositions. During assimilation of country rocks, fluids containing 3He and other volatiles derived from mantle magmas displaced or mixed with external groundwater containing radiogenic 4He derived from country rocks. In this belt, the bulk metal content of Au, Ag and Te was probably introduced by deep mantle‐derived mafic‐intermediate calc‐alkaline intrusions. However, our study does not exclude input of metals leached from underlying metasedimentary rocks and older Te‐bearing Au mineralization. The noble gas, hydrogen, oxygen and lead isotope compositions of fluid inclusions and ore minerals suggest that the deposits formed by mixing between magmatic fluids and convecting meteoric ground waters containing lead leached from surrounding country rocks. At deeper levels, isotopic evidence suggests that Au-Ag-Te (Bi) precipitated with pyrite, quartz, sericite, and carbonate minerals due to mixing with Te-rich fluids. At shallower levels, Au and Ag precipitated contemporaneously with base‐metal sulfides, hydrothermal quartz and sericite during episodic boiling as evidenced by silica morphology and mineral textures.The relatively uniform spacing of epithermal systems along NW- and NE-trending structures in the North Heilongjiang Belt was used to identify unexplored spaces within this mineral belt that are prospective for concealed low-sulfidation epithermal gold deposits. Although some of the Au-Ag deposits in this belt are enriched in Te, there is a lack of coeval alkaline igneous rocks that are commonly associated with Te-bearing gold deposits elsewhere in the world (e.g., Cripple Creek, Emperor, and Lihir Island).

Petrochemistry and mineralogy of pumice from the Sarychev Peak Volcano, Matua Island, Central Kuril Island

Background. The article presents the first results of a mineralogical and petrographic study of the pumice of the Sarychev Peak volcano, Matua island, the Central Kuril islands.Aim. To reconstruct the compositions of magmatic melts of a caldera-forming eruption of the proto-Matua volcano.Materials and methods. The main research methods included an X-ray fluorescence spectral analysis to determine the content of petrogenic, rare and trace elements, as well as an electron-probe microanalysis to study variations in the chemical composition of mineral inclusions of pumice.Results and conclusion. According to the content of SiO2 and the sum of alkalis, the composition of pumice varies from andesibasaltes (SiO2 = 55.94 wt.%) to dacites (SiO2 = 67.70 wt.%). According to the content of K2O, pumice can be classified as a moderate-potassium series of rocks. The inclusion minerals represented by plagioclase, amphibole, apatite and Fe-Ti oxides were crystallized at the same time from a water-saturated magmatic melt at a pressure of about 1.5–2.2 kbar. The igneous melt was enriched with volatile components of H2O, CO2, S, F and Cl.

Olivines and Their Melt Inclusions in Potassic Volcanic Rocks Record Mantle Heterogeneity beneath the Southern Tibet

Abstract Constraints on mantle heterogeneity are important for understanding geochemical differentiation and recycling in Earth’s interior. Alkali basalts are of particular interest in this context due to the clear signatures of recycled components that they yield. Previous studies have focused more on oceanic basalts than on continental mafic rocks because the chemical and isotopic characteristics of the latter are often modified by crustal contamination; however, high-forsterite olivine crystals and olivine-hosted melt inclusions may record the compositions of primitive melts before extensive crustal contamination, providing valuable insights into mantle heterogeneity. Here we report the results of high-precision major-, minor-, and trace-element and Pb isotope analyses of olivine phenocrysts and melt inclusions from the Sailipu potassic alkali basalts from southern Tibet, which constrain the mantle source of continental potassic alkali basalts. The minor- and trace-element compositions of the olivine phenocrysts (e.g. Ni and Ca contents and 100 × Mn/Fe, 10 000 × Zn/Fe, and Ni/Co ratios) suggest that the primary magmas were derived from a phlogopite-bearing pyroxenite source in which peridotite residues were also present. The low- and high-Li contents of the olivine phenocrysts suggest the recycling of continental crustal material in their mantle source. Comparing the major-element compositions (e.g. SiO2, TiO2, Al2O3, MnO, CaO, and Na2O contents), FCMS and FCKANTMS parameters, and pseudo-ternary projections of the primary Sailipu magmas with experimental data suggests that the primary magmas were partial melts of olivine-poor or carbonated olivine-poor lithologies with a small amount of peridotite residue. The negative Nb and Ta and positive Pb anomalies seen in primitive mantle-normalized trace-element patterns and the extremely low Nb/U ratios of the melt inclusions suggest that recycling of continental crust was the main process involved in enriching the mantle source of the Sailipu magmas. The heterogeneous Pb isotopic compositions of the melt inclusions (208Pb/206Pb = 2.089 – 2.158; 207Pb/206Pb = 0.851 – 0.858) are consistent with the presence of peridotite residue in this source. The subduction of Indian continental crust introduced enriched material (including carbonatites) into the mantle.

MELT INCLUSIONS IN OLIVINE AS A SOURCE OF INFORMATION ON THE COMPOSITION AND EVOLUTION OF DEEP MELTS OF AILLIKITES (ULTRAMAFIC LAMPROPHYRES) OF THE ILBOKICHI UPLIFT, THE SW SIBERIAN PLATFORM

Aillikites are kimberlite-like rocks, important for understanding the composition and processes occurring in the mantle. Melt inclusions represent a reliable source of information. The paper provides the first results of studies (Raman, EDS) on primary and secondary melt inclusions in olivine from the Ilbokich uplift aillikites. The composition of primary inclusions is close to that of parent melt of aillikites. It was significantly enriched in CO2, H2O, phosphorus and titanium. Phlogopite, diopside, dolomite, calcite, apatite, Ti-containing phases (brookite, perovskite, Ti-magnetite) and lizardite were identified in these inclusions. The similarity of the composition and ratios of the daughter phases with the aillikite matrix indicates a slight change in the parent melt when it is rising to the surface. As to the secondary inclusions, there are wide variations in compositions and a smaller amount of silicates, as compared to the primary ones. The main daughter phases are carbonates, e.g. dolomite, calcite, magnesite and alkaline carbonates. In addition, phlogopite, clinopyroxene, apatite, halite, pyrrhotite and magnetite, graphite and CO2 were discovered. The variability of the compositions of the secondary inclusions might be due to the silicate-carbonate immiscibility that appeared during the rising of the aillikite melt at pressures <4 GPa.

High MREE-HREE solubility in a carbonatite-derived hydrothermal fluid: Evidence from fluorite-hosted fluid inclusions in the Amba Dongar carbonatite complex, India

Recent experimental works suggest that complexation with alkalis, carbonate, and hydroxyl groups enhances rare earth element (REE) transport and HREE/LREE fractionation, seen in carbonatite-hosted REE deposits. The Amba Dongar carbonatite complex in western India hosts fluorite and REE-fluorcarbonate mineralization occurring as vug/vein fillings or as disseminated ores associated with calcite, dolomite, apatite, baryte, and quartz. In this study, we analyzed the major and trace element composition of fluorite-hosted fluid inclusions, and the trace element chemistry of calcite and fluorite, using laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) to characterize the nature of the hydrothermal fluid and the processes of mineral-fluid interaction. Fluorite contains aqueous bi-phase (liquid + vapor) fluid inclusions of variable size that furnish low salinities (0.4–2.2 wt% NaCl equivalent) and liquid-vapor homogenization temperatures (130 °C–155 °C). The fluid inclusions have high concentrations of alkalis (Na, K), Si, Al, Mg, and Mn, and their chemistry resembles orthomagmatic fluid derived from evolved carbonatite melts. They also have elevated MREE and HREE concentrations relative to the LREE, that is significantly higher than in many other hydrothermal settings. Such fluids with fractionated LREE/HREE were likely derived from residual brines post the LREE-mineralization stage, when the HREE still remained in solution. This report of hydrothermal fluids with elevated MREE and HREE solubility from natural carbonatites supports experimental findings that alkali‑carbonate-hydroxyl complexation helps to mobilize REE and fractionate the LREE from MREE and HREE. Magmatic calcite has LREE-enriched REE patterns while those of hydrothermally-altered calcite is nearly flat. The secondary calcite also has elevated concentrations of Na and K, which suggests that the alkali-rich fluids scavenged the REE from magmatic calcite and redistributed them into more insoluble REE-fluorcarbonates. The REE patterns of fluorite mimic those of its fluid inclusions, with the inclusions containing higher and more variable REE concentrations, suggesting that the REE signals of fluorite are coming from the ablation of fluid inclusions, and not from fluorite themselves.

From the lithosphere to the lower mantle: An aqueous-rich metal-bearing growth environment to form type IIb blue diamonds

A study of five diamonds containing mineral and fluid inclusions, selected among forty-nine specimens from the Cullinan Mine, South Africa, was carried out to better document the origin and formation of N-absent B-poor (type IIb) diamonds. The combination of several in-situ non-destructive techniques was used to identify the mineralogy and the chemical composition of primary and secondary inclusions. These include breyite, larnite, graphite, Fe-Ni-Cu native metallic alloys, sulfides of the pyrrhotite group, Ni-rich oxide and potential hydrous ferric sulfates. A common and abundant hydrous fluid containing H2O + CH4 was also identified. From the various observations, we suggest that these type IIb diamonds grew in an aqueous oxidized fluid reacting with a reduced mantle characterized by low oxygen fugacity. Remnant pressures recorded in primary breyite by Raman shifts and XRD measurements enabled the calculation of minimal entrapment pressures of inclusions using elastic geothermobarometry. Applying pressure corrections caused by elastic relaxation, minimum trapping pressures from 4.9 GPa to 5.6 GPa were calculated, suggesting lithospheric depths consistent with the occurrence of numerous graphite inclusions. The association of breyite and larnite, which is often considered as an indicator of sublithospheric origin, also occurs at pressures of 6 GPa or lower in a H2O-rich and carbonate/Ca-rich environment. The B-poor and N-absent features of type IIb diamonds do not require the classic subduction-related model of their formation. Whereas high-pressure minerals would host boron in cold subducting slabs, slabs are also important carriers of nitrogen into the deep mantle, with this latter element mostly absent in these diamonds. In our alternative model, the mantle is proposed as an alternative source of boron, whereby metallic alloys or N speciation between fluid and melt would still prevent the incorporation of nitrogen, leading to the expression of the blue, boron-related and N-absent features of type IIb diamonds. The observed mineralogical assemblage neither proves sublithospheric origin nor does it exclude lithospheric depths of formation for these diamonds. Hence, we propose that type IIb diamonds form in a mantle continuum, from sublithospheric to lithospheric depths.

Agglomeration behavior of rare earth inclusions and alumina inclusions at the interface between argon and molten steel

Nozzle clogging frequently occurs in steel containing rare earth (RE) due to the aggregation of RE inclusions, which seriously interferes with the application of RE in steel. To provide insights into nozzle clogging, the agglomeration behavior of inclusions in RE-containing steel was investigated by laboratory experiments and theoretical calculations. High-temperature confocal laser scanning microscopy (HT-CLSM) was applied to observe the behavior of inclusions at molten steel surfaces and their interactive forces. Kralchevsky–Paunov (K–P) model was used to predict the capillary force acting on different inclusions. The results show that the interactive forces that acted on inclusions were investigated as a function of inclusion size, inter-distance, and inclusion composition. It is found that the capillary force acting on the inclusions decreases in the order of Ce2O3 > CeAlO3 > Al2O3. This study verified the applicability of the K–P model in RE-containing steel, which can provide theoretical support to help solve the nozzle clogging problem during rare earth steel production.

Неметалеві включення в металі котельних безперервнолитих заготовок

The article presents results of studies of contamination of metal of undeformed continuously cast billets (CCB) for boiler tubes from carbon steel supplied by various manufacturers with non-metallic inclusions. Contamination was investigated by metallographic means using methods of observation under a microscope in light and dark fields of vision in polarized light. Application of these methods has made it possible to determine the inclusion types (silicates, oxides, sulfides) with high probability based on optical properties (color, transparency, etc.). Shape, size and type of inclusions and the nature of their location along the billet cross-section were determined for the data set of actual level of contamination of the CCB metal with non-metallic inclusions. In addition, the methods Sh and L according to DSTU 8966 were used. To determine the number, dimensions and types of inclusions, an automated control method using the VIDEOTEST-METAL 1.0 software was also used for the Axiovert 200MAT microscope. Composition of some non-metallic inclusions was studied by means of X-ray spectral microanalysis using the MS-46 microprobe of the Cameca Co. (France). It was established that irregular and rounded silicates of both homogeneous and heterogeneous composition (including individual large ones up to 150 μm in size) are main types of inclusions in metal of continuously cast billets. In most cases, these inclusions are located in axial and peripheral zones along the CCB section. Intermittent film precipitation of non-metallic inclusions of varying degrees of dispersion (mainly of small size) which can have a negative effect on service characteristics of tubes made from such CCB was also detected. The study results have important scientific and practical significance in conditions of wide use of such CCB in the production of tubes of responsible purpose. The obtained study results will make it possible to further develop an advanced methodology of assessing the contamination of non-deformed continuously cast billets (with scale) with non-metallic inclusions in their metal and introduce them in regulatory documents on the CCB. The results of studies of metal contamination with non-metallic inclusions will also be useful for improving the CCB production technology with the aim of producing boiler tubes of high operational reliability. Keywords: undeformed continuous cast tube billet, non-metallic inclusions, silicates, film precipitation of non-metallic inclusions.

Improved in situ analysis of lead isotopes in low-Pb melt inclusions using laser ablation-multi-collector-inductively coupled plasma-mass spectrometry.

In situ Pb isotope analyses of tiny melt inclusions using laser ablation-multi-collector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) are crucial for exploring the origins of mafic lavas. However, quantitative use of this technique with low-Pb (<10ppm) melt inclusions is difficult due to their low 204 Pb content and 204 Hg interference. Pb isotopic ratios of various reference glasses and olivine-hosted melt inclusions were determined using LA-MC-ICP-MS. Multiple ion counters were used to simultaneously determine signal intensities of all Pb isotopes and 202 Hg. An Hg signal-removal smoothing device reduced its signal in the gas blank by >80%. Instrumental mass bias was corrected using the standard-sample bracketing method. With 24-90 μm diameter laser spots, 2-4Hz repetition rates, and 2.5-4J cm-2 energy fluence, the analytical precisions of 20x Pb/204 Pb ratios (x = 6, 7, 8) for standards BHVO-2G, ML3B-G, NIST 614, NKT-1G, T1-G, GOR132-G, and StHs6/80-G were <1.0% (2RSD) when 208 Pb signals >100 000 cps. The Wangjiadashan melt inclusions have 206 Pb/204 Pb = 17.14-18.44, 207 Pb/204 Pb = 15.28-15.66, and 208 Pb/204 Pb = 37.12-38.68. The described method improves the precision and accuracy of in situ Pb isotope analysis in low-Pb melt inclusions using LA-MC-ICP-MS. The Pb isotopic compositions of the Wangjiadashan melt inclusions indicate the coexistence of LoMu and EMII+young HIMU components in the mantle source of weakly alkaline basalts.

Metallurgical Study of Iron Artifacts from Guryong-ri Site in Ungcheon, Boryeong

In the 6&lt;sup&gt;th&lt;/sup&gt; and 7&lt;sup&gt;th&lt;/sup&gt; centuries, 5 iron artifacts excavated form the Baekje Stone Tomb in Guryong-ri site, Ungcheon, Boryeong, were studied. The sample were metal microscopic observation, SEM-EDS analysis and Raman micro-spectroscopy analysis were conducted to understand the metallurgical characteristics. The microstructure observation showed the presence of ferrite and pearlite throughout, and differences in carbon content existed depending on the direction. Non-metallic inclusions were in the form of long lines, and most of them were wüstite, fayalite. It is indicated that the artifacts were forge welded using hypoeutectoid steel, with signs of carburizing and decarburizing processes. Some crystals with high P2&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;, TiO&lt;sub&gt;2&lt;/sub&gt;, CaO content were identified as sarcopside, ulvöspinel, and perovskite, respectively, through Raman spectroscopy. A comparison of the results with previous studies on the sites of Bujang-ri site in Seosan and Bongseon-ri site in Seocheon, which are adjacent sites in the coastal area, revealed that, while heat treatment technology was available, the artifacts were not heat-treated considering the purpose for use for these artifacts. The chemical composition of the non-metallic inclusions P&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;, TiO&lt;sub&gt;2&lt;/sub&gt;, CaO were plotted in proportions to SiO&lt;sub&gt;2&lt;/sub&gt; and compared with adjacent sites. Considering that the P&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;/SiO&lt;sub&gt;2&lt;/sub&gt; ratio was widely distributed, the refining technology was not uniform. In addition, the TiO&lt;sub&gt;2&lt;/sub&gt;/SiO&lt;sub&gt;2&lt;/sub&gt; ratio was found to be higher than that of other sites, meaning that a titanium-containing ore was used to manufacture the artifacts, unlike in surrounding sites, but it is not detected in all artifacts, so it may have been affected by various factors such as furnace walls in addition to raw materials. Although slag formers were used, considering the CaO/SiO&lt;sub&gt;2&lt;/sub&gt; ratio and the (Al&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;3&lt;/sub&gt;/SiO&lt;sub&gt;2&lt;/sub&gt;)/(CaO/SiO&lt;sub&gt;2&lt;/sub&gt;) ratio, which appear to be similar to the surrounding sites, but it is possible that CaO containing raw ore was used because it is also affected by the components of raw ore. As a result of the study, it is highly likely that ore different from that of the surrounding sites was used for production, but a more comprehensive comparative study with the surrounding sites is needed in the future.

Investigation of Cracks on Internal Surfaces of Extruded Cold Worked Thick Walled Pipes of an Age Hardened Al-Alloy

Thick seamless pipes of hardenable aluminum alloys demand close geometrical tolerances as well as high quality surface finish which are met by cold drawing after a series of different thermo-mechanical treatments. To meet the requirements of critical applications the final product undergoes stringent quality inspection procedures. State of the art quality assessment can detect even minor isolated defects. The production facilities develop their quality criteria suitable for specific applications. The present study investigated minute defects on the inside surface of thick seamless pipes, proposed mechanism of their formation and suggested the impact of defects on the end use. The root cause analysis was conducted, and measures were suggested to control the defects. Thick extruded seamless aluminum alloy pipes underwent a series of different thermo mechanical treatments; the final dimensions with required tolerances and the surface finish were achieved by adopting a 2-step cold drawing process. Cold drawing generated residual stresses which resulted in the formation of cracks in the material, preferentially at the defects generated during solidification and/or extrusion processes. The final product underwent stringent quality inspection, and the material was rejected if cracks of size 3 mm or larger were detected. The die scratches or notches generated on the inside surface of the pipes, during extrusion are assumed to grow if subjected to high stresses during subsequent processes, e.g. cold working. Observations at high magnification in SEM helped to determine the morphology of cracks. Radiographic testing did not detect any crack in the bulk material. Particles with faceted features indicated the presence of inclusion. Inclusions were detected in the form of strings along the direction of cold drawing. Energy dispersive spectrometry in SEM was used to determine the composition of inclusion detected in the vicinity of cracks. Almost all the inclusions were rich in silicon, iron, calcium along with carbon; it indicated that the inclusions were trapped particles of fluxes, slag, and brick powder. Particles rich in Ca, Na and/or Cl indicated entrapped flux, Fe and Si were mostly coming from aluminum scrap and refractory powder while presence of carbon indicated entrapped extrusion lubricant. Inclusions rich in a large variety of unwanted elements indicated presence of slag particles. Numerical analysis was conducted to develop a model in FEM in which scratches of different depths were introduced and autofrettage pressure was applied to determine the stresses generated according to the established Von Mises Model; the latter was used to establish the yield criteria. Finite Element Modelling concluded that when cold drawing pressure was applied on a pipe with a single notch of depth 0.3mm or three notches of depth 0.1 or greater at different locations the Von Mises stresses approached the yield strength of the pipe.

Evolution and deformability of inclusions in Al-killed steel with rare earth-alkali metals (Ca or Mg) combined treatment

The quality of stainless steel is closely related to the deformability of inclusions, which is significantly affected by their compositions. The present study first investigated the evolution of inclusion compositions in Al-killed steel with rare earth-alkali metals (Ca or Mg) combined treatment through four laboratory-scale experiments. The Ce contents in the final steel are 0.0080 wt%, 0.015 wt%, 0.016 wt% and 0.010 wt%, respectively. The Mg content is 0.0014 wt% in Ce–Mg combined treated steel, and the Ca content is 0.0015 wt% in Ce–Ca combined treated steel. The deformability of inclusions in both Ce2O3–Al2O3–CaO and Ce2O3–Al2O3–MgO systems was subsequently evaluated by calculating their Young's modulus at low temperature. The results show that irregular Al2O3 and MgAl2O4 with poor deformability are modified to CeAlO3 and Ce2O3 by Ce treatment, resulting in the decrease of Young's modulus of inclusions. The deformability of inclusions is further improved due to the transformation from lumped-like CeAlO3 to spherical CaO–Al2O3–Ce2O3 caused by Ca treatment, and some of these inclusions are the ones with low liquidus temperature. Thermodynamic analysis was used to discuss the control condition of the formation and evolution of inclusions. Accordingly, the appropriate addition amounts of Al, Mg, Ce, and Ca are expected to control inclusion compositions and properties, including deformability and liquidus temperature, thereby improving the steel performance.